ANALYSIS of ALTERNATIVES Public Version

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ANALYSIS OF ALTERNATIVES

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Legal name of applicants: Dow Italia Srl Rohm and Haas France S.A.S.

Submitted by: Dow Italia Srl

Substance: 1,2-Dichloroethane (EC No. 203-458-1, CAS No. 107-06- 2)

Use title: Industrial use as a sulphonation swelling agent of polystyrene-divinylbenzene copolymer beads in the production of strong acid cation exchange resins

Use number: 1

Disclaimer

This report has been prepared by Risk & Policy Analysts Ltd, with reasonable skill, care and diligence under a contract to the client and in accordance with the terms and provisions of the contract. Risk & Policy Analysts Ltd will accept no responsibility towards the client and third parties in respect of any matters outside the scope of the contract. This report has been prepared for the client and we accept no liability for any loss or damage arising out of the provision of the report to third parties. Any such party relies on the report at their own risk.

Table of contents

1 Summary ...... 1 1.1 Background to this analysis of alternatives ...... 1 1.2 Identification of potential alternatives for EDC and overall feasibility ...... 2 1.3 Technical feasibility of potential alternatives for EDC ...... 3 1.4 Economic feasibility of potential alternatives for EDC ...... 3 1.5 Risk reduction capabilities of the alternatives ...... 6 1.6 Availability of potential alternatives for EDC ...... 6 1.7 Actions needed to improve the suitability and availability of potential alternatives ...... 7

2 Analysis of substance function ...... 8 2.1 Introduction ...... 8 2.2 Background information on Ion Exchange Resins...... 9 2.3 Production and classification of IERs ...... 12 2.4 Overview of Dow’s IER activities ...... 15 2.5 Conditions of EDC use ...... 20 2.6 Technical feasibility criteria for alternative substances...... 25 2.7 Technical feasibility criteria for alternative technologies ...... 30

3 Annual tonnage ...... 31

4 Identification of possible alternatives...... 32 4.1 Introduction and list of possible alternatives ...... 32 4.2 Description of efforts made to identify possible alternatives ...... 32

5 Suitability and availability of possible alternatives ...... 55 5.1 Alternative 1: 1,2,4-Trifluorobenzene ...... 55 5.2 Alternative 2: DCM ...... 69 5.3 Alternative 3: Solventless sulphonation ...... 79

6 Overall conclusions on suitability and availability of possible alternatives ...... 89 6.1 Alternative substances and technologies considered ...... 89 6.2 Conclusions on comparison of alternatives to EDC ...... 89 6.3 Overall conclusion and future research and development ...... 92

7 Annex 1: Risk evaluation of alternative substances ...... 94 7.1 Methodological approach ...... 94 7.2 Reference values (DNELs, PNECs) for EDC and alternative substances ...... 95 7.3 Exposure Assessment ...... 106 7.4 Results of the comparative exposure assessment and risk characterisation ...... 107

8 Annex 2: Dow IER Products ...... 111

9 Annex 3: Substances excluded from further analysis following screening step 2 ...... 119

10 Annex 4: Justifications for confidentiality claims ...... 125

References ...... 126

1 Summary

1.1 Background to this analysis of alternatives

This Application for Authorisation (AfA) has been submitted jointly by two legal entities: Dow Italia Srl, and Rohm and Haas France S.A.S. The substance of concern is 1,2-dichloroethane (hereafter referred to as EDC), EC No. 203-458-1, CAS No. 107-06-2.

Both applicants are applying for the same use of EDC (‘Industrial use as a sulphonation swelling agent of polystyrene-divinylbenzene copolymer beads in the production of strong acid cation exchange resins’), which is undertaken within similar closed (batch) processes at their respective production plants in Fombio, Italy and Chauny, France. The applicants’ activities are associated with a combined EDC use of '''''#B'''''.

Strong acid cation exchange resins (SAC ERs) are a sub-category of ion exchange resin (IER) that find use across a very diverse range of downstream sectors, from water softening applications to waste decontamination in the nuclear industry. SAC ERs are characterised by their ability to exchange cations or split neutral salts and are useful across the entire pH range (Dow, 2000).

EDC’s effectiveness and properties as a polystyrene-divinylbenzene (PS-DVB) sulphonation swelling agent allow the process to achieve high yields of acceptable quality SAC ERs (across 50 different product grades), with short cycle times for sulphonation. The solvent is also highly recoverable in the process. Such parameters are extremely important when considering the highly competitive global market the applicants compete in.

The authorisation has been applied for so that EDC will continue to be used at the applicants’ plants until a suitable alternative becomes available. The argumentation in this AfA is based on two pillars:

 The lack of a technically and economically feasible (and sustainable) alternative for EDC, and  The demonstration that the socio-economic benefits from the continued use of the substance significantly outweigh the risks to human health, as shown in the accompanying Socio-economic Analysis (SEA) document.

Important note

Although ‘Dow Italia Srl’ and ‘Rohm and Haas France S.A.S.’ can be considered as separate legal entities, their activities fall under the remit of ‘Dow Water & Process Solutions’, a business unit of The Dow Chemical Company. Both legal entities are ultimately owned 100% by The Dow Chemical Company.

Consequently, in the context of this Analysis of Alternatives (AoA), the applicants’ activities must be considered ‘as one’ i.e. from the overall corporate strategy and business perspective of The Dow Chemical Company. However, where deemed particularly relevant, distinction is made between e.g. specific production processes.

This overall business perspective is also very important to consider when the feasibility of alternatives is taken into account, as the applicants are duty-bound to justify any proposed capital projects to The Dow Chemical Company. These will be required to pass all financial, technical, business, and sustainability justification ‘gates’, and, as The Dow Chemical Company operates globally, be compared to other high-level options including the exit of operations and shutdown of the affected production within the EU. These issues are discussed further in the corresponding SEA document, but the requirement for the applicants to justify their actions in the context of a competitive global market remains a critical factor for consideration within this AoA

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 1 1.2 Identification of potential alternatives for EDC and overall feasibility

Dow followed a detailed, stepwise and logical approach to screen 614 potential alternative substances for EDC (considering a wider pool of more than 1000 substances). The initial list was identified via the utilisation of Dow’s in house R&D software in combination with an in-depth review of the available scientific and technical literature. Substances were shortlisted (or were eliminated from further consideration) based on the results of several screening steps. The sequence of screening began with a laboratory validated assessment of PS-DVB copolymer swelling properties and was followed by a replication of sulphonation process conditions and a preliminary hazard assessment. The availability of remaining substances was also considered. For the identification of alternative techniques extensive literature searches were undertaken.

The above process resulted in the selection of three potential alternatives (two substances and one technique) which are analysed in detail in Section 5 of this AoA:

 1,2,4-trifluorobenzene (EC No. 206-684-9, CAS No. 367-23-7)  Dichloromethane (DCM) (EC No. 200-838-9, CAS No. 75-09-2)  Solventless sulphonation (technique).

The overall outcome of the applicants’ analysis with regard to these potential alternatives is shown in Table 1-1. Additional detail on feasibility aspects is provided in the following sub-sections.

Table 1-1: Overall conclusions on suitability and availability of shortlisted alternatives Potential alternative Key consideration 1,2,4- Solventless DCM trifluorobenzene sulphonation No Not at present (only partial Is the potential alternative No (could become feasible by implementation technically feasible? May 2023 at the earliest) possible, this is not acceptable) No Is the potential alternative (particularly considering the No No economically feasible? longer term sustainability of the substance) Yes Does the potential (although there are major alternative result in a Cannot be confirmed Yes concerns for longer term reduction of risk? sustainability) Is the potential alternative The substance is available. (and associated technology The process could become No No / process to implement it) technically feasible by May available? 2023 at the earliest Would the applicants be able to obtain corporate approval and capital No No No funding to implement the alternative?

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 2 1.3 Technical feasibility of potential alternatives for EDC The technical feasibility of the potential alternatives varies significantly, although a common element is that no alternative can be considered technically feasible to implement until significantly later than the EDC Sunset Date in November 2017.

For 1,2,4-trifluorobenzene, following promising results obtained from the screening exercise, the applicants began (in Q2 2014) an R&D plan for the implementation of the substance as an alternative for EDC. However, during the early phases of the plan (in Q1 2015) the applicants discovered that the use of the substance resulted in unsatisfactory levels of residual fluorine in final SAC ER products, which is an issue that cannot be overcome whilst maintaining a viable production process. In addition, consultation with internal subject matter experts has highlighted that use of the substance would leave the applicants’ glass-lined sulphonation reactors susceptible to corrosion and loss of integrity in service. Based on these factors, 1,2,4-trifluorobenzene was deemed a technically infeasible option.

For DCM, all necessary technical comparison criteria could be met but due to the required R&D activities, engineering work and process parameter modifications, the substance cannot be deemed a technically feasible alternative at this time (DCM must be utilised within a pressure driven sulphonation process, which differs to the current production processes in the applicants’ Chauny and Fombio plants). If the applicants were to implement this alternative, theoretically, this could be technically achieved by May 2023 at the earliest.

The solventless sulphonation technique offers no technical advantages over the EDC-based process with the exception that no solvent would need to be utilised. Copolymer swelling efficiency would be significantly poorer, and the process might also lead to an increase of polymeric leachables in the final SAC ER products. With the implementation of this technique (which, theoretically, could be achieved by November 2022 at the earliest) the final quality of the SAC ER’s would also be significantly impaired, to the extent that the manufacture of 40-60% of current EDC based SAC ER products at Chauny and Fombio would have to be terminated, as these could no longer be produced at a quality level acceptable for customers. In addition, production capacity for remaining products at both Chauny and Fombio plants would be reduced by an estimated 10-15%, due to both a reduction in yield (directly associated with the technique’s poorer swelling characteristics) and a significantly longer cycle time. Solventless sulphonation cannot be considered a technically feasible option. 1.4 Economic feasibility of potential alternatives for EDC

A summary of key economic feasibility considerations (and their importance) for each potential alternative is provided in Table 1-2, overleaf. Critically, none of the potential alternatives can be deemed economically feasible to replace EDC.

The following caveats which apply to the discussion of investment and operating costs within the table should also be noted (these issues are discussed further in Section 5):

 Information and values for 1,2,4-trifluorobenzene were gained during the early stages of an R&D plan on the substance (i.e. before it was discovered to be technically infeasible) and are presented in order to provide the indicative magnitude of costs associated with the substance’s implementation, if technical feasibility issues could have been overcome  For solventless sulphonation, information and values are based on the assumption that the technique can be utilised to manufacture 40-60% of current EDC-based SAC ER products at Chauny and Fombio, in line with the applicants’ technical feasibility analysis. Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 3 Table 1-2: Economic feasibility of potential alternatives for EDC Alternative Cost category 1,2,4-trifluorobenzene DCM Solventless sulphonation Investment costs (and ability to acquire finance) Research and development Major cost: €4-8 million Major cost: €1.6-2.4 million Major cost: €1.2-2 million activities Cost of changes to the process Major cost: €4-12 million per site (€8-24 million Major cost: €4-8 million per site (€8-16 Major cost: €1.6-4 million per site plant (acquisition of new total) million total) (€3.2-8 million total) equipment and cost of installation) Recertification and requalification Potentially a major cost due to the direct Potentially a major cost due to the Potentially a major cost due to the requalification and recertification costs (which direct requalification and recertification direct requalification and recertification would include the need for a full toxicological costs in addition to the potential loss of costs in addition to the potential loss of package costing at least €100,000) in addition customers who may switch to a non-EU customers who may switch to a non-EU to the potential loss of customers who may supplier supplier switch to a non-EU supplier Employee training costs Significant retraining would be required Significant retraining would be required Limited retraining would be required. although this would be a minor cost in the although this would be a minor cost in This would be a minor cost in the context of overall implementation the context of overall implementation context of overall implementation Applicants’ ability to acquire Must proceed via The Dow Chemical Company’s Must proceed via The Dow Chemical Must proceed via The Dow Chemical finances to implement alternative? corporate capital funding process. Company’s corporate capital funding Company’s corporate capital funding process. process. Funding to implement this alternative would not be given due to the very poor level of Funding to implement this alternative Funding to implement this alternative feasibility would not be given due to the would not be given due to the very regulatory climate and long-term poor level of feasibility economic feasibility considerations Operating costs (compared to EDC based process) Energy costs Increase due to longer process time Increase Increase due to longer process time and requirement for higher sulphonation temperatures Materials and service costs Increase by '''''''''''''' ''#F''''''''''''''''''''''''' due to the Slight increase Decrease, as no solvent is required in very high cost of purchasing 1,2,4- the process trifluorobenzene Labour costs No significant change expected. The cost of No significant change expected No significant change expected meeting worker health and safety requirements is undetermined Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 4 Table 1-2: Economic feasibility of potential alternatives for EDC Alternative Cost category 1,2,4-trifluorobenzene DCM Solventless sulphonation Maintenance and laboratory costs Increase due to fluorinated nature of No significant change expected No significant change expected compound Other costs Increase in costs associated with marketing, Increase (associated predominantly No significant change expected license fees and other regulatory compliance with emissions controls) activities Additional considerations Changes to product quality A major issue. Quality of products would Quality of products would be A major issue. Quality would decline to decline significantly if alternative was anticipated to be retained the extent that 40-60% of SAC ER implemented products could no longer be produced Changes in production volumes Was not anticipated to be a major issue during Not anticipated to be an issue from a A major issue. A 10-15% decrease in initial R&D. However, any step to remove process perspective overall production capacity would occur residual fluorine from the final products would with the implementation of this cause a process bottleneck and lead to poor alternative production economics and thus an unviable production process Overall summary Total cost of switching Investment costs of at least €12-32 million Investment costs of at least €9.6-18.4 Investment costs of at least €4.4-10 (investment costs, operating costs million million and other key factors) Significant increase in operating costs '''' '''' Significant increase in operating costs Significant increase in operating costs '''''''' ''''''''#F '''''' '''''''''''''''''''''''

Other key factors: Other key factors: Other key factors: - product quality decline - future regulatory status of substance - product quality diminished - significant decrease in overall SAC ER uncertain - significant decrease in overall SAC ER production capacity - capital investment and technical / production capacity - applicants would not be able to obtain funding engineering / analytical resources - applicants would not be able to obtain to implement this option required to implement this option are funding to implement this option substantial - applicants would not be able to obtain funding to implement this option

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 5 1.5 Risk reduction capabilities of the alternatives

In a separate detailed report (available as Annex 1 (Section 7) of this AoA) a comparative risk assessment for environmental and human health effects is described for 1,2,4-trifluorobenzene and DCM. No detailed assessment was undertaken for solventless sulphonation, as the technique removes altogether the need for a solvent within the process, and is therefore assumed to fulfil the requirement of leading to a reduction in overall risks to human health and the environment compared to the EDC1.

For 1,2,4-trifluorobenzene, it was concluded that sufficient data were not available to undertake a quantitative assessment. Consequently, it cannot be established that the substance leads to reduced risks for humans and the environment when used as a substitute for EDC.

DCM was concluded to lead to reduced risks for humans and similar risks for the environment when used as a substitute for EDC. However, the applicants have expressed major concerns with regard to the long-term sustainability of implementing the substance, particularly from a regulatory risk perspective, as it is from the same class of chlorinated organic solvents as EDC. It should also be noted that the substance is currently on the draft plan for entry to the Community Rolling Action Plan (CoRAP) for 2016. 1.6 Availability of potential alternatives for EDC

For 1,2,4-trifluorobenzene and DCM, the applicants considered the following factors (for the solventless sulphonation technique, as no solvent is required, only the last point was considered):

 Availability of the alternative in quantities sufficient for the applicants’ production processes  Availability of the alternative in the quality required by the applicants’ production processes  Access to the technology that allows the implementation of the alternative as a replacement for EDC.

For 1,2,4-trifluorobenzene, availability was identified as a major obstacle, as the substance is available from only one small-scale, low volume, custom synthesis type supplier. Reliability of supply is therefore a real uncertainty and with regard to quality, the supplier is not validated as credible at this stage. The applicants also do not have the required technology to implement the substance without unacceptable corrosion issues.

For DCM, the alternative substance can itself be considered available in the quantity and quality that would be required by the applicants; however, implementation could not be achieved until May 2023 at the earliest.

When considering the solventless sulphonation technique, given that it can only be considered a technically feasible replacement for 40-60% of the current Fombio and Chauny EDC based SAC ER product lines (and not until November 2022 at the earliest), the applicants do not consider the alternative technique to be available to them.

1 Some consideration can, however, be given to the increased energy consumption associated with the operation of this process, which may in turn be associated with an increase in greenhouse gas emissions.

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 6 1.7 Actions needed to improve the suitability and availability of potential alternatives

The applicants have outlined the scope of future R&D activities in Section 6.3.2 of this AoA document. Based on the assumption that the applicants are granted a sufficiently long authorisation review period and necessary R&D funding and approval are secured at the corporation level, efforts are likely to focus on two areas:

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The applicants are requesting an authorisation review period of 15 years. The request for this length of review period is based upon a ‘reasonable best case’ timeline in which it is anticipated that an alternative substance could theoretically be identified and implemented. It is also supported by a multitude of factors, such as the need to minimise business risks and guarantee the long-term continuity of SAC ER supply, thus justifying corporate investment in fresh R&D efforts at Chauny and Fombio, as opposed to other options such as business transferral to non-EU locations. Full explanation and justification for this length of review period is provided in Section 2.4 of the corresponding SEA document.

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 7 2 Analysis of substance function

2.1 Introduction

EDC is used by the applicants as a sulphonation swelling agent for PS-DVB copolymer beads, during their functionalisation into SAC ERs. SAC ERs are a category of IER that find use across a broad range of downstream sectors.

Before a more detailed description of the applicants’ activities is provided, it is necessary for the reader to become familiarised with the IER sector more generally. Consequently, this section begins with the provision of background information, which includes:

 An introduction to the ion exchange process  An overview of the broad range of conventional and prospective uses of IERs  Information on the production of IERs (and their subsequent classification).

Following the provision of this information, the applicants’ overall activities in IER production are described and a detailed overview of the sulphonation process and EDC’s critical role as a swelling agent is presented. This is followed by analysis of the applicants’ approach to information collection and an overview of technical feasibility parameters that must be taken into account when considering the functional criteria a potential alternative for EDC is required to fulfil.

This section has been structured as such, as a broad knowledge of the overall ‘IER sector’ is very important when understanding why the applicants’ specific use of EDC is critical and also in identifying why there are no alternatives that can be considered both technically and economically feasible. An understanding of the overall sector is also vital when considering the applicants’ non- use scenarios in the corresponding SEA document, as a refused authorisation would not only affect their production of SAC ERs, but would also have ramifications that extend across a broader range of Dow’s production activities.

Consideration of this AoA in the context of other EDC Authorisation Consortium AfAs

This AoA has been prepared by an independent third party working on behalf of Dow (i.e. Dow Italia Srl and Rohm and Haas France S.A.S.) and a further seven EU-based users of EDC who collectively formed an EDC Authorisation Consortium (EDCAC). Activities of the EDCAC can be summarised within three broad areas: Ion Exchange Resins, Pharmaceuticals and Slack Waxes.

Of note, separate to this AoA (and AfA), there is one additional company within the consortium whose activities fall under the remit of ‘Ion Exchange Resins’.

Despite similarities with regard to background information provided in the Dow and other relevant user’s AoA documents, it must be emphasised that the possibility to replace EDC is (to a significant extent) based on company-specific processing parameters and customer requirements, as well as a multitude of individual economic feasibility considerations. Consequently, the feasibility and availability of a ‘one size fits all’ alternative for Dow and the other applicant should not by any means be assumed.

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 8 2.2 Background information on Ion Exchange Resins

2.2.1 Introduction

Ion exchange is the reversible interchange of ions between a solid (ion exchange material) and a liquid in which there is no permanent change in the structure of the solid. Ion exchange is commonly used in water treatment and provides a method of separation for many processes involving other liquids. It has special utility in chemical synthesis, food processing, medical research, mining, agriculture, and a variety of other areas (discussed further below) (Dow, 2000).

The utility of ion exchange rests with the ability to use and reuse the ion exchange material. The process occurs in a variety of substances and it has been used on an industrial scale since the early 1900’s with the introduction of water softening using natural and, later, synthetic zeolites. Sulphonated coal, developed for industrial water treatment, was the first ion exchange material that was stable at low pH. The introduction of synthetic organic IERs in 1935 resulted from the synthesis of phenolic condensation products containing either sulphonic or amine groups which could be used for the reversible exchange of cations or anions (Dow, undated).

Conventional IERs comprise an insoluble matrix fabricated from an organic polymer substrate that has the form of beads (spherical form) with a diameter in the range 0.5 – 1 mm. The beads are typically porous, providing a high surface area. Conventional IERs have a polydispersed particle size distribution from about 0.3 mm to 1.2 mm (50-16 mesh) or are uniform particle sized resins with all beads in a narrow particle size range (Dow, 2000). Figure 2-1 shows examples of ‘typical’ IERs.

Figure 2-1: Examples of typical IER beads Source: Camden International (2014)

2.2.2 End uses

As noted above, ion exchange has a special utility in wide variety of processes. Table 2-1 presents some conventional and prospective applications of the broader range of ion exchange materials available, as described by Zagorodni (2007), and with some additional input from the applicants. The text and figures following the table highlight the common cyclic nature of IER use in some core applications.

Table 2-1: List of conventional and prospective applications of ion exchange materials Category Application Water preparation for different Preparation of pure and ultrapure deionised water purposes Water softening Potable water preparation Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 9 Table 2-1: List of conventional and prospective applications of ion exchange materials Category Application Removal of specific constitutes Dealkylisation Fluoride removal Removal of organic matter particularly colorants Oxygen removal Iron and manganese removal Cd2+ removal from drinking water Nitrate removal Ammonia removal Removal of radionuclides from drinking water Removal of other harmful irons from drinking water Nuclear industry Separation of uranium isotopes Waste decontamination Final storage of radioactive wastes Condensate polishing Decontamination and recuperation of Recycling of industrial water waste streams Removing of heavy metal ions Recuperation of metals Ammonia removal Recovery of calcium aconitate Removal of radioactive substances Isotope separation Eu3+ isotopes Lithium isotopes Boron isotopes Nitrogen isotopes Isotope analysis Pulp and paper industry Removal of inorganic salts from liquors Detoxification of by-products transferred for bio-cultivation Purification of sugars and polyhydric Purification of cane, corn, and beet sugars alcohols Purification of fructose Separation of monosaccharides Purification of glycerine Treatment of sorbitol Recovery of xylitol Food industry Removing off tasters and odours Recovery of glutamic-acid Purification of steviosides De-acidification of fruit juice Dairy Extraction of lactoperoxidase Purification of casein Winery Absorption of wine proteins in the production of wines Stabilisation of wine Amino acids Recovery and purification of biological Proteins and biochemical substances Enzymes DNA Antibodies Biotechnology Separation of lactic acid from fermentative broth Production of L-glutamine Production of citric acid Organic acids Recovery and purification in Uranium hydrometallurgy Thorium

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 10 Table 2-1: List of conventional and prospective applications of ion exchange materials Category Application Rare earths Tungsten Transition metals Gold, silver, platinum, palladium Solvent purification - Reagent purification - Preparation of inorganic salts - Catalysis Petroleum refining with zeolites Ethylbenzene synthesis Olefins isomerisation Catalytic reduction of nitrogen oxides Fuel ethers Bisphenol A production Pharmaceuticals and medicine Antibiotics Vitamins Active ingredients Taste masking Tablet disintegration Controlled and sustained drug release Immobilisation of drugs in a carrier function Soil science and technology Artificial soils Remediation of contaminated soils Evaluation of soil properties Buffering - Analysis Chromatography Sample preparation, separation, concentrating, purification Replacement of analyte Drying of different media Desiccation of solvents with zeolites Gas drying with polymeric exchangers and zeolites Sources: Zagorodni (2007) and applicants’ information

As highlighted by Ramaswamy, Huang & Ramarao (2013), ion exchangers are usually employed in cyclic processes (except when used on a very small scale). These cyclic operations involve sorption and desorption steps. For example, when considering water treatment applications such as water softening, a typical ion-exchange cycle will contain four steps (see Figure 2-2):

1. Backwash: removal of accumulated solids obtained by upflow of water to expand and fluidise the exchanger system 2. Regeneration: In order to restore the original ionic form of the ion exchanger, a reagent called regenerant is passed slowly through the exchanger 3. Rinse: Regenerant is removed by passing water through the exchanger 4. Loading: the contaminated solution is then passed through the exchanger until leakage is detected.

Figure 2-2: Typical ion-exchange cycle for wastewater treatment Source: Ramaswamy, Huang & Ramarao (2013) Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 11 Many ion-exchange columns operate in down-flow mode and are regenerated in the same direction. However, in order to obtain a better regeneration and lower leakage during loading, the regenerant can be passed counter-current to the loading flow. The retained solute can be a useful component in the chemical industry. The cycle is then modified to include a displacement step (see Figure 2-3).

Figure 2-3: Modified ion-exchange cycle to recover ‘interesting compound’ Source: Ramaswamy, Huang & Ramarao (2013) 2.3 Production and classification of IERs

2.3.1 Introduction

There are many aspects involved in the production of IERs. However, as noted by SCI (undated), the preparation and manufacture of these materials commonly distinguishes two steps:

 Formation of the polymer bead  Converting the bead to an active ion exchanger by attaching a suitable functional group.

The formation of the polymer bead substantially determines the characteristics of an ion exchanger, but decisive for its chemical mode of action are the functional groups. A broad schematic representation of this process is shown in Figure 2-4 and these steps are discussed further in the following sections.

Figure 2-4: Production of IERs Source: Lanxess (2010)

2.3.2 Formation of the polymer bead

A variety of polymeric substrates can be used in ion exchange synthesis, including polymers of esters, amides and alkyl halides (Fritz & Gjerde, 2009). However, resins based on PS-DVB copolymers appear to be the most widely used ion exchangers2 (a schematic representation of this copolymer is presented in Figure 2-5). Indeed, Dardel (2013) notes that approximately 90% of all IERs are based on this polystyrenic matrix and Dow (2002) states that this polymer system has stood

2 Polyacrylic IERs also appear to be widely commercially available in e.g. weak acid cation exchange resins (discussed further below). Here, for simplicity, in the discussion of production, focus will remain on the styrene-divinylbenzene copolymer.

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 12 the test of time as the most stable, physically and chemically, of any commercially available to date. With regard to this form of resin, polystyrene is the primary component, with a small amount of divinylbenzene added during polymerisation as a cross-linking agent. The cross-linking confers mechanical stability upon the polymer bead and dramatically decreases its solubility – subsequently, final resin properties can be varied significantly by changing the amount of divinylbenzene cross- linking agent (Dow, 2002).

Clearly, the polymeric substrates used in the production of IERs are highly important. However, it should be noted that from a physical structure point of view (as explained by Zaganiaris (2011)) resins can be categorised into two main types, based on the way they are produced. In the first, the IER beads are homogeneous and are called microporous (or gel type) IERs. In the second, designated as macroporous (or macroreticular) IERs, the resin beads are heterogeneous and consist of interconnected macropores surrounded by gel-type microbeads agglomerated together.

Historically, production of both types of polymer bead has been undertaken by suspension polymerisation in a stirred reactor. More specifically:

 Microporous resins are produced by a suspension polymerisation in which styrene and divinylbenzene are suspended in water as droplets. The substances are kept in suspension in the reaction vessel through rapid, uniform stirring, and the use of a surfactant. Addition of a catalyst (e.g. benzoyl peroxide) initiates the polymerisation. The size of the beads is dependent on the stirring rates (faster stirring = smaller beads) (Fritz & Gjerde, 2009)

 Macroporous resins are prepared by a special suspension polymerisation process, where the suspended monomer droplets also contain inert diluents; the diluent is a good solvent for the monomers (but not for the material that is already polymerised). Consequently, the resin beads formed contain pools of diluent distributed throughout the bead matrix. When polymerisation is complete, the diluent is washed out of the beads to form the macroporous structure, which results in rigid spherical beads with a high surface area (Fritz & Gjerde, 2009).

Figure 2-5: Schematic representation of styrene-divinylbenzene copolymer Source: Fritz & Gjerde (2009)

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 13 Individual beads of gel-type and macroreticular IER are illustrated, respectively, in Figure 2-6 and Figure 2-7.

Macroporous resins, with their large effective surface area, facilitate the ion exchange process, that can be used with almost any solvent, irrespective of whether it is a good solvent for the un-cross- linked polymer, and take up the solvent with little or no change in volume. They make more rigid beads, facilitating ease of removal from the reaction system. In the case of the microporous resins, since they have no discrete pores, solute ions diffuse through the particle to interact with exchange sites. Despite diffusional limitations on reaction rates, these resins offer certain advantages: they are less fragile, require less care in handling, react faster in functionalisation and applications reactions, and possess higher loading capacities (Sigma Aldrich, undated).

Figure 2-6: Schematic representation of a gel type IER bead Source: Zaganiaris (2011)

Figure 2-7: Schematic representation of a macroreticular IER bead Source: Zaganiaris (2011)

2.3.3 Addition of the functional group

Once produced, the polymer beads need to be chemically activated to make them perform as ion exchangers. In this stage, suitable functional groups are chemically introduced into the polymeric matrix3 in a variety of different processes. It is the addition of the functional groups that determines

3 In some instances, monomers are functionalised first and then polymerised into beads. Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 14 the chemical behaviour of the IER. When activated, there are four primary types of IER, classified depending on their main acid-base characteristics:

 Strongly acidic cation (SAC) exchange resins, containing sulfonic acid groups, e.g. sodium polystyrene sulphonate or poly(2-acrylamido-2-methyl-1-propanesulfonic acid)  Strongly basic anion (SBA) exchange resins, containing quaternary amino groups, for example, trimethylammonium groups, e.g. poly (acrylamido-N-propyltrimethylammonium chloride)  Weak acidic cation (WAC) exchange resins, containing carboxylic acids  Weak basic anion (WBA) exchange resins, containing primary, secondary and/or ternary amino groups, e.g. polyethylene amine.

SAC exchange resins can neutralise strong bases and convert neutral salts into their corresponding acids. SBA resins can neutralise strong acids and convert neutral salts into their corresponding bases. These resins are utilised in most softening and full demineralisation applications. WAC and WBA resins are able to neutralise strong bases and acids, respectively. These resins are used for dealkalisation, partial demineralisation, or (in combination with strong resins) full demineralisation (General Electric, 2012).

Additional types of IERs include blends of cation and anion exchange resins (‘mixed bed resins’) and ampholytic resins (which contains both an anion and a cation as bound ion). Some IERs are also prepared with chelating properties making them highly selective towards certain ions (Sigma Aldrich, undated).

The process of functionalisation varies significantly among the different categories of IER, and this can also have a significant impact on the cost of the final products. For example, in anion activation, processes are generally more complicated and expensive than for cation activation, with the IERs typically, although not exclusively, produced by a two-step process comprising chloromethylation and amination (SCI, undated).

In terms of the end products produced, Dorfner (1991) states that the following factors are decisive for the physical and chemical properties of a synthetic IER, and therefore prerequisites to be met during synthesis. These factors remain valid to this day:

 The IER must be highly polymeric and sufficiently cross-linked in order to be insoluble in water and other liquids and have good mechanic and thermic properties  The IER, having either a gel or a porous structure, must be sufficiently hydrophilic to make it possible for ions to diffuse through the structure at a finite and acceptable rate  The IER must contain an adequate number of accessible ionic exchange sites in order to yield a high exchange capacity  The IER must be as chemically stable as possible, so as to neither undergo degradation during use nor release parts or degraded parts of its structure  The IER must have a particle size distribution suitable for the envisaged application  The IER in the swollen state should be denser than water. 2.4 Overview of Dow’s IER activities

Since the 1940s, Dow has been an innovator in water separation technologies, known for a number of industry firsts—including the world’s first spiral-wound membrane technology for water treatment. Dow became a leader in reverse osmosis and IER technologies worldwide with the acquisition of Rohm & Haas in 2009.

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 15 Currently, the production of IERs by Dow is carried out under the remit of ‘Dow Water & Process Solutions’ (Both ‘Dow Italia Srl’ and ‘Rohm and Haas France S.A.S.’ legal entities are ultimately owned 100% by The Dow Chemical Company). Dow Water & Process Solutions are one of the largest global manufacturers of IERs with worldwide production, R&D and commercial operations (see Figure 2-8).

With regard to IER production, Dow Water & Process Solutions offer a comprehensive line of products for a diverse set of applications spanning several sectors. This includes industrial water resins, power generation resins, ultrapure water grade resins, food grade resins, chemical process and mining resins, drinking water grade resins, and residential and commercial resins. An outline of these products and their uses is provided in Section 8 (Annex 2). In addition to the production of IERs, Dow’s water and processes technology also includes:

 Reverse osmosis and nano-filtration  Fine particle filtration  Ultra-filtration  Electrodeionisation  Catalysts  Adsorbents; and  Selective media.

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 16

Figure 2-8: Dow Water and Process Solutions – Global operations Source: Dow (2013)

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 17 2.4.1 Preparation of SAC ERs

As highlighted in Section 2, the applicants use EDC as a swelling agent of PS-DVB copolymer beads, during their sulphonation. Sulphonation is the process in which the copolymer beads are functionalised into SAC ERs via the addition of sulphonic acid functional groups, which form the fixed ions of the ion exchanger. As noted by Jackson (1991), the sulphonic acid groups can be introduced onto the PS-DVB copolymers by reaction with sulphuric acid, sulphur trioxide, fuming sulphuric acid or chlorosulfonic acid (see Figure 2-9). Sulphuric acid is the most commonly employed sulphonation reagent (this is used by the applicants) and is used at elevated temperatures, sometimes in the presence of a catalyst.

Figure 2-9: Reaction schemes for the introduction of sulphonic acid functional groups onto PS-DVB copolymers Source: Jackson (1991)

A broader schematic of the SAC exchange resin production process is provided in Figure 2-10.

Figure 2-10: Synthetic procedure to produce SAC exchange resins Source: Dow (2000)

As can be seen from the above figure, in addition to the use of a sulphonating acid, it is also common to introduce a swelling agent during the sulphonation phase of SAC ER production. This is because (as highlighted by Harland (1994)) some of the most severe stresses and strains within a resin are sterically induced during activation of the copolymer with the functional group and the subsequent aqueous conditioning and rinses which complete the transition from a hydrophobic to a hydrophilic structure. In addition, upon hydration, IERs swell differentially because of the unsymmetrical distribution of crosslinking thereby creating further strain within the resin beads.

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 18 The introduction of a swelling agent (such as EDC) can relieve the strains imposed during activation, thereby easing greatly the steric resistance to activation of what would otherwise be a collapsed copolymer structure.

Essentially, the process of swelling opens up the copolymer so that reactants can penetrate beneath the surface. As noted by Sherrington (1998), the swelling process itself occurs largely “from outside to the interior” and this behaviour has been treated quantitatively using the so-called ‘shrinking core’ model4. Figure 2-11 schematically demonstrates the swelling and contraction of IERs in ‘good’ and ‘bad’ solvents5.

(a) shrinking glassy core to form an expanded gel in a good solvent (b) contraction of swollen gel on addition of a bad solvent with bursting of resin to osmotic shock Figure 2-11: Solvent response of gel-type resins Source: Sherrington (1998)

As noted by Dorfner (1991), experts can detect differences between cation exchange resins swollen with or without solvent (by microscopic examination), based on the inferior quality of the latter. Another benefit of using a sulphonation swelling agent is that the reaction time can be reduced. Without solvent to soften the copolymer bead, the reaction between the polymer and the acid is slower and it can take several hours for sulphonation to complete. In a plant that is running near capacity in a batch or semi-batch mode, it is important to reduce the time for any one batch, particularly where different products are made in the same equipment (Dow, 2006).

The use of swelling agents is also particularly important for highly cross-linked copolymers. This is because resins with a higher degree of cross-linking show more resistance to oxidising conditions that tend to de-crosslink the polymer. Activation becomes difficult because access to the interior of the bead is hindered by the high density of the matrix. The rate of exchange increases in proportion to the mobility of the ions inside the exchanger bead. If the structure is too dense, ionic motion is slowed down, thus reducing the operating capacity of the resin. The greater the ionic mobility in the resin, the poorer is the differentiation between the adsorption of ionic species with the same charge. Consequently, the degree of cross-linking in the resin must be increased when greater differences in ionic affinity are required (Ramaswamy, Huang, & Ramarao, 2013).

4 This is a major model that has been developed for non-catalytic fluid-solid reactions (Gbor & Jia, 2004). 5 It is noted that the swelling solvent does not appear to be as critical in ion-exchange synthesis of macroporous substrates. This is because their surface is already ‘exposed’ and ready to be converted into an ion exchanger (Fritz & Gjerde, 2009). Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 19 It is apparent (from, e.g. Sherrington (1998)) that EDC is a highly compatible and ‘good’ swelling solvent for the PS-DVB copolymer, and it is commonly considered as the benchmark solvent in the SAC ER production process. Another vital characteristic of EDC is its ability to remain stable under sulphonation conditions (in hot concentrated sulphuric acid).

In patent EP1685166, for example, Marvin et al (2012) reinforces the importance of this solvent, stating that EDC is the most common solvent used in gel cation exchange resin processes. Furthermore, patent EP1685166 A2 (Tegen, Tesch, & Harris, 2006) notes that the use of solvents, especially chlorinated solvents in gel cation exchange resin processes, has been a preferred method, and results in mechanically and osmotically stable cation exchange resins, with low bead breakage, adding that the most common solvent used in gel cation exchange resin processes is EDC. 2.5 Conditions of EDC use

2.5.1 Overview

The parameters of the applicants’ use of EDC are described in Table 2-2. Following the table, more specific information on the SAC ER production processes at Chauny and Fombio is provided.

Table 2-2: Parameters for EDC use in the manufacture of IERs Parameter Description EDC is used to swell PS-DVB copolymer beads during their sulphonation and functionalisation into (microporous) SAC ERs. This sulphonation process is undertaken at the applicants’ respective Chauny and Fombio IER manufacturing facilities.

Tasks performed by Swelling of the copolymer enhances the accessibility of sulphuric acid into its structure the substance and achieves the sulphonation of the aromatic rings. EDC’s effectiveness and properties allow the process to achieve high yields and acceptable quality of SAC ERs with short cycle times for sulphonation. The solvent is also highly recoverable in the process Physical form of the Liquid – 99.9% purity product Concentration of the <10ppm (<0.001%) residual EDC is present in the final SAC ER products. Some substance in the specialist grades also meet more stringent requirements product The following technical criteria have been identified for alternative substances (these are discussed further in Section 2.6 and a sub-set of the criteria also apply to the implementation of an alternative technique):

Copolymer swelling efficiency Chemical stability Thermal stability Critical properties Solvent recyclability and quality criteria Separation from water EDC must fulfil Separation from sulphuric acid Freezing point Residuals in final polymer product Sulphonation yield Cycle time Final SAC ER quality Environmental regulations

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 20 Table 2-2: Parameters for EDC use in the manufacture of IERs Parameter Description '''''''' '''''''' '''''#A'''''''''''''' '''''''''''''''' ''''' '''''''''''''''''''''''' '''''''''''''''''' ''' ''' '''''''''' ''''' '''''' '''''''''' ''''''''''''' ''' ''''''' '''''''''''''''. The solvent is charged once per batch of SAC ER Function conditions manufactured. EDC is highly recoverable in the process with a 95% reuse level (the (frequency of use remaining volume has to be added as fresh charge of EDC). and quantity used) As highlighted in Section 3, the Chauny facility uses ''''' #B ''''' of EDC and the Fombio facility uses ''''''#B '''''' As the process involves hot concentrated sulphuric acid and chlorinated solvent, chemical conditions require highly corrosion-resistant equipment. The process pH range is 0-3 for sulphonation and the sulphuric acid concentration greater than 90%-w.

''''' ''''''''''''''''' ''''''' '''''''''''''' '''''''''''''''''' '''''''''''''''''''''' ''' '''''''' ''''' '''''' ''''''''''''' '''''''''''''''''' ''' ''' ''''''''' ''''''' '''''''' ''''''''''''''''''''' '''#A '''''''''''''' ''''''''''''''''' ''' ''' ''''''''' ''''''' '''''''''''''''''' ''''''''''''''' '''''''''''''''''''' '''' ''''''''''''''''' '''''' ''''''''''''' ''''''''''''' ''''''''''' Process and performance '''' '''''''''''''' ''''''' '''''''''''''''''' ''''''''''''''''' '''''''''''''''''''''' ''' ''''''' ''''' ''''''' ''''''''''' ''''''''''''''' ''' ''' constraints '''''''''' ''''''' '''''' '''''''''''''''''''' ''''''''''#A ''''''' '''''''''''''''' ''' ''' ''''''''' ''''''''''' ''' ''''' '''''''''''''''''' '''''' '''''' ''''''''''''''' ''''' ''''''''''''''' ''''''''''''' '''''''''''''' '''''''''''''''''''''

Timing constraints for a good sulphonation process are related to the polymer structure and the use of a swelling solvent is required to achieve a cost effective cycle time. This is of particular importance for more highly cross-linked PS-DVB copolymers, which require longer sulphonation times to achieve the desired level of sulphonation It is not possible to remove EDC under the current process when technical and Can the use of EDC economic constraints are considered. The use of EDC is required to achieve cost be eliminated and effective processing, high quality resins and the appropriate (and approved) the process performance level for a wide variety of SAC ER markets and applications on the global continue? scale Customer Customers could accept resin made with or without EDC provided the product requirements specifications, quality and performance criteria are met. Customers will be driven by associated with the performance data as well as specifications such as exchange capacity, density, swelling use of the substance agent residuals in the polymer and mechanical resistance Extensive certification and qualification requirements must be fulfilled across the applicants’ product ranges. Requirements differ substantially depending on the end- use of the final SAC ERs. For example, SAC ERs used for drinking water applications will require certifications in accordance with NSF (see http://www.nsf.org/about-nsf/), WQA (see http://www.wqa.org/) and country-specific requirements to ensure safe use Industry sector and whereas SAC ERs used in e.g. the power generation industry will require qualifications legal requirements based on detailed technical factors such as extractables, total organic carbon levels for technical and physical stability. acceptability that must be met and the Chauny and Fombio are global product supply points and as such, certification and function must deliver qualification requirements are not limited to customers within the EU region.

The use of an alternative to EDC would trigger extensive recertification and requalification requirements. Associated costs and timescales have the potential to be highly variable

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 21 2.5.2 SAC ER production at Chauny and Fombio

Overview of activities at Chauny

The Chauny site is operated by Rohm and Haas France S.A.S., who were acquired by Dow in 2009. The site was built in 1948, covers an area of 53 hectares and has over 300 employees. It is classified as SEVESO II, high threshold.

On the site, IERs, adsorption resins and catalysts are manufactured. The site also houses laboratories for technical support and application development for clients, as well as for undertaking quality control. The IERs, adsorbent resins and catalysts produced at Chauny are used in a wide range of applications from water treatment to the food industry, pharmaceuticals, purifying minerals, energy, chemical formulation and catalysis. A schematic overview of the SAC ER production process at Chauny is provided in Figure 2-12. Further details are available in the corresponding CSR.

Overview of activities at Fombio

The Fombio site is operated by Dow Italia Srl. The site was acquired by Dow in the mid 1980’s from the Montedison Group and was originally constructed in the 1960’s. The site covers an area of approximate 18 hectares and has over 60 employees. It is classified as SEVESO II, high threshold.

On the site, IERs, copolymers and acrylic weak acid cations are manufactured. The site also houses laboratories for technical support as well as for undertaking quality control. The IER’s and copolymers produced at Fombio are used in a wide variety of applications, from water treatment to the food industry, pharmaceutical intermediates, purifying minerals, energy and catalysts. A schematic overview of the SAC ER production process at Fombio is provided in Figure 2-13. Further details are available in the corresponding CSR.

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 22 Spent sulphuric acid disposal EDC vents treatment Neutralisation  (carbon bed Atmosphere adsorption) Other raw materials Acid recovery

Recycled EDC Reactor Main EDC storage and Product SAC ER (product storage tanks process packaging Product activation) receiver

EDC recovery (for recycling)

Figure 2-12: Chauny process diagram

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 23 Spent sulphuric acid disposal

EDC vents treatment Emission (carbon bed point adsorption)

Other raw Wastewater materials Acid to WWTP recovery

Recycled EDC Reactor EDC storage Product Product SAC ER and process (product tanks finishing packaging Product receiver activation) and storage

EDC recovery (for recycling)

Figure 2-13: Fombio process diagram

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 24 2.6 Technical feasibility criteria for alternative substances

2.6.1 Introduction

The development of technical feasibility criteria for EDC and its alternatives has been based on a combination of consultation between the independent third party that has authored this AoA and the applicants, in addition to a review of available scientific literature.

Through the use of a detailed written questionnaire (disseminated in June 2014) the applicants were asked to provide details of the (ideally) measurable, quantifiable technical performance criteria which EDC meets and that any alternatives (substances and technologies) would also need to meet before they are seriously considered as replacements. These could relate to issues of molecular structure, solubility, transformation products, product purity, energy consumption, etc. anything that is relevant and important to the process in which EDC is used and the roles it plays.

In parallel, scientific literature delving into the parameters of the SAC ER production process and the assessment of the technical suitability of specific alternative technologies was collected and analysed (with the assistance of the applicant) and has been incorporated into the analysis. The role of EDC as a sulphonation swelling agent of PS-DVB copolymer beads in the production of SAC ERs has been described above in Section 2.5. The technical feasibility criteria that shall be used in the assessment of the technical feasibility of selected alternatives are as follows:

 Copolymer swelling efficiency  Chemical stability  Thermal stability  Solvent recyclability  Separation from water  Separation from sulphuric acid  Freezing point  Residuals in final polymer product  Sulphonation yield  Cycle time  Final SAC ER quality  Environmental regulations

The discussion below explains the relevance and importance of each of the criteria and presents in more detail the threshold values (or ranges) that will be used in Section 5 for the comparison of the shortlisted alternatives to EDC.

It should also be noted that, in many instances, technical comparison criteria are strongly interrelated and it is not possible to consider a criterion independently of several others.

2.6.2 Criterion 1: Copolymer swelling efficiency

Importance of the technical criterion

As highlighted above, the sulphonation process requires the PS-DVB copolymer to be swollen to enhance accessibility of sulphuric acid into the polymer structure and achieve the sulphonation of the aromatic rings. The ability of the solvent to sufficiently swell the copolymer during sulphonation will affect the quality (e.g. surface) of the beads, in addition to the efficiency of the process (less swelling will result in a reduced yield of SAC ERs per batch, as well as an overall reduction in plant

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 25 capacity). Consequently, good swelling of the PS-DVB copolymer beads with the solvent is required in order to achieve the best quality / performance / cost balance for the end products.

An example of the effect of swelling on the copolymer bead quality has been provided by the applicants in Table 2-3.

Table 2-3: Relationship between swelling solvents and resin bead quality Description Copolymer bead quality example This is the typical appearance of a SAC ER bead where EDC has been used as the swelling solvent. The bead is high quality (smooth, uncracked and complete)

This is the typical wrinkled appearance of a SAC ER bead made with the solventless process (or from solvents with poor swelling characteristics)

This example shows cracked beads. Alternative solvents must yield higher quality beads than this

Source: Applicants’ information

Threshold value / considerations

EDC is an excellent swelling solvent for the PS-DVB copolymers utilised by the applicant. Under test conditions (described in detail in Section 4.2.1 (screening step 3)) it achieves a 40% increase in dry copolymer swelling after 24 hours at room temperature conditions (this is based on a 10% DVB cross-linked PS-DVB copolymer, which is used as a testing ‘benchmark’6).

Potential alternatives will require the same (or higher) swelling efficiency in order to be economically viable options for the applicants.

2.6.3 Criterion 2: Chemical stability

Importance of the technical criterion

The ability of the swelling solvent to remain inert during the sulphonation process (i.e. whilst present in >94% sulphuric acid) is very important. Decomposition of solvent would generate black tars in the sulphuric acid and would render spent acid from the process unrecyclable. This would raise a significant waste issue from the sulphonation process which would be highly inefficient (and thus

6 The applicants’ range of cross-linked PS-DVB copolymers varies typically from 2-16% DVB, and different levels of cross-linking typically deliver different swelling results. The 10% cross-linked copolymer is utilised as a ‘benchmark’, as the applicants’ previous R&D experience shows that promising results achieved for this copolymer are often transferrable across other cross-linked copolymer grades.

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 26 uneconomic). Solvent decomposition would also contaminate the copolymer beads, resulting in an insufficient quality of SAC ER products for end users.

Threshold value / considerations

Potential alternative substances must be chemically inert under sulphonation conditions.

2.6.4 Criterion 3: Thermal stability

Importance of the technical criterion

In addition to chemical stability, any potential alternative substance must also show resistance to decomposition at process operating temperatures. As highlighted above, decomposition of solvent generates black tars in the sulphuric acid rendering the spent acid unrecyclable. This would raise a significant waste issue from the sulphonation process which would be highly inefficient (and thus uneconomic). Solvent decomposition would also contaminate the copolymer beads, resulting in an insufficient quality of SAC ER products for end users.

Threshold value / considerations

Potential alternative substances must be thermally stable at the full range of plant operating temperatures. The applicants’ stability threshold range is 25 ˚C to 140 ˚C.

2.6.5 Criterion 4: Solvent recyclability

Importance of the technical criterion

The applicants use distillation and condensation as a means of recovering the solvent from the process. This removes the solvent from plant waste and also eliminates the need to purchase new solvent (apart from a significantly smaller recharge volume).

If solvent could not be recoverable via this process, very large volumes of sulphuric acid containing high levels of swelling solvent would be wasted. Such an outcome would clearly be unsustainable.

Threshold value / considerations

The solvent must be recoverable in the process (via distillation and condensation). The current recovery rate for EDC in the process is 95%. Potential alternatives should achieve a similar or improved rate of recovery.

2.6.6 Criterion 5: Separation from water

Importance of the technical criterion

After distillation and condensation, water is also removed from the process. Consequently, the solvent and water must be separated (to allow the solvent to be recycled).

Threshold value / considerations

The solvent must have low water solubility in order to be separated from water, prior to being reused.

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 27 2.6.7 Criterion 6: Separation from sulphuric acid

Importance of the technical criterion

Residual solvent needs to be able to separate from sulphuric acid in order to be reused consistently. This is a mandatory requirement to allow spent sulphuric acid to be internally recycled (and externally re-processed), thus avoiding a large volume of waste of both solvent and sulphuric acid.

Threshold value / considerations

The alternative solvent must be able to separate from sulphuric acid.

2.6.8 Criterion 7: Freezing point

Importance of the technical criterion

Alternative solvents need to be in liquid form at low temperatures to avoid freezing in storage tanks during winter.

Threshold value / considerations

Alternative solvents should have a freezing point lower than -20 ˚C.

2.6.9 Criterion 8: Residuals in final polymer product

Importance of the technical criterion

Alternative substances must meet regulatory and specific application requirements with regard to levels of residual solvent in the final SAC ER product.

Threshold value / considerations

The applicants have no option to modify values for specifications against the current EDC resin grades. At a minimum, the level of residuals in the final products must be aligned with market needs and SAC ERs produced with an alternative solvent must meet all necessary quality control parameters and pass all application performance tests in this respect. ''''''' '''''''''''''''' '''' ''''''' ''''' ''''''' '''''''''''''''''''''' '''''''' '''''' ''''''''''''''''' '''''''''''''''''''''''''''' '''#E''''''''' ''''''''''''''' '''''''''''''' ''''''''''' ''''''''' ''''' '''''''''' '''''''' '''''' '''''''''.

2.6.10 Criterion 9: Sulphonation yield

Importance of the technical criterion

For an alternative to be economically feasible, its use should result in the same (or near to the same) yield of SAC ERs as produced when EDC is used in the process. In this respect, this criterion relates directly to the swelling of the SAC ER (and consequently the swelling efficiency of the solvent used in the process).

Threshold value / considerations

For each grade of SAC ER produced, the substance should achieve the same (or an improved) ion exchange yield as compared to the EDC-based process.

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 28 2.6.11 Criterion 10: Cycle time

Importance of the technical criterion

This criterion is directly related to copolymer swelling efficiency and is important for economic reasons. An increased cycle time would result in a decreased SAC ER yields (and thus reduced plant capacity) and also increase processing (e.g. electricity and maintenance) costs. Any increase in cycle time will therefore impact the competitive position of the applicant. It should also be noted that cycle time also differs based on the degree of cross-linking of the copolymer, with more highly crosslinked copolymers having longer cycle times. The applicant notes that a typical cycle time for the production of a SAC ER product batch will be between ''''''' '#A '''''''.

Threshold value / considerations

Potential alternative substances should allow for similar or improved cycle times for each grade of SAC ER produced by the applicants.

2.6.12 Criterion 11: Final SAC ER quality

Importance of the technical criterion

The applicants supply products to many ‘high-end’ SAC ER applications (e.g. within the nuclear, ultra pure water, food and biopharmaceutical sectors). Consequently, quality of the final SAC ERs is of extremely high importance. Any reduction in the quality (e.g. parameters such as moisture holding capacity, appearance (cracked beads, broken beads, non-smooth surface beads), leachables, physical stability, performance in end-uses and lifetime tests, and bead diameter) would not be acceptable in such applications.

Threshold value / considerations

The applicants have no option to modify values for specifications against the current EDC resin grades. At a minimum, the current specifications must be aligned with market needs and SAC ERs produced with an alternative solvent must meet all necessary quality control parameters and pass all application performance tests.

2.6.13 Criterion 12: Environmental regulations

Importance of the technical criterion

The applicants are legally obliged to comply with environmental regulations at the Chauny and Fombio plants and to meet local discharge permits associated with waste emissions. The applicants achieve compliance through the use of activated carbon beds as abatement systems to minimise emissions (see Figure 2-12 and Figure 2-13) (the use of activated carbon beds also forms part of the applicants’ recycling process, via a process of regeneration). If the applicant failed to fulfil environmental regulations they would face severe penalties.

Threshold value

Any potential alternative substance would have to be recoverable through activated carbon beds (adsorption and desorption), in order for the applicants to comply with local regulations for plant discharges to the atmosphere. Fombio’s environmental operating permit limits the EDC air

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 29 emissions to 5 mg/Nm3 and Chauny’s environmental operating permit limits EDC air emissions to 2 mg/Nm3. 2.7 Technical feasibility criteria for alternative technologies

This AoA also discusses the availability and suitability of alternative technologies. It will be explained that alternative technologies essentially involve a sulphonation process which removes the need for a solvent in the production of the SAC ERs.

Information submitted by the applicants and a review of the available literature confirms that the technical criteria that need to be considered for the comparison of the EDC-based technology to the use of a ‘solventless sulphonation’ process include the following7 (see above for information on the importance of each of these technical feasibility criteria, and their threshold values):

 Copolymer swelling efficiency  Sulphonation yield  Residuals in the final product (Note: in this instance residuals will not relate to levels of solvent, but polymeric leachables)  Cycle time  Final SAC ER quality.

As will be made clear in the following sections, it is testament to Dow’s R&D efforts that some success has been achieved in removing the need for solvent in the production of a ‘lower end’ niche SAC ER product. However, this technology is not currently technically or economically feasible for the wide range of SAC ERs produced with EDC by the applicants, and attempts to implement this alternative for a wider range of end products would put the applicants at a severe competitive disadvantage vis-à-vis their non-EU competitors.

7 As this process removes the need for the use of an alternative substance, many of the criteria discussed earlier no longer apply (i.e. chemical stability, thermal stability, solvent recyclability, separation from water, separation from sulphuric acid, freezing point, and environmental criteria).

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 30 3 Annual tonnage

As discussed, the applicants use EDC at two EU locations: Chauny, France and Fombio, Italy. Annual consumption of EDC for each facility is provided below and is based on 2014 data. '''''''' '''''''''''''''''''' '''''''''' ''''''' ''''''''''''''''''''''' '''' '''''''' ''''''' '''''''''' '''''''''''' '''''' '''''' ''' '''''''''' '''''''''''''''''''' ''''''''''' ''''''' '''''' '''''' '''''''''' '''' ''''''' ''''''''''''' '''''''''''' '''' ''''''' ''''''' '''''' '''#C & G'''''''''' ''' ''' '''''''''''''''''' '''''''' ''''''''''''''''''''''''''' ''''''' '''''''''''''' '''''''''''' '''' ''''''' '''''''''''' '''''''''''''' ''''' '''''''''''''''' '''''''''' '''''''''''''''''' '''''''' '''' ''' ''''''''''''''' ''''''''''''''''''''''' ''''' '''''' '''''''''''''''''' '''''''' ''''''''''''''' ''''''''' '''''' ''''''''''''' ''''''''''''''

Chauny: Confidential annual tonnage for EDC in SAC ER production: ''''''#B'''''''. Non-confidential annual tonnage band for EDC in SAC ER production: 1-50 tpa.

Fombio: Confidential annual tonnage for EDC in SAC ER production: ''''' #B ''''. Non-confidential annual tonnage band for EDC in SAC ER production: 1-50 tpa.

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 31 4 Identification of possible alternatives

4.1 Introduction and list of possible alternatives

The focus of this AoA will be on:

 Two alternative substances - 1,2,4-trifluorobenzene and DCM; and  One alternative technique - solventless sulphonation.

In arriving at this shortlist, the applicants have considered more than 1000 potential alternative substances and applied a systematic and thorough process of literature review and experimental laboratory work, investing €0.7-1 million on related R&D activities since mid-20128. In the following section, this R&D is described in further detail.

As the use of EDC is not of relevance to the downstream users of SAC ERs (customers will accept products as long as they meet the required technical and cost parameters), consultation with customers of Dow on the issue of alternative substances and technologies has not been undertaken. 4.2 Description of efforts made to identify possible alternatives

4.2.1 Research and Development

Past research

Since the advent of the synthetic organic IERs, Dow has carried out extensive R&D activities associated with the progression of IER technologies. With relevance to the applicants’ use of EDC, earlier work was undertaken several years ago at both Dow Italia and Rohm and Haas9 aimed at finding potential alternative substances for halogenated solvents as swelling agents in the production of SAC ERs, but this was not successful, as alternatives were unable to meet the required technical standards.

Other targeted activities have provided some results; for instance, Dow’s R&D efforts have resulted in the successful implementation of the solventless sulphonation technique (discussed further below) to produce a ‘lower end’ SAC ER product (it is explained in Section 5 why the solventless technology cannot be implemented across a wider range of the applicants’ production activities).

For the benefit of the reader and in relation to past R&D efforts, a number of relevant patents filed by Dow are highlighted in Table 4-1, below.

8 The R&D, regulatory, and manufacturing technology costs associated with this REACH driven initiative are currently projected to ''''''''''''' ''''''''''''''' #G'''''''''' '''''''''''' by the EDC Sunset Date in November 2017. 9 As noted in Section 2.4, Dow acquired Rohm and Haas in 2009. Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 32 Table 4-1: Relevant past R&D undertaken and patents filed by Dow Patent number (year Title Applicant Abstract / information from patent description of publication) Sulfonation of copolymers of US 2500149 A (1950) Dow Chemical Co This invention concerns an improved method of sulphonating substantially insoluble monovinyl-and polyvinyl- copolymers of a major amount of a monovinyl-aromatic compound and a minor amount of aromatic compounds a polyvinyl-aromatic compound. It pertains especially to the sulphonation of copolymers of styrene and divinylbenzene. The invention is concerned more particularly with an improved method of producing the sulphonated copolymers in the form of granules, preferably of spherical or eggshaped form and nearly free of unduly fine particles of smaller than 60 mesh size, which method involves sulphonation of the copolymers in the manner described in the patent High stability partially US3252921 A Dow Chemical Co This invention concerns sulphonated cation exchange resins possessing high physical sulfonated cation exchange (1966) stability and their method of preparation. It pertains especially to a method for partially resins sulphonating insoluble copolymers of a major proportion of a monovinyl aromatic compound and a minor proportion of a polyvinyl aromatic compound. The invention is concerned more particularly with a method of producing such partially sulphonated copolymers in the form of spheroidal beads which are characterised by a spheroidal layer of sulphonated copolymer enveloping an inner non-sulphonated copolymer core Method for preparation of US20030018090 / Rohm and Haas An improved process for preparing strong acid cation exchange resins by sulphonation of strong acid cation exchange EP1270609 A3 (2004) Company wet cross-linked copolymer in the absence of organic swelling solvents is disclosed. This resins process involves dewatering a cross-linked poly(vinylaromatic) copolymer to selected residual moisture levels of 3 to 35%, followed by non-solvent sulphonation, to provide strong acid cation exchange resins having enhanced physical stability and that are free of chlorinated-solvent contaminants Improved solventless US20050014853 A1 / Dow Global A process for the preparation of styrene-divinylbenzene gel cationic exchange resins by sulfonation of exchange resins EP1685166A2 Technologies Inc. sulphonation in sulphuric acid, without the addition of a swelling agent or acrylic co- (2005/2006) monomers, with relatively fast hydration rate. The use of temperature and acid concentration to increase the rate of sulphonation while controlling the side reaction of sulphone bridging minimises reaction time while maximising bead quality

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 33 Current research by Dow – consideration of potential alternative substances

Dow continues its research into the identification of a suitable alternative solvent and the placing of EDC into Annex XIV of the REACH Regulation has certainly provided further incentive for the development of a technically and economically feasible alternative to EDC, with an acceptable risk profile. Indeed, as part of the authorisation process, Dow has made fresh and extensive efforts to identify potential alternatives. This has involved a thorough review of literature as well as a systematic process of experimental laboratory work to screen a large number of potential alternative substances, identifying those that warrant further and detailed examination (in Section 5 of this AoA)10.

This ‘screening exercise’ can be broken down into four steps:

 Screening step 1: Initial identification of a long list of potential alternatives  Screening step 2: Assessment of swelling efficiency  Screening step 3: Assessment of stability and recyclability under sulphonation conditions  Screening step 4: Preliminary hazard assessment.

Each of these steps (and the subsequent results) is discussed in detail below, and by following this approach Dow has been able to concentrate efforts and resources on those alternatives that are potentially most feasible, whilst ensuring that the scope of the search for potential alternatives has been as all-encompassing as practicable.

It is important to note that whilst the applicants have made significant efforts to present the screening process and results as methodically as possible, reasoning for the inclusion or exclusion of substances from further consideration cannot always be based on the clear-cut attainment or non- attainment of e.g. a specific technical threshold value. On occasion and as to be expected within experimental R&D, there can be ‘exceptions to the general rule’ which require supplementary analysis11. In such instances the expert judgement and discretion of Dow R&D staff has been utilised.

Screening step 1: Initial identification of long list of potential alternatives

The purpose of this first step was to identify an initial list of potential alternative substances, which would be screened via the multi-step method described below.

The initial list began with Dow utilising their in-house R&D software, ChemComp(tm). ChemComp(tm) is comprised of a group of programs that allow users to predict solubility, evaporation rates, and flashpoints of solvent blends and solvent/resin blends. These programs also share a common database containing more than 600 solvents and more than 300 resins. The list of solvents was an obvious starting point. However, this was also complimented by a targeted literature search undertaken by Dow’s in house information research group ‘Technical Information Services’ (TIS) (Search and Analysis team).

10 The applicant’s efforts have also been the subject of a paper ‘Novel Swelling Solvent Screening Methodology for Highly Crosslinked Styrenic Copolymers using Hansen Solubility Parameters: 1. Analysis of Alternatives for Sulfonation Solvents’, which is to be presented in mid-2016 at the global Ion Exchange Conference (‘IEX’) in Cambridge, UK. 11 One such example is cyclohexane which can be considered a ‘bad’ solvent at room temperature and ‘good’ solvent at high (e.g. process) temperatures. Testing on this solvent, complementary to the applicants’ screening, found that its use resulted in rough copolymer bead surfaces and did not meet the quality requirements to replace EDC. Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 34 The objective of this literature search was to identify, in a broad manner, solvents that can be used for the sulphonation of cross-linked styrenic copolymers. In the rationale for the search it was also made very clear that the identification of any new ‘green’ solvents would be very welcome. Key information sources for the search of patents and technical literature are summarised in Table 4-2.

Table 4-2: Key information sources used in patent and literature searches Source Details Thomson Innovation http://info.thomsoninnovation.com/ Web of Science http://thomsonreuters.com/thomson-reuters-web-of-science/ SRI reports http://www.sri.com/ (Report 124A, ‘Ion Exchange Resins’ was utilised) STN http://www.cas.org/products/stn/dbss

Search results on patents and technical literature documents were organised separately and broken down into tiers (based on their titles, abstracts and Derwent abstract screening). Tier 1 results identified documents of interest; Tier 2 results identified documents of general/potential interest and Tier 3 results were the remainder of the set, determined to be most likely not of interest. The breakdown of search results can be seen in Table 4-3.

Table 4-3: Patent and technical literature search results Number of technical literature Tier Number of patents identified documents identified Tier 1 6 6 Tier 2 56 33 Tier 3 300 123

The Dow R&D team looked in detail at all (524) Tier 1, 2 and 3 results to identify potential alternatives (for the benefit of the reader details on Tier 1 patents and studies are provided, respectively, in Table 4-4 and Table 4-5). In addition, to compliment this research, literature review on Dow internal reports was also undertaken, along with internal interviews with experts in the field of polymer functionalisation and sulphonation.

Based on the outcome of this exercise, identified potential alternatives from the literature search (which included e.g. cyclohexane, nitropropane and 1,1,2-trichloroethane) were cross-referenced with the list of solvents in the ChemComp(tm) database to ensure the initial list of potential alternative substances was as comprehensive as possible.

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 35 Table 4-4: Tier 1 patent search results Patent number Title (year of Applicant Abstract / information from patent description publication) Production of cation exchange JP1087603A Tokyo Organic Purpose: To obtain the titled resin useful as a monobed for producing extremely high-purity resin (1989) Chem Ind Co Ltd purified water, by sulfonating a specific cross-linked copolymer in the presence of a swelling organic solvent at a specific temperature and readily removing an eluted substance from an anion exchange resin. Solution: A cross-linked copolymer which is cross-linked with a polyvinyl monomer and comprises a monovinyl aromatic monomer is sulphonated in the presence of an organic solvent (e.g. nitrobenzene) to swell the cross-linked copolymer at ≤85°C to give the aimed resin. The cross-linked copolymer is preferably obtained by subjecting the monovinyl aromatic monomer and another copolymerisable monomer to suspension polymerisation in the presence of the polyvinyl monomer. Sulphuric acid is used as the sulphonating agent Method for producing sulphonated JP2003277438A Mitsubishi Problem to be solved: To provide a method for producing a sulphonated polymer, by which a polymer (2003) Chemicals Corp haloalkyl group-containing polymer can efficiently be converted into an alkanesulfonic group-containing polymer in one step process not leaving an intermediate without accompanying the production of by-products due to side reactions such as hydrolysis. Solution: This method for producing the sulphonated polymer containing structural units represented by the general formula comprises sulphonating a polymer containing haloalkyl group-containing monomer units in the presence of a sulphite and an ionic liquid Sulphonation process for low US5280082A Camelot Cross-linked styrenic polymers may be sulphonated in a controlled manner in an organic crosslinked polystyrene (1994) Technologies solvent at elevated temperature using SO3 in the presence of a trialkyl phosphate. The process does not introduce further crosslinking into the polymer permitting it to have an extremely high water uptake. The resulting polymer is useful as a hydrogel The manufacturing method of an JP02961820B2 Mitsubishi Kasei Resin production comprises uniformly immersing mixtures of bifunctional aromatic ion exchange resin (1999) Corp monomer and monofunctional unsaturated aromatic monomer in aromatic cross-linked copolymer particulate consisting of a monofunctional aromatic monomer and a bifunctional unsaturated aromatic monomer containing up to 10 wt.% of a unit derived from a bifunctional unsaturated aromatic monomer and having up to 0.2 ml/g of a pore vol. per unit wt. and polymerising, in the presence of an initiator, then introducing ion exchange functional radical into the polymer particulate. Manufacture preferably comprises heat- treating aromatic cross-linked copolymer particulate of monofunctional unsaturated aromatic monomer and bifunctional unsaturated aromatic monomer, and containing up to 10 wt.% of a unit derived from the bifunctional unsaturated aromatic monomer to contain up to 0.2 ml/g of a pore volume per unit wt. monofunctional unsaturated aromatic monomer

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 36 Table 4-4: Tier 1 patent search results Patent number Title (year of Applicant Abstract / information from patent description publication) is styrene, vinyl-naphthalene, vinyl-toluene. The bifunctional aromatic monomer is divinylbenzene or divinylethyl benzene. Precipitates used at production of the copolymer comprise isooctane or hexane Process for preparation of JP2001261818A Lion Corp Problem to be solved: To provide a process for preparing of a sulphonate of a polymer in a sulphonate of polymer (2001) high purity and a high yield. Solution: The process comprises the sulphonating of a polymer having an aromatic ring in the main chain with a sulphonating agent in the presence of a solvent containing at least one compound between an ether compound and a carbonyl group-containing compound. The above polymer available is such a polymer as, for example, a polysulfone and a polyethersulfone Process for preparing ion exchange US5523327 A Sybron Chemical Ion exchange resins are prepared by a process comprising functionalising styrene- resins by chloromethylation of (1996) Holdings divinylbenzene copolymers, or other cross-linked vinyl copolymers, by sulphonation or crosslinked styrene copolymers in chloromethylation and amination, and achieving high ion exchange capacity and a low the presence of saturated degree of resin bead fragmentation, in the presence of hydrocarbon liquids, such as hydrocarbon swelling agents cyclohexane

Table 4-5: Tier 1 technical literature search results Author Title Abstract Zippi et al Sulfonation methods for In an effort to prepare polymer-based materials for the production of Nitrogen-13 for medical imaging applications, a (2005) poly(styrene/divinylbenzene) series of poly(styrene/divinylbenzene) derivatives were synthesised, sulphonated, and then pyrolysed. Nine different beads sulphonation methods were employed, and the resulting polymers were analysed by titration and elemental analysis to determine the best method Barreto de How to maintain the This work aims to describe the use of acetyl sulphate as sulfonating reagent of microporous beads based on styrene and Oliveira et al morphology of styrene- divinylbenzene which were prepared by aqueous suspension copolymerisation. The copolymer was chemically modified (2005) divinylbenzene copolymer by two different sulphonating agents, namely sulphuric acid and acetyl sulphate which is prepared “in situ” by mixing beads during the sulfonation acetic anhydride and sulphuric acid. The morphologic features of resin beads were analysed by optical microscopy and

reaction by scanning electron microscopy. The sulphonic group incorporation into the copolymer network was verified by infrared spectroscopy and quantified by using a standardised NaOH solution. The bead morphology maintenance depends on the sulphonating agent and reaction conditions Malik et al Sulfonated styrene- Maximum sulphonation and minimum carboxylation are desirable in sulphonated styrene−divinylbenzene cation- divinylbenzene resins: exchange resins. These characteristics may be achieved with greater control of porosity of the base copolymers. Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 37 Table 4-5: Tier 1 technical literature search results Author Title Abstract (2010) optimizing synthesis and Optimisation of the porosity by varying both the nature and amount of porogen, and cross-linking for maximising estimating characteristics of sulphonation and minimizing carboxylation, are reported. Predictors of the characteristics obtained by statistical analysis

the base copolymers and the of the data, and the ranges of conditions in which they can be employed, are discussed. The optimum conditions are resins. cross-linking 20% to 23% and pore volume 0.14 mL/g to 0.3 mL/g. The relationship of the particle size with porosity of the base copolymer and capacity of the resins is discussed. The effects of residual porogen/homopolymer on the sulphonation of these copolymers are also discussed Yan et al Sulfonation of highly The sulphonation of highly cross-linked macroporous styrene-divinylbenzene copolymers was studied as a function of (2000) crosslinked macroporous reaction temperature, time and diluents used in the preparation of the copolymers. The results show that when the styrene- divinylbenzene reaction is performed in different swelling media, the relationship between the exchange capacity and the degree of

copolymers crosslinking is different. Compared to the low cross-linked macroporous copolymer, the highly cross-linked one reacts with higher reaction rate, and the sulphonation could proceed at much lower temperature. The effect of the solvating power of swelling media on the exchange capacity, in this case, becomes very limited. The surface sulphonated, high cross-linked copolymers with exchange capacities of 1.19~1.35mmol/g could be obtained by carrying out the sulphonation at 35 ˚C for 3 hours Byun et al Sulfonation of crosslinked Symmetric microporous membranes based on polystyrene cross-linked with divinylbenzene were prepared. They were (1994) asymmetric membranes sulphonated with sulphonic acid and washed with solutions of gradually increasing pH to reduce environmental shock. based on polystyrene and The sulphonation was monitored by infrared spectroscopy, and changes in wettability and sulphur content were also divinylbenzene recorded. Morphologies and reverse osmosis performance of sulphonated membranes were measured, with both water flux and salt rejection increasing after treatment

Dooley & Superacid polymers from Superacid polymers were prepared by bringing metal halides (AlCl3, SnCl4, TiCl4, BF3, or SbF5) in contact with macroporous Gates (1984) sulfonated poly(styrene- sulphonic acid resins [sulphonated, cross-linked poly(styrene-divinylbenzene)]. The resulting solids were characterised by divinylbenzene): preparation chemical analysis, temperature-programmed desorption, transmission electron microscopy, and X-ray photoelectron

and characterization spectroscopy. They were also tested as catalysts for n-butane isomerisation at 0.5 bar and 60 to 120 °C. The polymers consist of supported metal oxyhalide particles, complexes of metal oxyhalides and sulphonate groups, and the remaining unreacted sulphonic acid groups. In the presence of HCl, these polymers were highly active catalysts for the butane isomerisation reaction, the activity being a consequence of a high proton-donor strength inferred to be associated with + H2Cl groups stabilised on the polymer surface by negative charge delocalisation over sulphonate–metal oxyhalide sulphonate groups

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 38 Screening step 2: Assessment of swelling efficiency

As highlighted in Section 2.6, swelling efficiency is one of the key criteria that a potential alternative substance for EDC must fulfil in the applicants’ use. The ability of the solvent to sufficiently swell the PS-DVB copolymer beads during sulphonation affects the quality of the final SAC ERs, in addition to the efficiency of the overall production process. Insufficient swelling of the copolymers will result in a process that is both technically and economically infeasible.

Consequently, with the list of solvents in the ChemComp(tm) database (and output of the applicants’ TIS literature search) as a starting point, the first step in assessing swelling characteristics of the potential alternative substances was undertaken by obtaining Hansen Solubility Parameters (HSP) for all (600+) substances on the list.

HSP were established by Charles M. Hansen in 1967 and are a tool for predicting if a material will dissolve in given solvent or solvent mixture. Mohamed & Wilson (2012) provides a useful summary of these parameters, which are divided into three contributions (dispersion forces (δd), dipolar interactions (δp) and H-bond capacity (δh)), as shown in the Equation (1).

(1)

The above three-dimensional solubility parameter (δT) is assumed to be a vector sum where the three components are treated as solubility coordinates. Hansen reported resin solubility values using a three-dimensional model and concluded that doubling of the dispersion forces (δd), a spherical volume of solubility would be formed for each resin. The sphere is described in Figure 4-1 where the solubility parameter value of a given compound can be visualised as a fixed point and referred to as a tri-point in a three-dimensional space. The coordinates of the tri-point are located by means of three solubility parameter values (δd, δp and δh). When the resin is mixed with a single solvent or multiple solvents with solubility parameter values lying within the sphere, the compatibility is considered ‘good’ while those solvents lying outside the sphere are considered ‘bad’.

Figure 4-1: A three-dimensional plot of the three solubility parameter (SP) contributions i.e., dispersion forces (δd), dipolar interactions (δp), and H-bond capacity (δh), to the total SP (δT). The tri-point represents a hypothetical polymer. Interaction radius is the shortest distance between the tri-point and the solvent Source: Mohamed & Wilson (2012)

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 39 As further explained by Mohamed & Wilson (2012), to aid the solubility parameter criterion of Hansen’s methodology for the selection of ‘good’ versus ‘bad’ solvents, the use of relative energy difference (RED) was proposed (see Equation (2)). In this approach, values of RED < 1 imply that the solvent is ‘good’ or the solvent is ‘bad’ when RED > 1.

(2) where Ra is the distance between centre of the polymer solubility sphere for the solvent-solvent system and Ro is the radius of the sphere; where Ra is calculated according to Equation (3).

(3) where δxR and δxS are the Hansen solubility parameters for the resin and solvent, respectively.

Following the methodology of Hansen, after Dow had obtained solubility parameters (δd, δp and δh) for all substances in the ChemComp(tm) database, efforts were focused on obtaining RED values so that the swelling efficiency for every potential alternative substance could be determined. Those solvents with a RED value >1 (‘bad solvents’) would be excluded from further consideration, and would not progress to the next screening step. HSP were also acquired across the range of PS-DVB copolymer beads utilised by the applicant (from laboratory experiments utilising different solvent probes with known HSP).

However, before the final ranking of solvent swelling efficiency took place using the RED values, extensive laboratory work was undertaken by Dow to validate the proposed approach. The validation was achieved via a series of experimental swelling tests on PS-DVB copolymers with 2%, 7%, 10% and 16% DVB cross-linking (this range of cross-linking represents the variety PS-DVB copolymers utilised by Dow in the production of SAC ERs).

This experimental work also utilised EDC plus a variety of solvents with a wide range of HSP values. These solvents represented the ‘most important’ solvent groups from the 600+ potential alternatives which had been identified: i.e. oxygenated solvents (esters, ethers, carbonates), vinyl containing monomers, alkanes (linear, branched and cyclic), aromatics and halogenated solvents (chlorinated and fluorinated) (linear alkanes, cyclic and aromatic (mono-, di-, tri- and tetra- substitution)). In the swelling tests, the copolymers were charged to graduated cylinders and combined with the testing solvent to cover the polymer beads which formed a packed bed in solvent. The initial volume of the copolymer was recorded and the system was left to equilibrate for 24 hours at room temperature. The volume of the packed bed was then measured after 24 hours and a value for the %- swelling was obtained.

Results of the applicants’ validation tests are presented in Figure 4-2, which demonstrates the linear fit achieved using %- swelling values obtained for the range of cross-linked PS-DVB copolymers, plotted against the RED values. As can be seen in the figure, a broad correlation is achieved between the RED values and the degree of swelling achieved. Experts within the Dow R&D team concluded that the experimental testing validated the assumed physicochemical behaviour of solvent-polymer interactions. Further validation with regard to the relationship between resin quality and RED value was also undertaken with Dow assessing polymer bead smoothness via microscopy (Table 4-6 demonstrates this relationship with examples of benchmark (10% cross- linked) PS-DVB copolymer beads swollen with a variety of solvents).

Based on results from the swelling tests and analysis of microscopy images, the applicants concluded that the ‘RED value’ approach to assessing the swelling efficiency of potential alternative substances was a valid one. Indeed, Dow’s R&D team confirmed that potential alternative substances with RED

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 40 values >1 would (in the vast majority of cases) swell the PS-DVB copolymers insufficiently and form IER beads of unsatisfactory quality. Clearly, however, Dow has also had to utilise the expert judgement of their R&D team to ensure that any potential alternatives that may ‘buck the trend’ were either further considered, or could be excluded on other technical feasibility grounds. As discussed, such expert judgement and discretion has been utilised throughout the screening process. a) 2% DVB cross-linked copolymer b) 7% DVB cross-linked copolymer

c) 10% DVB cross-linked copolymer (note: this is d) 16% DVB cross-linked copolymer the applicants’ ‘benchmark’ testing copolymer)

Figure 4-2: Copolymer swelling in 2%, 7%, 10% and 16% DVB cross-linked (PS-DVB) copolymers vs RED values for a selection of solvents Source: Applicants’ information

Table 4-6: Polymer bead smoothness demonstrated with different solvents Substance RED value Microscopy image of SAC ER bead EDC 0.53

Ethyl Acetate 1.15

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 41 Table 4-6: Polymer bead smoothness demonstrated with different solvents Substance RED value Microscopy image of SAC ER bead 1,3,5-Triisopropyl benzene 1.84

Cyclohexane 2.09

Isooctane 2.63

Source: Applicants’ information

Following the validation exercise, the collected HSP were used to determine RED vs swelling values for the entire list potential alternatives within the ChemComp(tm) database. Dow also undertook additional research to confirm that the initial list of solvents from ChemComp(tm) was as comprehensive as possible. This involved R&D experts studying the 1000+ solvents reported by Hansen (2007) and the Sigma Aldrich catalogue12 was also visited, with solvents reviewed for possible structural features that were not described by Hansen or available in ChemComp(tm).

Dow obtained only a few notable potential alternative substances from this additional search of literature (i.e. trifluorobenzenes (1,2,3-, 1,2,4- and 1,3,5-)). The HSP of these substances were estimated using the ‘HSPiP’ software13 and they were added to the ChemComp(tm) database, with RED/swelling values also calculated.

As a result of the above additional searches, a final ‘complete’ screening list was obtained by the applicants. This list contained 614 potential alternative substances, broken down into:

 355 oxygenated compounds  81 halogenated compounds  65 nitro and nitrogen containing compounds  30 aromatic compounds  24 alkanes (linear/branched)  16 cyclic alkanes  13 alkenes; and  8 thiols.

In addition there were 22 substances for which only commercially available trade names were available.

12 See: http://www.sigmaaldrich.com/catalog/AdvancedSearchPage.do 13 See: http://hansen-solubility.com/HSPiP.html Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 42 As a result of the modelling undertaken by the applicant, 516 of the 614 potential alternatives were excluded from further consideration. These substances were found to have RED values > 1, indicating that they were ‘bad’ swelling solvents for the copolymer (this list is displayed as a separate Annex in Section 9). As demonstrated by the applicants’ validation and laboratory exercises (and also utilising their expert judgement), the use of such solvents would result in inferior quality SAC ERs and longer, less economic processing times. As such ‘poor swelling’ alternatives could clearly not be considered either technically or economically feasible, they were removed from further consideration, leaving 98 potential alternative substances (see Table 4-8) proceeding to screening step 3.

Screening step 3: Assessment of stability and recyclability under sulphonation conditions

Following the swelling efficiency screening step, further experimental laboratory work was undertaken by Dow to assess the potential alternative substances under operational sulphonation conditions, and to obtain information on their stability and recyclability, as well as their influence on sulphuric acid recyclability and final SAC ER quality. This experimental work utilised EDC and 37 solvents representing an extension of substances from the ‘most important’ solvent groups (as identified in screening step 2). The full list of substances is provided in Table 4-7.

It should be noted that the list contains several substances not originally considered within the long list of alternative substances (these additional substances are highlighted grey in the table). Work on these additional substances is associated with the filing of a patent and study undertaken to understand the limits of halogenated aromatics with good swelling characteristics as well as resins with measurable properties close to the objectives of the work. This work was sanctioned alongside the screening exercise because, at that stage, the R&D team had developed good initial knowledge with regard to alternatives that were likely to present promising options for EDC replacement. In this case, the study and patent were specifically required to expand the applicants’ knowledge obtained from initially promising observations associated with trifluorobenzene isomers – which, as described below, progressed through the main screening stages)14.

Information on the stability and recyclability of these substances was highly useful and allowed for read-across results and transferrable expert interpretation on the large number substances that were being considered within this step, but for which no direct testing was taking place.

Table 4-7: Solvents for which experimental laboratory work was undertaken Substance CAS No Substance CAS No 1,2-dichloroethane (EDC) BENCHMARK 107-06-2 2,3-dichlorobutane 7581-97-7 1,1,2-trichloroethane 79-00-5 2,3-dimethyl butane 79-29-8 1-chloro 2,4-difluorobenzene 352-33-0 2,4-difluorotoluene 452-76-6 1,2-dichloropropane 78-87-5 2,4-dibromo - 1-fluorobenzene 1435-53-6 1,2,3-trifluorobenzene 1489-53-8 Cyclohexane methyl ether 108-87-2 1,2,3,4-tetrafluorobenzene 551-62-2 Cycloheptane 291-64-5 1,2,4-trichlorobenzene 120-82-1 Cyclohexane 110-82-7 1,2,4-trifluoro benzene 367-23-7 Cyclohexyl chloride 542-18-7 1,3,5-trifluoro benzene 372-38-3 Diethyl carbonate 105-58-8 1,3,5-triisopropyl benzene 717-74-8 Dimethyl carbonate 616-38-6 1,3-difluorobenzene 372-18-9 Divinyl benzene 1321-74-0 1,4-dichlorobutane 110-56-5 Ethyl acetate 78-93-3 1,4-dimethyl cyclohexane 589-90-2 Methyl cyclohexane 108-87-2 1,4-difluorobenzene 540-36-3 O-fluoro toluene 95-52-3

14 Further information with regard to these patent filing activities is provided in Section 5.1.2.

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 43 Table 4-7: Solvents for which experimental laboratory work was undertaken Substance CAS No Substance CAS No 1,5-dichloropentane 628-76-2 Perfluorohexane 355-42-0 1,6-dichlorohexane 2163-00-0 Tetrachloroethane 79-34-5 1-chloro 4-fluorobenzene 352-33-0 Toluene 108-88-3 2-bromobutane 78-76-2 Trichlorobenzene 120-82-1 2-fluoro, 1,3 dimethylbenzene 443-88-9 Xylene 1330-20-7

As detailed in Section 2.6, stability, recyclability and final SAC ER quality characteristics form critical technical feasibility criteria for the replacement of EDC. Failure to meet one of these criteria would automatically exclude a potential alternative substance from further consideration. The operational sulphonation conditions can be described as follows:

 The benchmark copolymer (10% cross-linked PS-DVB), sulphuric acid (98%) and solvent are charged into a reactor  The mixture is maintained for 1 hour at 30 ˚C and a heating ramp is then applied to arrive to the sulphonation condition (i.e. 130 ˚C)  Distillation is obtained for solvents that are stable and recoverable and the volume collected to estimate the %-recovery for each case  The sulphonation process proceeds for 2-4 hours at the hold temperature and the temperature is then lowered to 80 ˚C. At this temperature, the acid concentration is then diminished by adding acid of variable (lower) concentrations (followed by water to achieve a final pH level of in the effluent from the process  The resin is then measured with regard to the final volume obtained and its various quality parameters are recorded (including volume exchange capacity, moisture holding capacity, weight exchange capacity, particle size, perfect beads and whole beads).

The direct and read-across results of this screening step have been summarised in Table 4-8, below. This table contains the details for all 98 substances that passed the initial swelling screening stage (and values for EDC, as the benchmark), and has been organised based on solvent grouping, with individual substances in each group also ranked by RED value.

In some instances, results from this step demonstrated that whole groups of compounds could be dismissed from further consideration due to their unfavourable process related characteristics in the sulphonation reaction. For example, it was found that oxygenated solvents would decompose under the highly acidic reaction concentrations.

As a result of this screening step, 93 of the 98 potential alternative substances were excluded from further consideration. These substances failed at least one critical technical parameter. Five substances; DCM, 1,1,2-trichloroethane and three trifluorobenzene isomers (1,2,3-trifluorobenzene, 1,2,4-trifluorobenzene and 1,3,5-trifluorobenzene) progressed to the final screening step.

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 44 Table 4-8: Results of screening step 3 Solvent CAS number Solvent Swelling Is the substance Solvent recyclability Does sulphuric Is SAC ER quality group* ( RED stable in hot (decomposition or acid remain adequate? value) sulphuric acid? too high boiling recyclable in point)? the process? 1,2-dichloroethane (EDC) 107-06-2 1 0.53 Yes Yes Yes Yes BENCHMARK Bromotrichloromethane 75-62-7 1 0.13 No Unknown No Not adequate Iodo methane 74-88-4 1 0.25 No No No Not adequate Dichloromethane (DCM) 75-09-2 1 0.39 Yes Yes Yes Yes Di(2-chloroisopropyl) ether NA 1 0.41 No No No Not adequate Epichlorohydrin 106-89-8 1 0.42 No No No Not adequate Dibromomethane 74-95-3 1 0.46 No information No information No Not adequate available available 1,4-dichlorobutane 110-56-5 1 0.61 No (elimination Partial recovery No Not adequate reaction) 1,2,4-trifluorobenzene 367-23-7 1 0.6 Yes Yes Yes To be decided - resin cleanliness an issue 1,2,3-trifluorobenzene 1489-53-8 1 0.61 Yes Yes Yes To be decided - resin cleanliness an issue 1,1,2-trichloroethane 79-00-5 1 0.63 Yes Yes Yes Yes 1,3,5-trifluorobenzene 372-38-3 1 0.66 Yes Yes Yes To be decided - resin cleanliness an issue Cis-1,2-dichloroethylene 156-59-2 1 0.67 No No No Not adequate 1,2-dichloropropane 78-87-5 1 0.68 Partial stability Partial recovery. Tar No Yes (elimination formation with reaction) sulphonation 1,1-dibromomethane 74-95-3 1 0.69 No No No Not adequate 1,6-dichlorohexane 2163-00-0 1 0.69 No No No Not adequate 1,1,2,2-tetrachloroethane (r-130) 79-34-5 1 0.70 Yes Yes No Yes 1,5-dichloropentane 628-76-2 1 0.71 No (elimination No No Yes reaction) 1-bromopropane 106-94-5 1 0.71 No No No Not adequate Telone (1,3-dichloropropene) 542-75-6 1 0.72 No No No Not adequate Benzyl chloride 100-44-7 1 0.73 No No No Not adequate

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 45 Table 4-8: Results of screening step 3 Solvent CAS number Solvent Swelling Is the substance Solvent recyclability Does sulphuric Is SAC ER quality group* ( RED stable in hot (decomposition or acid remain adequate? value) sulphuric acid? too high boiling recyclable in point)? the process? Bromochloromethane 74-97-5 1 0.73 Unknown Unknown No Not adequate O-dichlorobenzene 1219803-83- 1 0.78 No (aromatic No No Not adequate 4 sulphonation) 2-bromobutane 78-76-2 1 0.78 No No No Not adequate 2,2,3-trichlorobiphenyl NA 1 0.82 No No No Not adequate 2-bromopropane 75-26-3 1 0.84 Unlikely Unknown No Not adequate 1,2,4-dichloro-3-fluoronitrobenzene NA 1 0.85 Yes No. (Tb too high) No Not adequate 1,1-dichloroethane (r-150a) 75-34-3 1 0.85 Yes Yes No Not adequate 1,3-dichloro-2-fluorobenzene 2268-05-5 1 0.86 Yes No No Not adequate Methylene diiodide 75-11-6 1 0.88 No No No Not adequate 2,4-dichloro-5-nitrobenzotrifluoride 400-70-4 1 0.88 Yes No No Not adequate Allyl chloride 107-05-1 1 0.91 No No No Not adequate Ethyl bromide 74-96-4 1 0.95 Unknown No No Not adequate (elimination reaction may occur) Cyclohexyl chloride 542-18-7 1 0.98 No (elimination No No Not adequate reaction) O-difluorobenzene 367-11-3 1 0.99 Yes Yes No Not adequate Ethyl cinnamate 103-36-6 2 0.35 No No No Not adequate Di-n-butyl phthalate 84-74-2 2 0.35 No No No Not adequate Bis(2-chloroethyl) ether 111-44-4 2 0.37 No No No Not adequate Cyclohexanone 108-93-0 2 0.40 No No No Not adequate Cresol glycidyl ether 2210-79-9 2 0.40 No No No Not adequate Ethylene glycol n-butyl ether NA 2 0.44 No No No Not adequate benzoate 2-methyl cyclohexanone 583-60-8 2 0.44 No No No Not adequate 1,4-cyclohexanediol diglycidyl ether 16850-39-8 2 0.47 No No No Not adequate Methyl benzoate 93-58-3 2 0.48 No No No Not adequate

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 46 Table 4-8: Results of screening step 3 Solvent CAS number Solvent Swelling Is the substance Solvent recyclability Does sulphuric Is SAC ER quality group* ( RED stable in hot (decomposition or acid remain adequate? value) sulphuric acid? too high boiling recyclable in point)? the process? Dicyclohexyl phthalate NA 2 0.52 No No No Not adequate 1,4-butanediol diglycidyl ether 2425-79-8 2 0.55 No No No Not adequate Ethyl benzoate 93-89-0 2 0.57 No No No Not adequate Diethyl succinate 123-25-1 2 0.58 No No No Not adequate Benzaldehyde 100-52-7 2 0.58 No No No Not adequate Cyclooctanone 502-49-8 2 0.59 No No No Not adequate Di-n-hexyl phthalate 1015854-55- 2 0.62 No No No Not adequate 3 1,6-hexanediol diglycidyl ether 16096-31-4 2 0.63 No No No Not adequate Dimethyl phthalate 131-11-3 2 0.63 No No No Not adequate Cycloheptanone 502-42-1 2 0.66 No No No Not adequate Isophorone 78-59-1 2 0.71 No No No Not adequate Cyclobutanone 1191-95-3 2 0.71 No No No Not adequate Cyclopentanol 96-41-3 2 0.71 No No No Not adequate 1,3,5-trioxane 110-88-3 2 0.71 No No No Not adequate Glycidyl methacrylate 106-91-2 2 0.73 No No No Not adequate Acetophenone (methylphenyl ketone) 98-86-2 2 0.77 No No No Not adequate Tetrahydropyran 142-68-7 2 0.78 No No No Not adequate Cyclopropyl methyl ketone 765-43-5 2 0.80 No No No Not adequate 2-methoxy-2-phenylpropane 935-67-1 2 0.80 No No No Not adequate Cyclopentanone 120-92-3 2 0.81 No No No Not adequate Mesityl oxide (4-methyl-3-penten-2- 141-79-7 2 0.81 No No No Not adequate one) Butoxybenzene (butyl phenyl ether) 1126-79-0 2 0.81 No No No Not adequate 1,3-dioxolane 646-06-0 2 0.82 No No No Not adequate 1,2-butylene oxide 106-88-7 2 0.83 No No No Not adequate Dioctyl phthalate 117-81-7 2 0.83 No No No Not adequate Anisole (methylphenyl ether) 100-66-3 2 0.86 No No No Not adequate Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 47 Table 4-8: Results of screening step 3 Solvent CAS number Solvent Swelling Is the substance Solvent recyclability Does sulphuric Is SAC ER quality group* ( RED stable in hot (decomposition or acid remain adequate? value) sulphuric acid? too high boiling recyclable in point)? the process? Tributyl phosphate 126-73-8 2 0.86 No No No Not adequate Tetrahydrofuran 109-99-9 2 0.87 No No No Not adequate Vinyl acetate 108-05-4 2 0.87 No No No Not adequate Methyl n-propyl ketone 107-87-9 2 0.88 No No No Not adequate Methyl ethyl ketone 78-93-3 2 0.88 No No No Not adequate Diisononyl phthalate 28553-12-0 2 0.89 No No No Not adequate Benzoic acid 65-85-0 2 0.90 No No No Not adequate N-butyl benzyl phthalate 85-68-7 2 0.93 No No No Not adequate N-methyl-2-pyrrolidone 2687-44-7 2 0.94 No No No Not adequate Methyl -3-methoxypropionate 3852-09-3 2 0.95 No No No Not adequate Diisodecyl phthalate 26761-40-0 2 0.96 No No No Not adequate Diethyl ketone 96-22-0 2 0.96 No No No Not adequate Methyl n-amyl ketone 110-43-0 2 0.97 No No No Not adequate Ethoxybenzene (ethyl phenyl ether) 103-73-1 2 0.98 No No No Not adequate Methyl methacrylate 80-62-6 2 0.99 No No No Not adequate Tricresyl phosphate 1330-78-5 2 0.99 No No No Not adequate Toluene 108-88-3 3 0.78 No (aromatic No No Not adequate sulphonation) Dimethyl disulfide 624-92-0 4 0.36 No No No Not adequate Dimethyl sulfide 75-18-3 4 0.96 No No No Not adequate Pyridine 110-86-1 5 0.43 Yes No No Not adequate Toluene diisocyanate 26471-62-5 5 0.53 No No No Not adequate Pyrrole 109-97-7 5 0.55 No No No Not adequate Benzonitrile 100-47-0 5 0.59 No No No Not adequate Quinoline 91-22-5 5 0.73 No No No Not adequate Tetraethy urea NA 5 0.73 No No No Not adequate Nitrobenzene 98-95-3 5 0.88 No No No Not adequate

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 48 Table 4-8: Results of screening step 3 Solvent CAS number Solvent Swelling Is the substance Solvent recyclability Does sulphuric Is SAC ER quality group* ( RED stable in hot (decomposition or acid remain adequate? value) sulphuric acid? too high boiling recyclable in point)? the process? P-nitrotoluene 99-99-0 5 0.98 No No No Not adequate N,n-dimethyl propionamide 758-96-3 5 1.00 No No No Not adequate Allyl isocyanate 1476-23-9 5 1.00 No No No Not adequate *1= Halogenated, 2 = Oxygenated, 3= Aromatics, 4= Thiol, 5 = Nitro, Nitrogen containing

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 49 Screening step 4: Preliminary hazard assessment

Based on the outcome of preliminary feasibility considerations in screening steps 1-3, a list of five potential alternative substances (DCM, 1,1,2-trichloroethane, 1,2,3-trifluorobenzene, 1,2,4- trifluorobenzene and 1,3,5-trifluorobenzene) was identified. The purpose of this screening step was to assess the intrinsic hazard properties of these substances and to identify and deselect those which have critical hazard properties (e.g. CMR properties) that would render them unsuitable as potential substitutes for EDC. The following information was retrieved:

 Registration status (which is also a first indication of market availability)  CLP hazard classification  Any other relevant information on SVHC properties (e.g. existing restrictions, evaluations of carcinogenicity by other organisations (e.g. IARC), evidence for endocrine disrupting activity).

To this end, ECHA’s website15 was consulted and the respective substances were searched by CAS number, with information on the registration status as well as the classifications retrieved. Also, any information on other REACH-related activities (e.g. listing as a SVHC and information on restriction/authorisation status) was obtained and evaluated with regard to potential consequences associated with using the substance as alternative to EDC.

Furthermore, eChemPortal16 was consulted to check any involvement in other regulatory programmes and existing evaluations (e.g. OECD SIDS reports, US HPVIS, EU Risk Assessment Reports). Relevant findings are documented in the Table 4-9 below.

Table 4-9: Preliminary hazard screening of potential alternative substances Substance CAS No. Registration Classification * Comments Conclusion status DCM 75-09-2 Full Carc. 2 H351 Annex XVII: Eligible, but registration, STOT Single Exp. 3 restricted considerations of >1000 H336, regarding use in potential tonnes/y Skin Irrit. 2 H315 paint strippers carcinogenicity Eye Irrit. 2 H319 IARC (Vol 110, require detailed 2014): Group 2A evaluation (probably carcinogen to humans) 1,1,2- 79-00-5 Intermediate Carc. 2 H351 Annex XVII: Suspected trichloroeth use only Acute Tox. 4 H302 restricted carcinogen, but ane Acute Tox. 4 H312 regarding supply equivocal Acute Tox. 4 H332 to the general evidence (negative public and/or for in genotoxicity diffusive tests in vivo) applications such Potentially eligible as in surface if other strong cleaning and arguments in cleaning of fabrics favour of the IARC (Vol 71, substance 1999): Group 3 1,2,3- 1489-53- Preregistered Flam. Liq. 2 H225 Few data available trifluoroben 8 only Skin Irrit. 2 H315 for evaluation zene Eye Irrit. 2 H319 STOT SE 3 H335

15 http://echa.europa.eu/search-chemicals 16 http://www.echemportal.org/echemportal/

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 50 Table 4-9: Preliminary hazard screening of potential alternative substances Substance CAS No. Registration Classification * Comments Conclusion status 1,3,5- 372-38-3 Preregistered Flam. Liq. 2 H225 Few data available trifluoroben only Skin Irrit. 2 H315 for evaluation zene Eye Irrit. 2 H319 STOT SE 3 H335 1,2,4- 367-23-7 Preregistered Flam. Liq. 2 H225 Few data available trifluoroben only Skin Irrit. 2 H315 for evaluation zene Eye Irrit. 2 H319 STOT SE 3 H335 *Code for classification column: Bold: Harmonised Classification according to Annex XI of Reg. 1272/2008, normal: Class proposed in registration dossier (joint entry); italics: notified classification only

Based on the results of this screening activity, two substances (DCM and 1,1,2-trichloroethane) can be considered of questionable suitability due to their carcinogen Cat 2 classifications. The applicants have major concerns with regard to the implementation of such alternatives from a long term sustainability and regulatory risk perspective. Furthermore, on a more practical level, they would also be highly unlikely to receive Dow corporate level approval and capital funding for the execution of projects associated with their implementation.

Despite these issues, for completeness of the AoA it was decided that the most technically promising of the two substances would proceed to Section 5 and be subject to more detailed analysis. DCM was chosen for this assessment as it has already been proven on a commercial scale ''''''''''''''''' '''' ''''''''''''' ''''''#A'' '''''''''''''' '''''''''''''' '''''' '''''''.

Current research by Dow - consideration of potential alternative techniques

The ECHA guidance on REACH Authorisation (ECHA, 2011) states that: “a technical alternative could be a physical means of achieving the same function of the Annex XIV substance or perhaps changes in production, process or product that removes the need for the Annex XIV substance function altogether”.

Taking this into consideration, alternative techniques in the context of the applicants’ use of EDC essentially include the development and/or implementation of an alternative synthetic route and/or process that would allow the production of the desired SAC ERs without reliance on EDC.

In this instance, the alternative technique ‘solventless sulphonation’ has been identified and is of clear significance. In reality, ‘solventless sulphonation’ refers to a range of possible implementations of a technique. This means that this alternative can be carried out in a variety of different ways by altering the process parameters and conditions. As highlighted in the discussion of past R&D, Dow has successfully managed to implement a solventless technique to produce a lower-end (lower value), niche SAC ER product at their Chauny facility.

When compared to the EDC based process, the solventless technique essentially involves the removal of the swelling solvent and the modification of processing parameters (temperature and sulphuric acid concentration), in order to increase the rate of sulphonation while controlling the side reaction of sulphone bridging to minimise reaction time while maximising bead quality, to the extent possible.

Relevant patents on the technique filed by the applicant have been identified in Table 4-1 whereas Table 4-10 identifies additional patents available in open literature. Much of the information in the

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 51 patents presents solventless sulphonation as a promising potential alternative technique and it is for this reason that a detailed assessment is provided in Section 5.3.

One obvious point to highlight is given that Dow has focused some of its past R&D on this area, and has experience of the implementation of the process, if solventless sulphonation was a technically and economically feasible alternative to EDC based SAC ER production there would be little incentive for the applicants to apply for the authorisation of the continued use of EDC.

Based on the patent literature by the applicant and others, the main process differences in the use of EDC and the solventless techniques are related to reaction time and temperature:

 Reaction time: Longer reaction times are required for solventless techniques in order to achieve comparable degree of sulphonation (Bachmann, Feistel, Seidel, Siekiera, & Karl-Heinz, 2001). The reaction time is of course related to reaction temperature  Reaction temperature: Higher temperatures are claimed to be required for solventless techniques in comparison to processes employing EDC (Bachmann, Feistel, Seidel, Siekiera, & Karl-Heinz, 2001). The solventless techniques require temperatures above the glass transition

temperature (Tg) of the beads for sulphonation to occur (Dow, 2006). The Tg can be expected to be dependent on the degree of cross-linking within the polymer, with higher degrees of cross- linking requiring higher temperatures. This would result in longer heating and cooling ramps to reach the desired temperature. This would further slow the process cycle time.

Taking into account the above observations and process knowledge held by the applicants, the assessment of solventless sulphonation will demonstrate that attempts to implement this alternative further would be technically and economically infeasible and place Dow’s Chauny and Fombio facilities at a severe competitive disadvantage vis-à-vis their non-EU competitors.

Given t

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 52 Table 4-10: Examples of solventless sulphonation in the open patent literature Patent number Title Applicant Abstract Notes and example conditions (year of publication) Copolymerizing divinylbenzene US6228896 Iab The invention relates to a process for the preparation of Produced EDC comparable 7.8% and styrene, sulfonating with B1 (2001) Ionennausta mechanically and osmotically stable, high-capacity strongly acidic cross-linked beads: concentrated sulfuric acid uscher cation exchangers having a particle size of ≥0.1 mm by sulphonation Temperature: 105-130 °C using without addition of inert Gmbh of gel-like or porous bead polymers with sulphuric acid without the EDC; 135-165 °C without. chlorine-containing swelling Bitterfeld use of inert chlorine-containing swelling agents and/or of co- Reaction times: 6 hours using agents monomers based on acrylonitrile. According to the invention, such EDC; 10 hours without. strongly acidic cation exchangers can be prepared by sulphonation 1-2% broken beads of gel-like and porous bead polymers, prepared by copolymerization of styrene and divinylbenzene having a cross-linker content of up to 65% by weight of divinylbenzene with and without inert composition, with 80-96% strength sulphuric acid at temperatures of 125-180 °C and a reaction time of up to 20 h. According to the novel process, SAC exchangers can be prepared without the use EDC, with quality features and material characteristics identical or similar to products produced by the conventional processes Sulphonation process US20020022 Klipper et al The invention relates to a process for preparing strongly acidic Acrylic ester resin beads rather 671 A1 macroporous or strongly acidic monodisperse-gel-type ion than divinylbenzene/styrene (2002) exchangers, particularly macroporous monodisperse, macroporous resins heterodisperse, or monodisperse-gel-type cation exchangers, by treating the respective basis polymer with sulphuric acid in stepwise cycles at graded concentrations. The invention further relates to the cation exchangers prepared by this process and to their uses Sulfonating a (meth)acrylic ester- US20040006 Dimotsis et The invention relates to a process for preparing gel-type cation Acrylic ester resin beads rather containing cross-linked bead 145 A1 al exchangers of high stability by sulphonation of cross-linked than divinylbenzene/styrene polymer in the absence of (2004) (meth)acrylic ester-containing bead polymers with sulphuric acid resins swelling agent using a sulfuric having a concentration of 90 to 95% in the absence of a swelling acid, wherein the temperature agent during the sulphonation is increased by the heat of reaction and/or heat of dilution

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 53

4.2.2 Conclusion

Dow has followed a detailed, stepwise and logical approach to screen 614 potential alternative substances for EDC (considering a wider pool of more than 1000 substances). The initial list was identified with Dow utilising their in-house R&D software (ChemComp(tm)) in combination with an in depth review of the available scientific and technical literature. In a laboratory validated process, the 614 substances underwent screening based on the modelling (or measurement) of their PS-DVB copolymer swelling properties. 516 potential alternative substances (those with RED values >1) were dismissed from further consideration, based on technical and economic feasibility grounds. A subsequent screen, replicating sulphonation process conditions was then undertaken. This was carried out on a subset of the remaining 98 alternatives (with representative substances for the range of the chemical groups being considered). Based on the laboratory results as well as interpretation and review by Dow R&D experts, 93 of the 98 potential alternative substances were excluded from further consideration. These substances failed at least one critical performance parameter and were found to be either non-stable and / or non-recyclable in the sulphonation process. This left five substances; DCM, 1,1,2-trichloroethane and three trifluorobenzene isomers (1,2,3-trifluorobenzene, 1,2,4-trifluorobenzene and 1,3,5-trifluorobenzene) to be considered further.

As part of the sulphonation screen, Dow was able to conclude that DCM has very good technical characteristics. This is perhaps unsurprising as the substance has been used on a commercial scale in the production of SAC ERs. For 1,1,2-trichloroethane, the substance also passed initial technical feasibility considerations. With regard to the trifluorobenzene isomers, despite passing stability and recyclability parameters, some uncertainty remained about the quality of the SAC ERs that could be obtained from the process. To conclude the screening, a preliminary hazard assessment of the remaining substances was undertaken with information retrieved on registration status, EU hazard classification and any other relevant information on SVHC properties (e.g. existing restrictions, evaluations of carcinogenicity by other organisations (e.g. IARC), evidence for endocrine disrupting activity). The eChemPortal17 was also consulted to check any involvement in other regulatory programmes and existing evaluations (e.g. OECD SIDS reports, US HPVIS, EU Risk Assessment Reports).

DCM and 1,1,2-trichloroethane were found to have questionable hazard properties from a longer term sustainability and regulatory risk perspective. Given major concerns surrounding the implementation of such potential alternatives, it was decided that only one of the two substances (DCM) would be shortlisted and given further consideration in Section 5 of the AoA. For the trifluorobenzene isomers, insufficient data were available to make this initial evaluation, and consequently none could be excluded on hazard property grounds. However, given the similar nature of the substances, Dow concluded to undertake further tests only on the most promising isomer (1,2,4-trifluorobenzene). This substance had the lowest RED value of the isomers and would serve as a representative substance for the group (i.e. if it was demonstrated that the substance was not a feasible option, results could be read-across for the ‘1,2,3-’ and ‘1,3,5-’ isomers). Another factor in the applicants’ decision to progress with one trifluorobenzene isomer was due to the availability of the substance in sufficient volumes to allow extensive testing (and potential pilot scale tests) to take place – for the ‘1,2,3-’ and ‘1,3,5-’ trifluorobenzene isomers, this was not a possibility.

With regard to alternative techniques, given that Dow is currently implementing the process of solventless sulphonation and a variety of promising claims on the process are available in the scientific and technical literature, this potential alternative is also assessed in Section 5.

17 See: http://www.echemportal.org/echemportal/

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 54

5 Suitability and availability of possible alternatives

5.1 Alternative 1: 1,2,4-Trifluorobenzene

5.1.1 Substance ID and properties

Name and other identifiers of the substance

The following table presents the identity of 1,2,4-trifluorobenzene.

Table 5-1: Identity of 1,2,4-trifluorobenzene Parameter Value Source EC number 206-684-9 1 EC name 1,2,4-trifluorobenzene 1 CAS number 367-23-7 1 IUPAC name 1,2,4-trifluorobenzene 3 1,2,4-Trifluorbenzol Other names 3 Benzene, 1,2,4-trifluoro-

Molecular formula C6H3F3 2 SMILES notation C1=CC(=C(C=C1F)F)F 3 Molecular weight 132.08 3

Molecular structure 3

Sources (accessed on 29 August 2014): 1. European Chemicals Agency: http://echa.europa.eu/ 2. European Inventory of Existing Commercial chemical Substances (EINECS): http://esis.jrc.ec.europa.eu/ 3. Chemspider: http://www.chemspider.com/

Physicochemical properties

The following table presents the key physicochemical properties of 1,2,4-trifluorobenzene.

Table 5-2: Physicochemical properties of 1,2,4-trifluorobenzene Property Value Remarks Source Physical state at 20 °C and Colourless Liquid 1 101.3 kPa Melting/freezing point -63.15°C USEPA EPISuite estimate 3 88 - 91 °C at 760.00mm Boiling point 2 Hg Density 1.264 g/mL at 25 °C 1 Vapour pressure 57.4 at 25 °C USEPA EPISuite estimate 3 Generated using ACD/Labs’ Surface tension 25.2±3.0 dyne/cm 3 ACD/PhysChem Suite Water solubility 1483.2 mg/L USEPA EPISuite estimate 3 Partition coefficient log Kow is 2.52 USEPA EPISuite estimate 3 Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 55

Table 5-2: Physicochemical properties of 1,2,4-trifluorobenzene Property Value Remarks Source Flash point 4 °C 1 Flammability No data - Explosive properties No data - Self-ignition temperature No data - Oxidising properties No data - Granulometry Not relevant - Sources (accessed on 08 April 2015): 1. Pfaltz & Bauer: https://www.pfaltzandbauer.com/MSDS/T22845%20%20MSDS16%20%20051711.PDF 2. Acros Organics: https://www.fishersci.ca/viewmsds.do?catNo=AC188420050 3. Chemspider: http://www.chemspider.com/

5.1.2 Technical feasibility

Introduction

A number of steps are taken here for the assessment of the technical feasibility of 1,2,4- trifluorobenzene. These include:

 Step 1: Comparison of 1,2,4-trifluorobenzene to EDC against the technical feasibility criteria. A detailed explanation of the technical shortcomings/differences to the EDC-based SAC ER production process is provided  Step 2: Description of practical steps required for the implementation of the alternative. An analysis is given of the R&D, engineering and process modifications required for the conversion of the applicants’ Chauny and Fombio plants to the alternative substance and a timeframe for such implementation is provided.

Comparison of 1,2,4-trifluorobenzene to EDC against key technical performance criteria

The use of 1,2,4-trifluorobenzene as a potential alternative for EDC was proposed due to the substance’s initially promising characteristics, as identified during the screening exercise (see Section 4.2). As a result of these characteristics, in Q2 2014, the applicants began the implementation of a detailed R&D plan (alongside the latter stages of the screening phase) to assess whether the substance could be considered a fully technically feasible option for the replacement of EDC. The following practical steps were taken:

1. An additional R&D search for structurally analogous solvents to trifluorobenzene was undertaken (see Table 4-7 and its preceding discussion) 2. A thorough prior art search was carried out with 1,2,4-trifluorobenzene in the context of the sulphonation process - Initial patent writing activities took place (involving the services of a patent lawyer over 2 weeks) - Additional assessments were made by an intellectual capital manager (over 2 weeks) - A provisional patent was filed (International Publication Number WO 2015/160562 A1). 3. Literature search results were analysed and conclusions were formed 4. Solvents were obtained for laboratory analysis 5. Sulphonation work at the applicants’ laboratories was undertaken 6. Final SAC ER properties were characterised 7. Estimations of HSP for new solvents were derived (based on computational chemistry)

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 56

8. Samples were shipped to Dow’s Midland R&D facility in the USA for further analysis 9. A methodology to quantify residual fluorine in the final SAC ER products was developed18.

The search carried out for analogous solvents was undertaken in order to understand the limits of halogenated aromatics with good swelling characteristics, as well as resins with measurable properties close to the objectives of the work. This work did not identify a solvent with superior characteristics to 1,2,4-trifluorobenzene and thus the assessment continued to concentrate on this substance. In line with the results obtained from the R&D undertaken by the applicants, Table 5-3 presents a comparison of 1,2,4-trifluorobenzene’s performance against the detailed list of technical comparison criteria, identified in Section 2.6.

As can be seen, there are a number of criteria that the substance cannot fulfil. Most pertinent is the presence of undesirable levels of residual fluorine (identified at 100 ppm) in the final SAC ER products, which would lead to a quality level that would not be accepted by many customers (e.g. those requiring nutritional or nuclear grade resin certifications). Removal of residual fluorine was attempted via hot water washing over several hours, ''''''''''#A'''''''' solvent washing, and steam treatment without success.

The applicants concluded that the levels of residuals within the final products would be a ‘show stopper’ with regard to the uptake of the potential alternative, and following this discovery the R&D plan for the substance was halted. Other methods of removing the residuals would include the use of organic solvents and would be counterproductive, rendering the process uneconomical, whilst also generating a solvent containing fluorinated hydrocarbon which would itself result in a significant waste issue and the requirement of additional (unsustainable) capital projects. The applicants also judged the likelihood of additional and proportional R&D activities overcoming the technical barriers as very low - any technology that can remove the residual fluorine from the resins would be highly likely to result in longer manufacturing cycle times, significantly increasing overall operating costs and decreasing SAC ER production capacity.

Another significant issue with the presence of residual fluorides concerns the potential for damage to the applicants’ own processing equipment. This issue has been consulted on with internal Dow corrosion and glass-lined equipment subject matter experts. The following points can be highlighted:

 The use of 1,2,4-trifluorobenzene or a similar fluorinated compound will likely generate low levels of free fluoride ions either entering the system as trace level contaminants or as by- products of trifluorobenzene decomposition at elevated temperature. Under the applicants’ acidic process conditions, any free fluoride would be converted to hydrogen fluoride. This would lead to corrosion of glass lined sulphonation reactors used by the applicants.

 The topic of trace levels of hydrogen fluoride in sulphuric acid has been further discussed with technical support groups at both Pfaudler and De Dietrich, major suppliers of glass-lined equipment. Both companies have confirmed that there is no safe threshold level for hydrogen fluoride that is acceptable for glass-lined equipment. In the presence of even trace levels of hydrogen fluoride, reduced service life of such equipment is inevitable.

 With the implementation of 1,2,4-trifluorobenzene, establishing an accurate prediction of production vessel reliability and service life would be unworkable. Once the glass-lining of a

18 Standard analytical methods such as X-ray fluorescence, inductively coupled plasma mass spectrometry, and atomic absorption spectroscopy will not work for the quantification of fluorine, as it is a molecule that is not easy to ionise.

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 57

sulphonation reactor is compromised, extensive damage to the steel substrate may ensue and lead to a possible loss of primary containment. Such a scenario would be wholly unacceptable.

Based on these issues, the professional opinion of Dow’s corrosion and glass-lined subject matter experts is that 1,2,4-trifluorobenzene (or any similar fluorinated compound) cannot not be considered as a practical alternative for replacing EDC when the sulphonation process entails the use of a glass-lined reactor susceptible to corrosion and loss of integrity in service. Consideration to the cost and technical implications of replacing the existing reactors has been considered unwarranted given the technical feasibility shortcomings of the alternative and the uncertainties over the achievable risk reduction associated with 1,2,4-trifluorobenzene.

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 58

Table 5-3: Comparison of 1,2,4-trifluorobenzene to EDC according to technical feasibility criteria Criteria Threshold or acceptable range for Values for 1,2,4-trifluorobenzene (comparison and comments) Conclusion replacing EDC Copolymer swelling efficiency At least 40% vs. initial dry PS-DVB 63% swelling achieved Acceptable copolymer Chemical stability Stable in >94% sulphuric acid Stability as measured by solvent % recovery is comparable to EDC on Unacceptable the laboratory scale. However, there is a significant risk of hydrogen fluoride generation is the applicants’ glass lined process equipment (sulphonation reactors). This is unacceptable Thermal stability Stable at temperatures of 25 – 140 °C Recovery in laboratory scale sulphonation reactions at 140°C is Unacceptable comparable to EDC. However, there is a significant risk of hydrogen fluoride generation is the applicants’ glass lined process equipment (sulphonation reactors). This is unacceptable Solvent recyclability >95% recyclability Recyclability similar to EDC on the laboratory scale Initial results acceptable but additional R&D work would be required to fully assess Separation from water Separation of solvent / water in a tank The MSDS reports the substance to be insoluble in water. Additional Acceptable and re-use options laboratory testing has confirmed the substance is not miscible in water and will phase separate from water in mixture Separation from sulphuric Separation (recycling) from sulphuric Not determined at this time Unknown acid acid must be achievable in the process Freezing point < -20 °C -63°C (see Table 5-2) Acceptable Residuals in final polymer The alternative needs to meet specific Laboratory testing has shown 100 ppm of fluorine in final resin after Unacceptable product application and/or regulatory extensive hot water, solvent and steam treatments. This level of requirements residual impurity is unacceptable and could cause corrosion issues for downstream users’ equipment Sulphonation yield At minimum the alternative should Comparable yield to EDC achieved for copolymer cross-linking levels of Acceptable achieve the same ion exchange yield 2%, 7%, 10% and 16% DVB for every grade of SAC ER as compared to the EDC bases process

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 59

Table 5-3: Comparison of 1,2,4-trifluorobenzene to EDC according to technical feasibility criteria Criteria Threshold or acceptable range for Values for 1,2,4-trifluorobenzene (comparison and comments) Conclusion replacing EDC Cycle time Similar to current performance to Same sulphonation time in laboratory work delivered typical routine Unacceptable remain competitive for every resin properties, when compared to EDC runs. grade However, if implemented as an alternative residual fluorine would need to be removed. This would require the development of a post- treatment cycle time which would result in significantly longer manufacturing cycle times, decreasing SAC ER production capacity and efficiency Final SAC ER quality At minimum the specifications to be Quality in terms of perfect beads, volume capacity, moisture retention Unacceptable aligned with market needs capacity and weight capacity are comparable to EDC. However, levels of solvent residuals in the final products are unacceptable and can be considered a ‘show stopper’ Environmental regulations Comply with local plant discharge Not determined at this time Unknown regulations at both plant locations

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 60

Required steps to make 1,2,4-trifluorobenzene a technically feasible alternative to EDC

As highlighted above, the applicant does not consider 1,2,4-trifluorobenzene to be a technically feasible alternative to EDC, due primarily to the unacceptable levels of residual fluorine present in the final SAC ERs when this substance is used and the potential risk of significant corrosion issues at the Chauny and Fombio plants, as well as to waste acid re-processors and customer’s equipment.

As a result of this conclusion, the applicants cannot provide a realistic overview of steps that would allow 1,2,4-trifluorobenzene to be implemented as a technically feasible alternative to EDC. However, before it was discovered that the substance was not a viable option, a provisional timeframe of the theoretical steps to implement 1,2,4-trifluorobenzene as an alternative to EDC had been formulated by the applicants. This original analysis is provided in the table below, and is presented with the clear caveat that the timeframe and steps are associated with a process that assumes levels of residual fluorine in the final products would not have been identified as a critical issue.

Table 5-4: Theoretical steps to allow 1,2,4-trifluorobenzene as an alternative to EDC Duration of each Notes Step step (and total duration) 1. R&D work 36 months Screening in laboratory - copolymer swelling efficiency, SAC ER quality (first series of parameters: exchange capacity, moisture holding capacity, perfect beads), recyclability, waste acid reprocessing, environmental (air and water emissions), materials of construction compatibility. SAC ER quality (second series of parameters: Residual impurity profile, mechanical stability (compression, osmotic shock attrition) 2. Modification of process 36 months Define and demonstrate full process conditions (usage, parameters reaction conditions, solvent removal, recovery and recyclability for solvent and acid streams, product post treatment, environmental controls) across entire SAC ER product lines impacted 3. Engineering work 24 months (from Full scale process scope definition, capital project execution, complete process start up and commissioning plan for raw material handling, definition) production and waste treatment / environmental (air emissions) 4. Full recertification and 18 months Can only take place once substance has been fully requalification implemented within the applicants’ plants. This is the minimum timeframe required (see additional discussion in following section) Theoretical total 90 months Assuming full customer acceptance timeframe to implement* *Note: The total duration accounts for overlaps between phases of engineering work and process parameter modifications

Conclusion of technical feasibility of 1,2,4-trifluorobenzene as an alternative to EDC

Based on the applicant’s original R&D plan (which began in Q2 2014) 1,2,4-trifluorobenzene had the potential to become a technically feasible alternative for EDC by Q4 2021. However, during early phases of the plan’s implementation, the applicants discovered that the use of the substance resulted in unsatisfactory levels of residual fluorine in final SAC ER products.

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 61

Experts within the applicants’ R&D team have concluded that success in removing residual fluorine whilst maintaining a viable process would be very unlikely to materialise. Consequently, R&D activities associated with the substance ceased and it has been concluded to be a technically infeasible option to implement as an alternative for EDC. This conclusion was further validated by internal subject matter experts within Dow, who concluded that use of the substance would leave the applicants glass-lined sulphonation reactors susceptible to corrosion and loss of integrity in service.

5.1.3 Economic feasibility

Important note

Economic feasibility for 1,2,4-trifluorobenzene was initially assessed during the primary stages of a comprehensive R&D plan on the potential implementation of the alternative at the applicants’ Chauny and Fombio facilities. During these initial stages, it was assumed that the R&D plan would be successful and that the substance would become a technically feasible option for the replacement of EDC without any major obstacles. As discussed in the previous section (in Q1 2015), Dow’s ongoing testing demonstrated that the substance could not be considered a technically feasible alternative for EDC. Despite this, the applicants have decided to retain the original analysis of economic feasibility, for the benefit of the reader, to provide a theoretical indication of the magnitude of costs associated with the implementation of 1,2,4-trifluorobenzene, if technical feasibility issues could have been overcome

The cost of converting from EDC to 1,2,4-trifluorobenzene needs to consider both investment costs and changes to operating costs.

Investment costs for the implementation of the alternative

There are several key investment costs for switching from EDC to 1,2,4-trifluorobenzene (estimates have been provided based on the knowledge of Dow internal experts):

Access to technology and R&D: Based on the applicant’s initial understanding of what the requirements would have been to overcome technical feasibility hurdles to implement 1,2,4- trifluorobenzene, preliminary R&D investments were estimated to be in the range of €4-8 million.

Plant conversion costs: there are three key steps under this:

 Plant downtime: Significant downtime is expected for customer validation of plant scale products although this cannot be quantified (EDC use would also need to continue during the qualification transition period). Downtime would also have impacts on production levels and associated sales of SAC ERs (this would depend on the quality of products obtainable and customer acceptance). Significant high end business would be at risk if customers rejected process and product modifications  Acquisition of replacement equipment: A precise estimate for the additional new equipment required to be able to store, handle, use, recover and recycle 1,2,4-trifluorobenzene could not be formulated by the applicants and it is also unclear what equipment would be required to produce an acceptable range of products and control all environmental emission sources from process vents and waste water streams. Based on preliminary considerations, a broad estimate for investments is in the range of €4-12 million per site (€8-24 million in total). The lifetime of new equipment is also uncertain and significant concerns exist with regard to free fluoride generation potentially creating catastrophic equipment corrosion

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 62

 Cost of installing new equipment (engineering cost): The applicants have included engineering costs in the above total estimation of €8-24 million. A separate and more precise estimate cannot not be provided.

Recertification and requalification19: With regard to the recertification requirements associated with the implementation of 1,2,4-trifluorobenzene, Dow utilised the Decernis ‘gComply’ tool to assess the substance’s current regulatory status (gComply is a global substance database and library of full-regulations covering over 180 countries and 80,000 regulations applicable to food, consumer, and chemical substances and products20). Search results from gComply indicate that 1,2,4- trifluorobenzene is not listed under any relevant ‘positive’ lists for substances certified for use in drinking water applications. This infers that a full toxicological package would be required prior to recertification (estimated at a cost of at least €100,000). Furthermore, the recertification process would only be able to start after 1,2,4-trifluorobenzene was fully implemented within the Chauny and Fombio plants, and would take (at a minimum) an additional 18 months to achieve on top of the theoretical R&D, engineering and process parameter modification actions discussed above. Taking these considerations into account, it is clear that recertification requirements would be a significant economic hindrance to the uptake of the alternative, although no estimate for ‘total costs’ can be provided.

For requalifications, despite their downstream focus, the applicants note that it is highly unlikely that their customers would wish to invest their own time and internal resources to perform the required studies that need to be produced in order to requalify their products, meaning that Dow is likely to be obliged to pay the associated costs, if they wished to remain a customer’s supplier of SAC ERs. As Chauny and Fombio are global product supply points, requalifications are not limited to customers within the EU region and associated costs have the potential to be highly variable. The timeline associated with a full requalification is expected to be in the region of 18 months. Reliable estimates for overall requalification costs associated with the implementation of 1,2,4-trifluorobenzene cannot be provided, but would likely be significant. Furthermore, even if Dow were to fund the necessary requalification programs, it is likely that business would be lost to competing products that can be readily supplied from outside the EU and already have the required qualifications.

An indicative overview of applications that would be particularly affected by recertification and requalification requirements is provided in Table 5-5.

19 Note: In the context of the applicants’ activities, recertification relates to the fulfilment of legal requirements for the use of SAC ERs in specific applications (e.g. drinking water). These requirements can be internal or external and are often implemented at national level. Requirements for requalification share similarities with recertification, although the requalification process is typically focussed more on ensuring that particular industries or downstream users are able to obtain products with particular technical specifications that meet their precise needs. 20 See http://www.decernis.com/products/regulatory-reference/. Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 63

Table 5-5: Indicative assessment of recertification and requalification requirements associated with the implementation of 1,2,4-trifluorobenzene and an alternative to EDC SAC ER end use sector What requirements need to be met? Potable water NSF (see http://www.nsf.org/about-nsf/), WQA (see http://www.wqa.org/) and country specific recertification requirements would need to be met Food contact Requalifications would be required based on e.g. extractables, impurity profiles and total organic carbon levels Power generation in fossil fuel Requalifications would be required based on e.g. extractables, total organic and nuclear power facilities carbon levels and physical stability Semiconductor (ultra-pure Requalifications would be required based on e.g. extractables, total organic water) carbon levels, particle throw, resin performance and physical stability

Retraining: Significant retraining costs would be faced as 1,2,4-trifluorobenzene would be a completely new chemical to introduce at both Chauny and Fombio facilities. Such retraining would be required for the storage, handling, use, recovery, recycling, environmental, health, safety, and regulatory requirements to work. An estimated cost for retraining is not available.

Important note: Investment in capital equipment would be funded via the Dow corporate capital funding process. The project would be required to pass all financial, technical, business, and sustainability justification gates, and be compared to other options up to and including the exit of operations and shutdown of the affected production areas within the EU manufacturing footprint. Based on these considerations, the applicants note that they would not be able to obtain funding for the implementation of 1,2,4- trifluorobenzene. These issues are discussed further in the corresponding SEA document

Changes to operating costs

The following table presents the array of operating cost elements considered by Dow and provides a comparison of the costs arising under EDC and 1,2,4-trifluorobenzene. ''' ''''''''''''' ''''' '''''''''''' '''''''' '''''' ''''''''''''' ''''''' ''''' ''''''''''''''' ''' '''''''''''' ''''#D '''''''' '''''' '''''''''''' ''''''''''''''' '''''''''''''''''''''''''' ''''''''''''' '' '''''''''''''' '''''''''''''''''' ''''' '''''' '''''''''''''''''''''' '''''''''''''''''''''' ''''''' ''''''' ''''''' ''''' '''''''''''' ''''''''''''' '''''''' ''''''''''''''''''' ''''''' '''''''''''''''' ''''''' ''''''''''' '''''''''''''''''''''' ''''''''' ''' ''''''''''''''''''' ''''' ''''''''''''''.

Given that the applicants produce 50 relevant grades of SAC ER, it is not practical to provide a comparison of operating costs for each individual grade. Consequently, %-range estimates have been used to demonstrate how much each cost category contributes to operating costs across the applicants’ EDC-based SAC ER manufacturing activities. Where presented as a monetised value, the overall change in operating costs has been calculated utilising the average per tonne production cost as the benchmark.

Again, it must be emphasised that the comparison here was formulated prior to the applicant’s discovery that 1,2,4-triflurobenzene is technically infeasible due to unacceptable levels of residual fluorine in the final SAC ER products and the risk of significant corrosion issues for the applicants, external waste re-processors and downstream users.

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 64

Table 5-6: Comparison of operating costs for production of SAC ERs between EDC and 1,2,4-trifluorobenzene Operating cost category Contribution to current Effect on cost element if EDC is overall operating cost (%) replaced by 1,2,4-trifluorobenzene Energy costs Electricity '''' #F'''''' Increase (due to longer processing times and additional product washes) Oil or gas (please specify) ''''''#F ''''' Increase (due to longer processing times and additional product washes) Materials and service costs Cost of process solvent (currently EDC) ''''#F ''''' Increase by factor of ca. 100. The applicant estimates this will increase typical final product cost by approximately ''''''''#F '''''''.

The replacement ratio is anticipated to be 1:1 or somewhat higher Raw materials (excluding water and EDC '''''''#F ''''''' Increase but including their delivery costs) Water '''''#F '''' Increase Environmental service costs (e.g. waste ''''''#F '''' Undetermined at this point in time treatment and disposal services) although anticipated to be higher as the compound is fluorinated Transportation of product ''''''#F '''' Same Labour costs Salaries, for workers on the production '''''#F '''''''''' Same line (incl. supervisory roles) Costs of meeting worker health and safety '''''#F ''''' Undetermined at this point requirements (e.g. disposable gloves, masks, etc.) Maintenance and laboratory costs Costs associated with testing, equipment ''#F '''' Increase (anticipate to be higher as downtime for cleaning or maintenance the compound is fluorinated) (incl. maintenance crew costs and lab worker costs) Other costs Marketing, license fees and other ''#F ''' Increase (anticipated to be higher as regulatory compliance activities the compound is fluorinated) Other general overhead costs (e.g. ''#F ''''' Undetermined at this point insurance premiums, administration, etc.) Overall change in operating costs (%) Typical final product cost per tonne will increase by '''''#F '''''' '''''''''#F '''''''''''''''''', based on the increased solvent cost alone. Additional operating cost increases cannot be quantified at this time

Energy: It has been indicated that energy costs would increase due to the requirement for longer processing times and additional product washes.

Materials and services: This is where the main operating cost difference would arise, based on the relative price of 1,2,4-trifluorobenzene in comparison with EDC. As will be discussed in Section 5.1.5, 1,2,4-trifluorobenzene has very limited availability and the substance, when compared with EDC, is

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 65 also very expensive at a price of approximately €55,000t21. Such a high cost is unacceptable and would result in a ''''''''''''' ''''''#F''''''''''' ''''''''' ''''''''''''''. This would raise the applicants’ average per tonne production cost by ''''''''''''#F '''''''''''. It would not be economically feasible for Dow to absorb these costs as a large proportion of the applicants’ SAC ERs (i.e. those for the commoditised water treatment market) are associated with low profit margins. '''''''''''' ''''''' '''''''''''''''' '''''''''' '''''''''' ''''''' ''''''''''''' ''''''''''''''''''''''' '''''''' '''''''''''' '''''''''''' '''' ''''''' '''''' '''''''''''''' ''''''''''' ''''' '''''''''' '''' '''''''''' ''#H ''''''' '''''''''''''''' ''' ''''''''''''' '''' ''''''' '''''''''''''''' ''''' '''''''''''''' '''''''''' '''' ''''''' '''''''''''' '''''''''''''''''''''''''''' ''''''''' ''''''''''''''''' '''''''''' ''''' ''''''''' '' The highly competitive nature of the market also means that if Dow raised their SAC ER prices, competitors would be likely to hold their own prices to capture market share (these issues are discussed further in the corresponding SEA document).

Environmental service costs are also anticipated to increase as the reprocessing of waste sulphuric acid with fluoride impurities may be associated with corrosion issues.

Labour costs: No significant costs changes are likely to arise.

Maintenance costs: Anticipated to be higher than for EDC, as the compound is fluorinated and corrosion issues may ensue.

Other costs: The applicants anticipate that marketing, license fees and other regulatory compliance activities will increase as the substance in question is fluorinated.

Operating costs – additional considerations

Soft benefits: In the following table, the applicants have summarised their expectations in relation to any indirect or ‘soft’ benefits that might arise from the replacement of EDC with 1,2,4- trifluorobenzene. The table confirms that no such benefits are likely to arise.

Table 5-7: Benefits that might arise from substitution of EDC by 1,2,4-trifluorobenzene Likelihood to materialise Indirect monetary benefit with 1,2,4-trifluorbenzene Increased revenue from enhanced company reputation or product image No Entry into new markets No Better creditworthiness No Improved ratings by investment brokers and agencies No Reduced insurance premiums No Likelihood to materialise Other ‘soft’ benefits with 1,2,4-trifluorbenzene Better relations with authorities (incl. reduced regulatory compliance costs) Uncertain Increased customer satisfaction No Differentiation from competitors Uncertain Better public shareholder and community relations Uncertain Increased job motivation and satisfaction, less absenteeism and illness No Source: Applicants’ information

21 The substance has been found to be available only from one small scale custom synthesis type supplier. Price data has been obtained by Dow’s internal purchasing department, extrapolated from a per kg cost.

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 66

Conclusion on the economic feasibility of 1,2,4-trifluorobenzene as an alternative to EDC

As the applicants’ R&D activities have resulted in the conclusion that 1,2,4-trifluorobenzene is not a technically feasible option (production of sufficiently high quality SAC ER products cannot be achieved), the use of this alternative must also be considered economically infeasible.

Theoretically, even if Dow were to ignore its technical inadequacies, conversion to 1,2,4- trifluorobenzene would require significant modifications to the Fombio and Chauny plants. Including previously anticipated R&D and the cost of installing new equipment, preliminary investment costs could be expected to be in the region of €12-32 million, excluding any requalification/ recertification and worker retraining costs. In addition, there would be reduced turnover and profit during implementation due to plant downtime. Operating costs would also increase by at least '''''''''''''''' ''''''''#F '''''''''''''''', meaning that commercially viable SAC ER production would not be possible. 1,2,4- trifluorobenzene cannot be considered an economically feasible alternative for EDC.

5.1.4 Reduction of overall risk due to transition to the alternative

Classification and labelling

A search of the ECHA C&L Inventory22 (undertaken on 8 April 2015) shows that harmonised classification and labelling information is not available for the substance. An overview of the notified classifications for the substance is provided in Annex 1.

Comparative risk assessment

Annex 1 (Section 7) to this AoA document presents a detailed analysis of the hazards and risks of the selected potential alternative substances. The reader is referred to the Annex, while here a short summary of findings is presented only.

1,2,4-trifluorobenzene is not registered under REACH, consequently no reference values are available from the ECHA dissemination portal. No other reference values could be found. Notified classifications indicate that the substance is a flammable liquid, possesses irritating properties and a relevant short-term toxicity.

Extensive literature searches could not identify suitable data to derive reference values for human health and ecotoxicity. Also, no closely related substances with sufficient data could be identified to justify read-across approaches.

In conclusion, sufficient data are not available to assess for 1,2,4-trifluorobenzene quantitatively. Therefore, at present, it cannot be stated that the substance leads to reduced risks for humans and the environment, when used as a substitute for EDC.

5.1.5 Availability

Three elements of availability can be considered:

22 European Chemicals Agency (C&L Inventory): http://echa.europa.eu/regulations/clp/cl-inventory Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 67

 Access to the technology that allows the implementation of the alternative as a replacement for EDC.

With regard to the quantity of 1,2,4-trifluorobenzene required, it is noted that the replacement ratio in the SAC ER production process is anticipated to be similar (or perhaps slightly higher) than for EDC. Consequently, one can assume that a comparable annual consumption of 1,2,4-trifluorobenzene would be required (i.e. a combined figure of ''''#B '''''' for Chauny and Fombio - see Section 3).

However, it is apparent that obtaining even such relatively low volumes of the substance will be highly problematic. An online search using the substance’s CAS number was undertaken on the ECHA Dissemination Portal23 on 8 April 2015. Information from the portal notes that the substance has not been registered under REACH (although a pre-registration is available). The substance is not considered available from an EU source, meaning it would have to be imported. Although the need to import (and register) 1,2,4-trifluorobenzene is not necessarily problematic, Dow’s purchasing department have researched the market and identified only one small scale, low volume, custom synthesis type supplier. Reliability of supply is therefore a real uncertainty and with regard to quality, the supplier has not been validated as credible at this stage.

Furthermore, as concluded in Section 5.1.2, 1,2,4-trifluorobenzene is a technically infeasible alternative and the applicant does not have the technology that would enable the substance to be implemented as a viable alternative.

5.1.6 Conclusion on suitability and availability for 1,2,4-trifluorobenzene

Based on a multitude of factors, 1,2,4-trifluorobenzene cannot be considered as a potential alternative to EDC. Firstly, results from R&D undertaken on the substance (subsequent to the screening phase) have found it to be a technically infeasible alternative. Of primary concern is the fact that its use results in high levels of residual fluorine in the final SAC ER products, rendering their quality unacceptable. Based on this parameter alone the alternative can also be considered economically infeasible as the applicants will clearly not be able to market sub-standard SAC ER end products. In addition, consultation with internal subject matter experts has highlighted that use of the substance would leave the applicants glass-lined sulphonation reactors susceptible to corrosion and loss of integrity in service.

Even if Dow’s R&D had shown that technical feasibility hurdles could have been overcome, major issues would remain with regard to economic feasibility, with investment costs estimated to be in the region of €12-32 million and unsustainable operating cost increases of at least ''''''#F'''''''. There is also a high level of uncertainty with regard to the applicants’ ability to source sufficient volumes of the substance, which can be considered a somewhat specialist, synthesis type chemical typically only available at laboratory scale sizes.

In addition to these aspects, a quantitative assessment of hazard properties of the substance is not possible due to insufficient data and it cannot, therefore, be concluded that the use of 1,2,4- trifluorobenzene would constitute a lower risk than EDC.

In conclusion, 1,2,4-trifluorobenzene is not a technically feasible, economically feasible or available alternative, and its use cannot be confirmed to result in a lower risk than EDC.

23 ECHA Registered substances database: http://echa.europa.eu/web/guest/information-on- chemicals/registered-substances Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 68

5.2 Alternative 2: DCM

5.2.1 Substance ID and properties

Name and other identifiers of the substance

The following table presents the identity of the substance.

Table 5-8: Identity of DCM Parameter Value Source EC number 200-838-9 1 EC name Dichloromethane 1 CAS number 75-09-2 1 IUPAC name Dichloromethane 1 Methylene dichloride Other names 2 Methylene chloride

Molecular formula CH2Cl2 2 SMILES notation C(Cl)Cl 2 Molecular weight 84.9326 2

Molecular structure 2

Sources (accessed on 8 April 2015): 1. European Chemicals Agency: http://echa.europa.eu/ 2. Chemspider: http://www.chemspider.com/

Physicochemical properties

The following table presents the key physicochemical properties of DCM. The information has been collected from the ECHA dissemination portal.

Table 5-9: Physicochemical properties of DCM Property Value Remarks Source Physical state at 20°C and 101.3 kPa Liquid 1 Melting/freezing point -95 °C at 101.3 kPa 1 Boiling point 40 °C at 101.3 kPa 1 Density 1.33 g/cm³ at 20 °C 1 Vapour pressure 58400 Pa at 25 °C 1 Surface tension Not relevant 1 Water solubility 13200 mg/L at 25 °C and pH 7 1 Partition coefficient log Kow is 1.34 Estimated value 1 Flash point No flashpoint 1 Flammability Not flammable 1 Explosive properties Not relevant 1 Self-ignition temperature 605 °C at 101.3 kPa 1 Oxidising properties Not relevant 1 Granulometry Not relevant 1 Source (accessed on 8 April 2015): 1. European Chemicals Agency: http://echa.europa.eu/

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 69

5.2.2 Technical feasibility

Introduction

A number of steps are taken here for the assessment of the technical feasibility DCM. These include:

 Step 1: Comparison of DCM to EDC against the technical feasibility criteria. An explanation of the technical differences to the EDC-based SAC ER production process is provided  Step 2: Description of practical steps required for the implementation of the alternative. An analysis is given of the R&D, engineering and process modifications required for the conversion of the applicants’ Chauny and Fombio plants to the alternative substance and a timeframe for such implementation is provided.

Comparison of DCM to EDC against key technical performance criteria

The use of DCM as a potential alternative for EDC has been proposed due to the substance’s good technical feasibility characteristics, as highlighted in Section 4.2. Use of DCM as a swelling agent during copolymer sulphonation is also highlighted in a Dow patent, by Strom et al (1992). ''''''''''''''' '''''''''' ''' ''''''''''''''' ''' '''''''''''''''''''''' '''''''' ''''''''''''''''''''''''' ''''''''''''' ''''''''''''''' ''''''''''''' '''' '''''''' '''' '''''''''''''''''''''' '''''''' '''''' '''''''''''''''''''' '''' ''''''' '''''''''''''''''' '''' ''''''' ''''''' '''' ''''''' '''' '''''''''''' ''''''''''''' '''''''''''''''' ''''''''''''''''''' '''' ''''''' ''''' ''''''''''''''''''' ''''''''''''' ''''''''' ''' ''''' '''' '''''''''''''#A ''' '''''''''''' '''''''''''''''''''''' ''''''' '''''''' ''''' ''''''' ''''''''''''''''''' ''''''''''''' ''''''' ''''''''''''''' '''''''''''' ''''' ''''''''''''''''''''' '''' '''''''''''''' ''''''''''' '''''''''' '''''''''' '''''''''' '''''''''''''''''''''' ''''' '''''''' '''''''' '''''''''' ''''''''''''''''''' '''''''' ''''''''' '''' '''''' '''''''''''''' '''''''''''''''' ''''''''''' '''' '''''''''' With this in mind, the comparison of DCM’s performance to EDC in Table 5-10 against the full list of technical comparison criteria, identified in Section 2.6, indicates that the alternative is technically feasible. However, as will be described below, the substance is by no means a drop in replacement for EDC at Chauny and Fombio and a variety of additional factors also make this potential alternative a non-feasible and non-sustainable option for the replacement of EDC.

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 70

Table 5-10: Comparison DCM to EDC according to technical feasibility criteria Criteria Threshold or acceptable range for DCM (comparison and comments) Conclusion replacing EDC Copolymer swelling At least 40% vs initial dry PS-DVB efficiency copolymer Chemical stability Stable in >94% sulphuric acid Thermal stability Stable at temperatures of 25 – 140°C Solvent recyclability >95% recyclability Separation from water Separation of solvent / water in a tank and re-use options Separation from sulphuric Separation (recycling) from sulphuric acid acid must be achievable in the process Freezing point < -20°C Residuals in final polymer The alternative needs to meet specific ''''''''''' ''''' '''''''' ''''''''''''''''' #A'''' ''''''''' '''' ''''''' '''''''''''''''''''' '''' ''''''' '''''' '''' '' product application and/or regulatory ''''''''''''' '''''''' ''''''''''''' ''''''' ''''''''''''''''''''' '''''''' ''''''''''''''' the substance meets all Acceptable requirements necessary technical feasibility requirements for SAC ER production Sulphonation yield At minimum the alternative should achieve the same ion exchange yield for every grade of SAC ER as compared to the EDC bases process Cycle time Similar to current performance to remain competitive for every resin grade Final SAC ER quality At minimum the specifications to be aligned with market needs Environmental regulations Comply with local plant discharge regulations at both plant locations

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 71

Required steps to allow DCM as an alternative to EDC

Although DCM has good technical feasibility characteristics ''''''' ''' '''' '''''''''' '''' ''''''' '''' ''''''''''''' ''''''' ''''''''''' '''''''''''''''' ''''''' '''''' ''''''''''''' #A''''''''''''''' ''''''''' ''''''''''''' ''''''' '''''''''''''''''''' '''''''' ''''''''''''''''''''' DCM is not a drop-in replacement for EDC and processes at Chauny and Fombio would have to be altered significantly if this substance were to be used successfully. One of the main differences between the EDC and DCM-based sulphonation processes is that fact that DCM utilises a pressure driven sulphonation. As a consequence, the replacement of EDC by DCM would have noteworthy practical (e.g. engineering) implications for Dow’s Chauny and Fombio SAC ER production facilities. The required R&D and engineering work has been summarised in the following table, along with information on the necessary modifications to process parameters.

Table 5-11: Steps to technically implement DCM as an alternative for EDC Step Duration of each step Notes (and total duration) 1. R&D work 24 months Significant R&D resources would initially be required to define the ‘new’ pressure driven manufacturing process, demonstrate acceptable product quality for each SAC ER product and define necessary environmental controls, and waste handling measures 2. Modification of 24 months Define and demonstrate full process conditions (usage, process parameters reaction conditions, solvent removal, recovery and recyclability for solvent and acid streams, product post treatment, environmental controls) across entire product lines impacted 3. Engineering work 24 months (from Full scale process scope definition, capital project execution, complete process start up and commissioning plan for raw material handling, definition) production and waste treatment / environmental (air emissions) 4. Full recertification 18 months Can only take place once substance has been fully and requalification implemented within the applicants’ plants. This is the minimum timeframe required (see discussion in the following section) Theoretical total 66 months Assuming full customer acceptance. Based on timeframe to implementation at the Sunset Date, May 2023 is the earliest implement* date this alternative could be put into full operation *Note: The total duration accounts for overlaps between phases of engineering work and process parameter modifications

Conclusion on the technical feasibility of DCM

Despite DCM being able to meet the necessary technical comparison criteria, due to the R&D activities, engineering work and process parameter modifications required for its implementation, the substance cannot be deemed a technically feasible alternative before the Sunset Date. If the applicants were to implement the alternative, theoretically, this could be achieved by May 2023, at the earliest. However, as will be demonstrated in the following sections, DCM is not considered to be an economically feasible alternative for EDC, particularly when long term sustainability considerations are taken into account.

5.2.3 Economic feasibility

The cost of converting from EDC to DCM needs to consider both investment costs and changes to operating costs. Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 72

Investment costs for the implementation of the alternative

There are several key investment costs for switching from EDC to DCM (estimates have been provided based on the knowledge of Dow internal experts):

Access to technology and R&D: Dow estimates that R&D efforts required to convert the SAC ER product lines from EDC to DCM at Chauny and Fombio facilities would take 24 months. This would involve multiple full-time staff working to define process conditions and demonstrate that fully acceptable product quality can be achieved. The required investment costs for this R&D work are projected to be in the range of €1.6-2.4 million.

Plant conversion costs: There are three key steps under this:

 Plant downtime: Limited downtime is expected for customer validation of pilot-plant scale products, as it is predicted that products manufactured using DCM would be of sufficient quality. However, this of course needs to be confirmed, and use of EDC would also need to continue during this qualification transition period (to ensure continuity of SAC ER supply)  Acquisition of replacement equipment: Major new equipment at both Chauny and Fombio will be required for production facilities to implement DCM. The equipment will be required to allow sulphonation reactors to run under pressure and to control all environmental emission sources from process vents and wastewater streams (emission related issues will be magnified at the Chauny plant, where DCM is already used for production of an intermediate product at another area on site, and strong environmental pressures to significantly reduce emissions of this substance are already faced). Precise costs for retrofitting DCM into the Chauny and Fombio sites do not exist at this time, although necessary investments can be estimated to be in the €4-8 million range per site (€8-16 million in total), assuming that there are no local regulatory issues surrounding site operating permits and the approvals required to use DCM  Cost of installing new equipment (engineering cost): The applicants have included engineering costs in the above estimation of €8-16 million for the retrofit of the Chauny and Fombio sites. A separate and more precise estimate cannot be provided.

Recertification and requalification: With regard to the recertification requirements associated with the implementation of DCM, Dow utilised the Decernis ‘gComply’ tool to assess the substance’s current regulatory status. Search results from gComply indicate that DCM is present on several ‘positive’ lists for substances certified for use in a variety of applications (e.g. drinking water and food contact materials) inferring that initial data requirements associated with recertification costs will be limited. However, it should be recognised that the recertification process would only be able to start after DCM was fully implemented within the Chauny and Fombio plants, and would take (at minimum) an additional 18 months to achieve on top of the theoretical R&D, engineering and process parameter modifications discussed above. Taking this into account, it is clear that recertification requirements would be a significant economic hindrance to the uptake of the alternative, although no estimate for ‘total costs’ can be provided.

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 73 are likely to be significant. Furthermore, even if Dow were to fund the necessary requalification programs, it is likely that business would be lost to competing products that can be readily supplied from outside the EU and already have the required qualifications.

An indicative overview of applications that would be particularly affected by recertification and requalification requirements has been provided in Table 5-5.

Retraining: DCM would be a completely new chemical to introduce at the Fombio manufacturing site. It is currently used on a limited basis at the Chauny site in a production area not related to the use applied for. Significant retraining would be involved for the storage, handling, use, recovery, recycling, environmental, health, safety, and regulatory requirements to work with this chemical. An estimated cost for retraining is not available at this time.

Important note: As noted earlier, investment in capital equipment would be funded via the Dow corporate capital funding process. The project would be required to pass all financial, technical, business, and sustainability justification gates, and be compared to other options up to and including the exit of operations and shutdown of the affected production areas within the EU manufacturing footprint. Based on these considerations, the applicants note that they would not be able to obtain funding for the implementation of DCM. These issues are discussed further in the corresponding SEA document.

Changes to operating costs

The following table presents the array of operating cost elements considered by Dow and provides a comparison of the costs arising under EDC and DCM. ''' '''''''''''''' ''''' ''''''''''''' '''''''' '''''' '''''''''''' '''''''' '''' ''''''''''''''' ''' ''''''''''''' '''' ''''''' ''''' '''''' '' '''''''''''' '#D'''''''' '''' '''''''''''''''' '''''''''''''''''''''''' '''''''''''''' '' '''''''''''''' ''''''''''''''''''''' ''''' ''''''' ''''''''''''''''''''''' '''''''''''''''''''' ''''''' '''''' ''''''' '''' ''''''''''' '''''''''''' ''''''' '''''''''''''''''' ''''''' '''''''''''''''' '''''' ''''''''''' '''''''''''''''''''''' '''''''' ''' ''''''''''''.

Given that the applicants produce 50 relevant grades of SAC ER, it is not practical to provide a comparison of operating costs for each individual grade. Consequently %-range estimates have been used to demonstrate how much each cost category contributes to operating costs across the applicants’ EDC-based SAC ER production activities.

Table 5-12: Comparison of operating costs for production of SAC ERs between EDC and DCM Operating cost category Contribution to current Effect on cost element if EDC is overall operating cost (%) replaced by DCM Energy costs Electricity '''''#F ''''' Increase Oil or gas (please specify) '''''#F ''''' Increase Materials and service costs Cost of process solvent (currently EDC ''''#F ''' Slight increase (from ''''''' ''''#F '''''''''''') The replacement ratio is anticipated to be 1:1 Raw materials (excluding water and EDC '''''#F '''''' No significant change expected but including their delivery costs) Water '''''#F '''''' No significant change expected Environmental service costs (e.g. waste ''''#F '''''' Increase due to new waste systems treatment and disposal services) Transportation of product '''''#F ''''' No significant change expected

Labour costs Salaries, for workers on the production '''''''#F '''''''' No significant change expected line (incl. supervisory roles) Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 74

Table 5-12: Comparison of operating costs for production of SAC ERs between EDC and DCM Operating cost category Contribution to current Effect on cost element if EDC is overall operating cost (%) replaced by DCM Costs of meeting worker health and '''#F '''''' No significant change expected safety requirements (e.g. disposable gloves, masks, etc.) Maintenance and laboratory costs Costs associated with testing, '''#F ''' No significant change expected equipment downtime for cleaning or maintenance (incl. maintenance crew costs and lab worker costs) Other costs Marketing, license fees and other ''#F '''' Same or higher in future depending on regulatory compliance activities regulatory sustainability of DCM Other general overhead costs (e.g. '''#F ''' Increase (emissions controls) insurance premiums, administration, etc.) Overall change in operating costs (%) Increase (due mainly to environmental controls)

Energy: As compared to the existing EDC system, energy costs associated with the process would increase due to consumption from additional equipment, pumps, motors and instruments (as required for the pressure driven process).

Materials and services: Increases in the cost of the alternative solvent itself are expected as DCM has a slightly higher price than EDC at '''''''#F '''''. However, such a slight increase would have a very small effect on overall operating costs. Environmental service and emission controls are likely to be the cost elements where the main increases would arise. Requalifications for new waste streams due to additional emissions control equipment related to the volatility of DCM would be required with both the Chauny and Fombio production sites also requiring ongoing evaluation of WWTP and air emissions control systems to ensure compliance with local permit levels.

Labour costs: No significant changes in labour costs are anticipated to arise with the use of this alternative.

Maintenance and laboratory costs: No significant changes in maintenance and laboratory costs are anticipated to arise with the use of this alternative.

Other costs: The applicant anticipates the potential for future regulatory activities surrounding DCM. On this basis ‘other costs’ would be anticipated to increase.

Operating costs – additional considerations

Expectations in relation to any indirect or ‘soft’ benefits that might arise from the replacement of EDC with DCM have also been summarised by the applicants in the following table. As can be seen, no such benefits are likely to arise.

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 75

Table 5-13: Benefits that might arise from substitution of EDC by DCM Likelihood to materialise with Indirect monetary benefit DCM Increased revenue from enhanced company reputation or product image No Entry into new markets No Better creditworthiness No Improved ratings by investment brokers and agencies No Reduced insurance premiums No Likelihood to materialise with Other ‘soft’ benefits DCM Better relations with authorities (incl. reduced regulatory compliance costs) No Increased customer satisfaction No Differentiation from competitors No Better public shareholder and community relations No Increased job motivation and satisfaction, less absenteeism and illness No Source: Applicant’s information

Conclusion on economic feasibility

Overall, the conversion from EDC to DCM would require significant modifications to the Fombio and Chauny plants. Including ongoing R&D and the cost of new equipment, preliminary investment costs could be expected to be in the region of €9.6-18.4 million. In addition, although not anticipated to be as severe as for 1,2,4-trifluorobenzene, there would be reduced turnover and profit during implementation due to the plant downtime, as well as certain recertification, requalification and retraining costs.

Important aspects affecting operating costs are not currently quantifiable, but are believed to be significant. This is due to the combined effect of a small increase in the cost of the alternative, as well as increases in costs associated with environmental services (for waste treatment and disposal) and the control of emissions to achieve ongoing operating permit compliance. As discussed for 1,2,4- trifluorobenzene, market conditions make it impossible for the applicants to absorb price increases, or pass these on to downstream users and the implementation of this potential alternative would likely result in low end margins, placing the applicants at a competitive disadvantage.

Importantly, the applicants must also consider the long term economic feasibility of this substance (as a chlorinated organic solvent) which is believed to be highly questionable from a regulatory risk perspective24. Based on this multitude of factors, DCM is not considered an economically feasible alternative for EDC.

5.2.4 Reduction of overall risk due to transition to the alternative

A search of the ECHA C&L Inventory (undertaken on 8 April 2015) shows that harmonised classification and labelling information is available for the substance, as shown in the following table.

24 DCM is currently on the draft plan for entry to the CoRAP for 2016. The final plan is expected to be published in March 2016.

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 76

Table 5-14: Harmonised classification and labelling of DCM according to CLP criteria Classification Labelling Hazard Hazard Class and Statement Hazard Statement Code(s) Pictogram Signal Word Code(s) Category Code(s) Code(s) GHS08 Carc. 2 H351 H351 Wng Source: European Chemicals Agency (C&L Inventory): http://echa.europa.eu/regulations/clp/cl-inventory

Annex 1 (Section 7) of this document presents a detailed analysis of the hazards and risks of the selected potential alternative substances. The reader is referred to the Annex, while here a short summary of findings is presented only.

-5 For this comparative risk assessment a DMELlong-term inhalation workers for EDC associated with a 1 x 10 risk level was derived from the exposure-risk relationship published by the Risk Assessment Committee (ECHA, 2015).

For the environmental assessment a PNECfreshwater was used, which is the same as derived in the registration dossier and by other evaluating bodies.

DCM was evaluated as a potential alternative substance.

For this substance the DNEL as derived in the registration dossier was used for the comparative assessment. A tentative PNECfreshwater was derived, taking into account available aquatic toxicity data.

EDC and DCM were evaluated using a scenario of handling the substance in a closed system with unloading of the substance from large, dedicated facilities.

ERC: Industrial use of processing aids in processes and products, not becoming part of articles (ERC 4)

PROC: Use in closed process, no likelihood of exposure (PROC 1)

Transfer of substance or preparation (charging/discharging) from/to vessels/large containers at dedicated facilities (PROC 8b)

Based on the quantitative results of this comparative assessment, the alternative substance DCM seems to be advantageous with regard to potential for human health effects. It appears to lead to slightly higher RCRs for the aquatic environment compared to EDC. Based on this information, DCM is considered to lead to reduced risks for humans (and similar risks for the environment), when used as a substitute for EDC.

It is, however, important to highlight the increasing regulatory pressures associated with the use of chlorinated organic solvents; on this basis and from a regulatory risk perspective the applicants do not believe DCM is a long term sustainable option for the replacement of EDC.

5.2.5 Availability

Three elements of availability can be considered:

 Availability of the alternative in quantities sufficient for the applicants’ production processes Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 77

 Availability of the alternative in the quality required by the applicants’ production processes  Access to the technology that allows the implementation of the alternative as replacement for EDC.

With regard to the quantity required, an online search using the substance’s CAS number was undertaken on the ECHA Dissemination Portal25 on 8 April 2015. Information from the portal shows that the substance has been registered under REACH with an individual 1-10 tonnes per annum submission, and a joint submission of 100,000 – 1,000,000 tonnes per annum. Registrants include a Dow subsidiary separate to the applicants (Dow Deutschland Anlagengesellschaft mbH).

Given the relatively low volume of substance that would theoretically be required by the applicants to replace EDC (''''' #B''''''' based on current values in Section 3) it is not envisaged that there would be any difficulties with regard to sourcing the alternative substance at the required quantity. Sourcing the required quality of DCM would also not be an issue.

However, as discussed in Section 5.2.2, the applicants do not at present (and could not by the Sunset Date) have access to the technology to implement the substance as an alternative for EDC.

Furthermore, even if it was possible to successfully overcome economic and technical feasibility hurdles to implement the alternative, the applicants firmly believe uncertainty would remain with regard to future ability to obtain the substance (due to the regulatory risk associated with chlorinated organic solvents). Such uncertainty would certainly restrict the applicants’ ability to obtaining capital funding that would be required for the implementation of the substance as an alternative to EDC.

5.2.6 Conclusion on suitability and availability for DCM

The above discussion has explained that although DCM is a proven swelling solvent for PS-DVB copolymers in the production of SAC ERs ''''''''''''''''' ''''' ''' '''''''''''#A'''' ''''''''' ''''''''''''' ''''' ''''''''''' and it exhibits adequate characteristics in relation to technical feasibility criteria, the substance could not be implemented at the applicants’ existing Chauny and Fombio plants by the Sunset Date. This is due to significant and time consuming R&D, engineering and process modification requirements – much of which is related to the alternative pressure driven sulphonation that is required when this substance is utilised.

When considering economic feasibility, investment costs relating to ongoing R&D, new equipment and engineering are expected to be in the region of €9.6-18.4 million, with this estimate also not taking into account reduced turnover and profit during implementation (due to plant downtime) as well as extensive retraining and recertification costs. Increases to operating costs are not currently quantifiable, but are believed to be significant and are mainly associated with environmental services and emission controls. Furthermore, given the current highly competitive market conditions these increased costs could not be passed onto the applicants’ customers.

Even if the applicants were able to overcome immediate economic and technical feasibility hurdles to implement the DCM, in the long term it is not considered to be a sustainable option given the increasing regulatory pressure associated with the use of chlorinated organic solvents. In this respect, it should be emphasised that there is very little scope for the applicants to justify the major capital, R&D and regulatory funding required for implementing DCM. Investment would have to be

25 ECHA Registered substances database: http://echa.europa.eu/web/guest/information-on- chemicals/registered-substances Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 78 sourced via the Dow corporate capital funding process with the option passing all financial, technical, business, and sustainability requirements (which it would not do). The process would be likely to include a comparison of ‘other options’ by Dow (such as the cessation operations and shutdown of the affected production areas within the EU). These issues are discussed further in the corresponding SEA document. 5.3 Alternative 3: Solventless sulphonation

5.3.1 Description of the alternative technique

The solventless sulphonation technique essentially involves the removal of the swelling solvent and the modification of processing parameters (temperature and sulphuric acid concentration), in order to increase the rate of sulphonation while controlling the side reaction of sulphone bridging to minimise reaction time while maximising copolymer bead quality, to the extent possible (a more in- depth description of this alternative technique is provided in Section 4).

The use of solventless sulphonation as a potential alternative for the EDC based process has been analysed in detail based on the fact that this technique is already recognised and commercially utilised in SAC ER production, and is also in (limited) use by the Rohm and Haas France S.A.S. Chauny plant.

With regard to the current use of solventless sulphonation at Chauny, it must be highlighted that the technique is used to produce a single grade of SAC ER which is produced on a relatively small scale for a commodity market section (water softening). Within this market, the product serves a niche where customers require SAC ERs produced without the use of solvents and are willing to accept a lower quality product in comparison to those produced via the EDC based process.

The fact that the applicant already utilises this technique does not necessarily facilitate its expanded implementation, as knowledge of the current process cannot simply be transferred across to the 50 EDC-based SAC ER products the applicants produce. These products have highly variable requirements, serve a wide variety of applications and, as the applicants are operating within a highly competitive global market, they must ensure a cost competitive position is maintained whilst meeting customers’ requirements and demands.

5.3.2 Technical feasibility

Introduction

A number of steps are taken here for the assessment of the technical feasibility of the alternative technique, solventless sulphonation. These include:

 Step 1: Comparison of solventless sulphonation against the technical feasibility criteria. A detailed explanation of the technical shortcomings/differences to the EDC-based SAC ER production process is provided  Step 2: Description of practical steps required for the implementation of the alternative. An analysis is given of the R&D, engineering and process modifications required for the conversion of the applicants’ Chauny and Fombio plants to the solventless sulphonation process and a timeframe for such implementation is provided.

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 79

Comparison of solventless sulphonation to the EDC based process against key technical performance criteria

Table 5-15 presents a comparison of solventless sulphonation performance against the full list of technical comparison criteria (specific to this technique), identified in Section 2.6.

Table 5-15: Comparison of solventless sulphonation and the use of EDC according to technical feasibility criteria Criteria Threshold or acceptable Solventless sulphonation (comparison Conclusion range for replacing and comment) applicants’ EDC based sulphonation process Copolymer At least 40% vs initial dry Copolymer beads do not swell Unacceptable swelling copolymer experiences comparably in a solventless process efficiency Residuals in final Need to meet the No solvent residuals, but more Unknown polymer product regulatory requirements polymeric leachable impurities may be present in final SAC ERs Sulphonation At minimum the alternative Sulphonation yield would be reduced Unacceptable yield should achieve the same significantly when compared to the ion exchange yield for EDC based sulphonation process every grade of SAC ER as compared to the EDC bases process Cycle time Similar to current Cycle time would increase significantly Unacceptable performance to remain resulting in a decrease in SAC ER competitive for every resin manufacturing capacity at Chauny and grade Fombio Final SAC ER No option to modify values Quality of SAC ER beads would be Unacceptable quality for specifications vs the significantly reduced if this technology current EDC resin grades. is implemented At minimum the current specifications to be aligned with market needs

Detailed presentation of technical characteristics of the alternative

Copolymer swelling efficiency: Copolymer beads do not swell comparably in a solventless sulphonation process. This has direct implications for product yield, and quality – as described further below.

Residuals in final product: As this process removes the need for a solvent, there will clearly be no solvent residuals in the final SAC ERs. However, the reduction in copolymer swelling could lead to an increase in polymeric leachable impurities in the final products. From a quality perspective, this would be unacceptable for many customers.

Sulphonation yield: As a direct result of the lower swelling efficiency, the yield of SAC ERs from the solventless process will also be reduced when compared with the EDC based process. The reduced yield would therefore result in a decrease in SAC ER manufacturing capacity at both Chauny and Fombio.

Cycle time: A key disadvantage associated with solventless sulphonation is the major increase in time required for the sulphonation reaction to take place. Without solvent in the process to soften the

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 80

PS-DVB copolymer, reactions between the copolymer beads and sulphuric acid would be considerably slower and it would take significantly longer for sulphonation to complete. In a plant that is running near capacity in a batch or semi-batch mode, it is important to minimise production times, particularly where different products are made with the same equipment. The applicants estimate that increased cycle time would decrease overall SAC ER manufacturing capacity by 30% across the two plants when considering their entire end product mix. However, as will be discussed below, only a proportion of the applicants’ lower end market products would be attainable via the solventless process. For these products, the applicants estimate a smaller, albeit still significant, manufacturing capacity decrease of 10-15%.

Final SAC ER quality: The solventless process produces inferior quality SAC ER products compared to the EDC-based process. Products sulphonated with EDC appear smooth and homogeneous whereas those sulphonated without a solvent appear rough and irregular. Moisture holding capacity, appearance (cracked/broken/non-smooth beads), bead diameter, and physical stability are all diminished.

Figure 5-1 and Figure 5-2 demonstrate smooth and rough IER surfaces achieved with EDC in comparison to the solventless process.

a) EDC b) Solventless sulphonation

Figure 5-1: Microscopic comparison of polymer bead smoothness achieved with EDC based and solventless sulphonation processes Source: Applicants’ information

a) Smooth surface of an Ion Exchange Resin b) Rough surface of an Ion Exchange Resin

Figure 5-2: Confocal surface laser microscopy result showing ‘smooth’ and ‘rough’ IER surfaces Source: Applicants’ information

The decline in quality achieved via this process would be unacceptable, particularly in the applicants’ higher-end applications (e.g. satisfactory quality would not be achieved for those SAC ERs produced for the nuclear, ultra-pure water, food and biopharmaceutical industries). As a result, it is estimated that 40-60% of current EDC based SAC ER products produced at Chauny and Fombio would no longer be accepted by customers, if they were produced via this technique. Reduction in quality could Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 81 potentially be deemed acceptable for lower end markets with less stringent quality requirements (i.e. for water softening applications), however, separate economic factors (further discussed below) make even the partial uptake use of this alternative infeasible.

Required steps to allow solventless sulphonation as an alternative

The implementation of solventless sulphonation as a replacement for the EDC based process would have noteworthy practical implications for Dow’s Chauny and Fombio SAC ER production facilities. Perhaps most pertinently, and as highlighted above, the process could only be implemented for 40- 60% of the current EDC based SAC ER product range at these sites. In order for Dow to maintain their current range of SAC ER products, further R&D activities may also be required outside the EU to assess the feasibility of, and implement or scale up production, for those products which could no longer be produced within the EU (these issues are explored further in the corresponding SEA document). The required efforts for the (partial) implementation of this alternative by the applicants have been summarised in the following table.

Table 5-16: Steps to allow the technical implementation solventless sulphonation as an alternative to EDC Step Duration of Notes each step (and total duration) 1. R&D work 18 months Significant R&D resources would be required to define the manufacturing process, and demonstrate product quality and performance for the 40-60% of SAC ER products (approximately 25 formulations) for which this alternative technology could theoretically be implemented.

The loss of SAC ER manufacturing capacity will also have to be evaluated in addition to potential inability to supply customers within the EU region 2. Modification of 18 months In order to ensure product quality and performance are acceptable process parameters for customers, process conditions and cycle times would have to be tested, modified and optimised for all SAC ER products produced via this technique 3. Engineering work 24 months (to Existing SAC ER production equipment (used with the EDC-based execute a process) would have to be decommissioned and demolished. portfolio of Capital projects would also be required for the implementation of global projects) the solventless technique at Fombio and further implementation of the technique at Chauny.

Capital projects might also be necessary at non-EU facilities to produce additional volumes of products requiring the use of the EDC-based process. Internal and external resources and capital project funding would be required to implement engineering works at all affected manufacturing facilities 4. Full recertification 18 months Can only take place once substance has been fully implemented and requalification within the applicants’ plants. 18 months would the minimum timeframe required (see additional discussion in following section) Theoretical total 60 months Timeframe assumes full customer acceptance timeframe to implement* *Note: The total duration accounts for overlaps between phases of engineering work and process parameter modifications

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 82

Conclusion on the technical feasibility of solventless sulphonation

With the exception that no solvent would need to be utilised, the solventless sulphonation technique offers no technical advantages to the EDC based process. Copolymer swelling efficiency would be significantly poorer, and the process might also lead to an increase of polymeric leachables in the final SAC ER products. With the implementation of this technique the final quality of the SAC ER’s would also be significantly lowered, to the extent that 40-60% of current EDC based SAC ER products at Chauny and Fombio could no longer be produced at a quality level acceptable for customers.

In addition, production capacity for the remaining products at both Chauny and Fombio plants would be reduced by an estimated 10-15%, due to both a reduction in yield (directly associated with the poorer swelling characteristics) and a significantly longer cycle time.

Based on a theoretical R&D timescale beginning at the EDC Sunset Date, if the applicants were to implement the alternative to the extent possible (in 40-60% of current EDC based SAC ER products), this could be achieved by November 2022 at the earliest. Furthermore, customer acceptance of products would by no means be guaranteed until each individual SAC ER had been developed, qualified, scaled up, and validated.

The applicants do not consider solventless sulphonation a technically feasible option.

5.3.3 Economic feasibility of solventless sulphonation

Investment costs for the implementation of the alternative

The investment costs provided here relate to the applicants’ theoretical and partial (40-60%) implementation of the solventless process, as discussed above (estimates have been provided based on the knowledge of Dow internal experts). Several types of cost must be considered:

Access to technology and R&D: As highlighted above, the applicants estimate that initial R&D efforts required to convert the SAC ER product lines from EDC to solventless sulphonation at Chauny and Fombio facilities would take 18 months. Such activities would involve multiple full-time staff working to define process conditions and demonstrate that fully acceptable product quality can be achieved for the targeted product mix. The required investment costs for this work are projected to be in the region of €1.2-2 million.

Plant conversion costs: there are three key steps under this:  Plant downtime: Although no accurate estimate can be provided, significant downtime is expected for customer validation of plant scale products (EDC use would also need to continue during this qualification transition period). Downtime would also have impacts with regard to production levels and associated sales of SAC ERs (this will depend on the quality of products obtainable and customer acceptance). Significant high end business would be at risk if customers rejected process and product modifications  Acquisition of replacement equipment: Dow estimates costs of between €1.6–4 million at both Chauny and Fombio (€3.2-8 million in total). Additional equipment and investment would also be required to debottleneck the main production lines in order to sustain the required production capacity  Cost of installing new equipment (engineering cost): The applicant has included engineering costs in the above equipment estimation of €3.2-8 million. A separate and more precise estimate cannot be provided.

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 83

Recertification and requalification: Despite the fact that only 40-60% of the applicants’ SAC ERs could be replaced by the solventless process, the implementation of this technique would still trigger major recertifications and (customer and regulatory) requalifications. Currently, a drinking water certification is held for a solventless resin produced at the Chauny plant. Under the theoretical R&D and modification activities proposed at this site (and in line with implementation of a solventless process at Fombio), certification of this resin would need to be repeated in line with relevant changes made at the production plants. Recertification can only start after the new production process is considered stable and has been optimised in the plants. It is estimated that due to e.g. compliance testing, the recertification process would take at a minimum an 18 months (depending on the data packages required, the time needed to generate the data, and the time needed to process the recertification submissions) to achieve on top of the theoretical R&D, engineering and process parameter modifications discussed above.

Again considering the limited proportion of SAC ERs that the solventless technique could theoretically replace, the applicants’ requalifications will likely be concentrated on potable water (and similar) applications. Consequently, NSF (see http://www.nsf.org/about-nsf/), WQA (see http://www.wqa.org/) and country specific requirements would need to be met.

Despite the downstream focus of requalifications, the applicants note that it is highly unlikely that their customers would wish to invest their own time and internal resources to perform the required studies that need to be produced in order to requalify their products, meaning that Dow would be likely to be obliged to pay the related costs if they wished to remain a customer’s supplier of SAC ERs. As Chauny and Fombio are global product supply points, requalifications are not limited to customers within the EU region and associated costs have the potential to be highly variable. The timeline associated with a full requalification is expected to be in the region of 18 months. Reliable estimates for overall requalification costs associated with the implementation of the solventless technique cannot be provided but would likely be significant. Furthermore, even if Dow were to fund the necessary requalification programs, it is likely that business would be lost to competing products that can be readily supplied from outside the EU and already have the required qualifications.

Retraining: The applicants envisage that limited retraining would be required for the implementation of solventless sulphonation. This would be primarily focused on changes to the manufacturing processes, product recipes, and quality impacts.

Important note: As noted earlier, investment in capital equipment would be funded via the Dow corporate capital funding process. The project would be required to pass all financial, technical, business, and sustainability justification gates, and be compared to other options up to and including the exit of operations and shutdown of the affected production areas within the EU manufacturing footprint. Based on these considerations, the applicants note that they would not be able to obtain funding for the further implementation of solventless sulphonation. These issues are discussed further in the corresponding SEA document.

Changes to operating costs

The following table presents the array of operating cost elements considered by Dow and provides a comparison of the costs arising under EDC and solventless sulphonation. ''' '''''''''''' ''''' ''''''''''''' '''''''' ''''''' '''''''''''' '''''''' ''''' '''''''''''''' ''' '''''''''''' '''' '''''''' ''''' ''''''' ''' ''''''''''''' '''''''''' '''' '''''''''''''''''' ''''''''''''''''''''''''' '''''''''''' '' ''''''''''''''' ''''''''''''''''''''' ''''' '''''' ''''''''#D'''''''''''' ''''''''''''''''''''' '''''''' ''''''' ''''''' '''' '''''''''' '''''''''''''' '''''''' '''''''''''''''''' ''''''' '''''''''''''' '''''' ''''''''''' '''''''''''''''''''''' '''''''' '''' ''''''''''''.

Given that the applicants produce 50 relevant grades of SAC ER, it is not practical to provide a comparison of operating costs for each individual grade. Consequently, %-range estimates have Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 84 been used to demonstrate how much each cost category contributes to operating costs across the applicants’ EDC-based SAC ER production activities26.

Table 5.17: Comparison of operating costs for production of SAC ERs between applicants’ current process utilising EDC and solventless sulphonation Operating cost category Contribution to current Effect on cost element if EDC is overall operating cost (%) replaced by solventless sulphonation Energy costs Electricity '''''#F '''' Increase Oil or gas (please specify) '''''#F ''''' Increase Materials and service costs Cost of process solvent (currently EDC) ''#F ''''' Decrease (no cost) Raw materials (excluding water and EDC '''''''#F '''''''' Same but including their delivery costs) Water '''#F '''''''' Same Environmental service costs (e.g. waste '''''#F''''' Decrease treatment and disposal services) Transportation of product '''''#F '''' Same

Labour costs Salaries, for workers on the production '''''''#F '''''''' Same line (incl. supervisory roles) Costs of meeting worker health and '''''#F ''''' Same safety requirements (e.g. disposable gloves, masks, etc.) Maintenance and laboratory costs Costs associated with testing, '''#F ''' Same equipment downtime for cleaning or maintenance (incl. maintenance crew costs and lab worker costs) Other costs Marketing, license fees and other '''#F ''' Same regulatory compliance activities Other general overhead costs (e.g. ''#F '''' Same insurance premiums, administration, etc.) Overall change in operating costs (%) Increase

Energy costs: Higher sulphonation temperatures are required with solventless sulphonation as compared to the EDC based process (addition of swelling solvents to the PS-DVB copolymer lowers the average glass transition temperature and permits sulphonation to progress at lower temperatures). Consequently, with the solventless process the time to heat up the reactor and reactants would become a larger portion of the production time (which is also significantly increased) and more energy would be required in the process.

26 Although this process can technically be adopted for only 40-60% of SAC ERs produced at Chauny and Fombio, the applicants are unable to provide a more detailed breakdown of the current operating costs associated with this specific fraction of SAC ER products, for comparison. Therefore, this operating cost comparison should serve as indicative only.

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 85

Materials and service costs: A decrease in material and service costs would be seen, as no solvent will need to be purchased by the applicant. As a result, waste treatment and disposal costs would also decrease.

Labour costs: No significant cost changes would be likely to arise.

Maintenance and laboratory costs: No significant cost changes would be likely to arise.

Other costs: No other general overhead costs cost changes would be likely to arise.

Operating costs – additional considerations

SAC ER production capacity: In addition to the consideration of ‘per tonne’ operating costs, it is also very important to recognise potential effects the implementation of the solventless sulphonation technique will have on the applicants’ overall manufacturing capacity for SAC ER products. As highlighted above, the implementation of this technique, in addition to rendering the manufacture of 40-60% of products impossible, it would also reduce the applicants’ overall SAC ER manufacturing capacity at the Chauny and Fombio plants.

Considering only those products that the applicants could still produce (i.e. those for water softening applications), and assuming the applicants were able to scale up sales of these SAC ERs to account for volumes of the other SAC ERs that would be lost, the associated increases in cycle times are expected to result in an overall manufacturing capacity decrease of 10-15%. The SAC ER market for water softening applications is already extremely price sensitive and commoditised in value. Consequently, the applicants would not be able to raise prices and recoup losses associated with a capacity decrease, as competitors would be likely to hold prices on their own products to capture market share from Dow.

Such a reduction in capacity would also have direct and severe knock-on effects for ancillary operations undertaken by the applicants and other Dow subsidiaries. These issues are explored further in the corresponding SEA document, but include e.g. a reduction in copolymer demand and production, tie-in AER production and mixed bed resin production.

Soft benefits: In the following table, the applicants have summarised their expectations in relation to any indirect or ‘soft’ benefits that might arise from the replacement of EDC with solventless sulphonation. The table confirms that no such benefits would be likely to arise.

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 86

Table 5-18: Benefits that might arise from replacement of EDC by solventless sulphonation Likelihood to materialise with Indirect monetary benefit solventless sulphonation Increased revenue from enhanced company reputation or product image No Entry into new markets No Better creditworthiness No Improved ratings by investment brokers and agencies No Reduced insurance premiums No Likelihood to materialise with Other ‘soft’ benefits solventless sulphonation Better relations with authorities (incl. reduced regulatory compliance costs) Uncertain Increased customer satisfaction No Differentiation from competitors Uncertain Better public shareholder and community relations Uncertain Increased job motivation and satisfaction, less absenteeism and illness No Source: Applicants’ information

Conclusion on economic feasibility

There are several economic disadvantages associated with the extended use of the solventless technique by the applicants. First and foremost is the fact that the use of this technique would result in the final quality of the SAC ER’s significantly declining, to the extent that 40-60% of current EDC based SAC ER products at Chauny and Fombio could no longer be produced at a quality level acceptable for customers, and their production would therefore cease.

For those products in which the solventless technique could theoretically be utilised, investment costs relating to R&D and new equipment are expected to be in the region of €4.4-10 million with this estimate also not taking into account reduced turnover and profit during implementation due to plant downtime as well as requalification, recertification and retraining costs.

Increases to operating costs per tonne of SAC ER produced cannot be quantified but are expected to rise to an unsustainable level (particularly when it is considered that the applicant would be producing SAC ERs only for the highly commoditised and competitive water softening market). This is mainly due to longer SAC ER batch production times associated with the solventless process. This factor would also have a negative impact with regard to the overall SAC ER manufacturing capacity at both Chauny and Fombio plants, which would be reduced by an estimated 10-15%.

As a result of this multitude of factors, the solventless sulphonation technique cannot be considered an economically feasible option.

5.3.4 Reduction of overall risk due to transition to the alternative

As this alternative removes altogether the need for a solvent to swell the PS-DVB copolymer beads, it can be considered to result in a reduction of hazards and risks when compared with the EDC-based process. Consequently, unlike 1,2,4-trifluorobenzene and DCM, a detailed analysis of these aspects for solventless sulphonation is not provided in Annex 1. Some consideration should be given to the increased energy consumption associated with the operation of this process (as identified above), as this can be associated with an increase of greenhouse gas emissions (on a per unit output basis). However, quantification of these impacts cannot be undertaken.

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 87

5.3.5 Availability of the technology According to ECHA (2011) “alternative techniques can be regarded as available when they are developed enough to allow implementation in the relevant industrial sector and they are reasonably accessible without undue delay to the operator”.

Clearly, given that from a technical perspective solventless sulphonation can only be considered a theoretically feasible replacement for 40-60% of the current Fombio and Chauny EDC based SAC ER product lines (and not until well beyond the Sunset Date), the applicants do not consider the alternative technique to be ‘available’ to them. Additional availability barriers can be associated with the very poor economic feasibility associated with the use of the technique, i.e. the applicants would not be able to raise investment in capital equipment that would need to be acquired via the Dow corporate capital funding process. These issues are discussed further in the corresponding SEA document.

5.3.6 Conclusion on suitability and availability for solventless sulphonation

The above discussion has explained that, although solventless sulphonation is implemented on a small scale at the Chauny facility (to produce an individual grade of SAC ER), the extended use of this technique by the applicants is technically and economically infeasible, and cannot be considered available.

Firstly, due to the poorer quality of products obtained by this technique, its extended use could technically be considered to replace only 40-60% of the current Fombio and Chauny EDC based SAC ER products. Such partial implementation is clearly not acceptable and it would exclude the applicants from several high value markets. Furthermore, even when assuming this limited level of implementation, the wider scale introduction of the technology could not be achieved by the applicants until November 2022 at the earliest, due to major and time consuming R&D, engineering, process modification and recertification / requalification requirements.

When considering economic feasibility, investment costs relating to R&D, new equipment and engineering associated with the limited implementation of the alternative are expected to be in the region of €4.4-9.7 million, with this estimate also not taking into account reduced turnover and profit during implementation (due to plant downtime as well as requalification, recertification and retraining).

Increases to operating costs per tonne of SAC ER produced cannot be quantified but are anticipated to rise to an unsustainable level. This is predominantly due to longer SAC ER batch production times associated with the solventless process, as well as the requirement for higher process temperatures. Longer production times would also have a negative impact with regard to the overall SAC ER manufacturing capacity at both Chauny and Fombio plants, which would be reduced by an estimated 10-15%. These effects are magnified when it is considered that the applicant would be producing SAC ERs only for the highly commoditised and competitive water softening market, where losses of profits could not be recouped by increasing costs of SAC ERs. This is because non-EU competitors could continue to supply their already qualified and approved products to the applicants’ current customer base.

The solventless sulphonation process can be considered to result in a reduction of hazards and risks when compared with the EDC based process. In conclusion, the solventless sulphonation technique is not technically feasible, economically feasible or available, although its use is anticipated to result in a lower risk than EDC. Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 88

6 Overall conclusions on suitability and availability of possible alternatives

6.1 Alternative substances and technologies considered

Dow followed a detailed, stepwise and logical approach to screen 614 potential alternative substances for EDC (considering a wider pool of more than 1000 substances). The initial list was identified via the utilisation of Dow’s in house R&D software in combination with an in depth review of the available scientific and technical literature. Identified substances survived (or were eliminated from further consideration) based on the results of several screening steps. The sequence of screening began with a laboratory-validated assessment of copolymer swelling properties and was followed by a replication of sulphonation process conditions and a preliminary hazard assessment. The availability of remaining substances was also considered. For the identification of alternative techniques, extensive literature searches were undertaken.

The above process resulted in the selection of three potential alternatives (two substances and one technique) which were assessed in detail in Section 5 of this AoA:

 1,2,4-trifluorobenzene  DCM  Solventless sulphonation (technique). 6.2 Conclusions on comparison of alternatives to EDC

6.2.1 Conclusions on technical feasibility

The technical feasibility associated with the potential alternatives varies significantly, although one common element is that no alternative can be considered technically feasible to implement until significantly beyond the EDC Sunset Date in November 2017.

For 1,2,4-trifluorobenzene, following promising results obtained from the screening exercise, the applicants began (in Q2 2014) an R&D plan for the implementation of the substance as an alternative for EDC. However, during the early phases of the plan (in Q1 2015) the applicants discovered that the use of the substance resulted in unsatisfactory levels of residual fluorine in final SAC ER products, which is an issue that cannot be overcome whilst maintaining a viable production process. In addition, consultation with internal subject matter experts has highlighted that use of the substance would leave the applicants glass-lined sulphonation reactors susceptible to corrosion and loss of integrity in service. Based on these factors, 1,2,4-trifluorobenzene was deemed a technically infeasible option.

For DCM, all necessary technical comparison criteria have been met but due to the required R&D activities, engineering work and process parameter modifications, the substance cannot be deemed a technically feasible alternative at this time (DCM must be utilised within a pressure driven sulphonation process, which differs to the current production processes in the applicants’ respective Chauny and Fombio plants). If Dow was to implement the alternative, theoretically, this could be achieved by May 2023 at the earliest.

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 89

The solventless sulphonation technique offers no technical advantages to the EDC based process with the exception that no solvent would need to be utilised. Copolymer swelling efficiency is significantly poorer, and the process may also lead to an increase of polymeric leachables in the final SAC ER products. With the implementation of this technique (which could be achieved by November 2022 at the earliest) the final quality of the SAC ER’s would also be significantly diminished, to the extent that the manufacture of 40-60% of current EDC based SAC ER products at Chauny and Fombio would have to be terminated, as these could no longer be produced at a quality level acceptable for customers. In addition, production capacity for remaining products at both Chauny and Fombio plants would be reduced by an estimated 10-15%, due to both a reduction in yield (directly associated with the technique’s poorer swelling characteristics) and a significantly longer cycle time. Clearly, solventless sulphonation is not a technically feasible option.

6.2.2 Conclusions on economic feasibility

Economic feasibility considerations have taken into account investment costs and changes to operating costs associated with the implementation of the potential alternatives.

For 1,2,4-trifluorobenzene, as the applicants’ R&D activities resulted in the conclusion that the substance is not a technically feasible option (production of sufficient quality SAC ER products cannot be achieved and would therefore cease), its use must also be considered economically infeasible. Even if it was assumed that technical feasibility obstacles could be overcome, as was assumed to be the case at the start of the applicants’ R&D programme, high levels of investment (expected to be in the region of €12-32 million) would be required and operating costs would increase by at least '''''''#F ''''''''' per tonne of SAC ER produced. Such costs would also render the uptake of 1,2,4- trifluorobenzene an economically infeasible option.

For DCM, conversion from EDC would require significant modifications to the Fombio and Chauny plants. Including ongoing R&D and the cost of new equipment, preliminary investment costs could be expected to be in the region of €9.6-18.4 million. Changes to operating costs are not quantifiable, but are believed to be significant. This is due to the combined effect of a small increase in the cost of the alternative, as well as increases in costs associated with environmental services (for waste treatment and disposal) and the control of emissions. When considering DCM, the applicants must also gauge the longer term economic feasibility of the substance. This is believed to be highly uncertain (from a regulatory risk perspective) due to the fact that DCM sits in the same category of solvent as EDC. In this context, the applicants do not consider DCM to be an economically feasible option and, in any case, they would not be able to acquire approval and funding from the Dow Corporation to implement such an option.

Solventless sulphonation is associated with several economic disadvantages. First and foremost is the fact that the use of this technique will result in the termination of 40-60% of current EDC based SAC ER products at Chauny and Fombio. For those products in which the solventless technique could theoretically be extended, investment costs relating to R&D and new equipment are expected to be in the region of €4.4-10 million. Increases to operating costs per tonne of SAC ER produced cannot be quantified but are expected to rise to an unsustainable level (particularly when it is considered that the applicant would be producing SAC ERs only for the highly commoditised and competitive water softening market). This is mainly due to longer SAC ER batch production times associated with the solventless process. This factor would also have a negative impact with regard to the overall SAC ER manufacturing capacity at Chauny and Fombio, which would be reduced by an estimated 10-15%, further magnifying the economically infeasible nature of this option.

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 90

On top of the substance specific values discussed above, it must be noted that some factors (such as plant downtime, recertification, requalification and retraining costs) have not been assessed quantitatively within the AoA. The significant nature of these aspects should not, however, be underestimated. For example, when considering recertification and requalification that would be required for the implementation of any of the alternatives, due to the global nature of the SAC ER market in which the applicants operate, customers may wish to forego the inconvenience associated with these procedures (e.g. their need to internally test a ‘new’ product) and simply obtain an equivalent certified or qualified SAC ER from a non-EU based supplier. The extent to which such an implication could occur would not be measurable until an alternative was implemented, but regardless of investment and operating costs, would have the potential to cause significant economic disruption to the applicants’ SAC ER production activities.

Any changes to the applicants’ production activities also have to be considered in the context of current highly competitive market conditions which make it very difficult for them to absorb price increases, or pass these on to downstream users (these issues are further discussed in the corresponding SEA document).

6.2.3 Conclusions on risk reduction capabilities of the alternatives

A detailed analysis of the hazards and risks of the selected potential alternative substances was undertaken by the applicants. For 1,2,4-trifluorobenzene, as sufficient data are not available for a quantitative assessment, it cannot be concluded that the substance leads to reduced risks for humans and the environment when used as a substitute for EDC.

DCM was concluded to lead to reduced risks for humans and similar risks for the environment when used as a substitute for EDC. However, it is important to note that the applicants have, from a regulatory risk perspective, expressed major concerns with regard to the long term sustainability of implementing this chlorinated organic solvent.

With regard to solventless sulphonation, as this alternative removes altogether the need for a solvent to swell the PS-DVB copolymer beads, it can be considered to result in a reduction of hazards and risks when compared with the EDC based process. However, some consideration should be given to the increased energy consumption associated with the operation of this process, which would be associated with an increase of greenhouse gas emissions.

6.2.4 Conclusions on availability of alternatives

For 1,2,4-trifluorobenzene and DCM the applicants considered the following factors (for the solventless sulphonation technique, as no solvent is required, only the last point was considered):

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 91

For DCM, the alternative substance can itself be considered available in the quantity and quality that would be required by the applicant; however, implementation could not be achieved until May 2023.

When considering the solventless sulphonation technique, given that it can only be considered a technically feasible replacement for 40-60% of the current Fombio and Chauny EDC based SAC ER product lines (and not until November 2022), the applicants do not consider the alternative technique to be ‘available’ to them. 6.3 Overall conclusion and future research and development

6.3.1 Overall conclusion

The overall outcome of the applicants’ analysis is shown in Table 6-1.

Table 6-1: Overall conclusions on suitability and availability of shortlisted alternatives Potential alternative Key consideration 1,2,4-trifluorobenzene DCM Solventless sulphonation No Is the potential Not at present (only partial alternative No (could become feasible by implementation possible, technically feasible? May 2023 at the earliest) this is not acceptable) No Is the potential (particularly considering alternative No the longer term No economically sustainability of the feasible? substance) Yes Does the potential (although there are major alternative result in a Cannot be confirmed Yes concerns for longer term reduction of risk? sustainability) The substance is available. Is the potential The process could become alternative No No technically feasible by May available? 2023 at the earliest Would the applicants be able to obtain corporate approval No No No and capital funding to implement the alternative?

6.3.2 Future research and development activities

The applicants, as part of The Dow Chemical Company group, are at the forefront of R&D and innovation in the IER industry and have been actively pursuing the implementation of a potential alternative for EDC in the sulphonation process for many years, as detailed in Section 4.2.1. Significant funds have also been dedicated to the applicants’ current, intensified R&D programme (which started in mid-2012) in association with this AfA, with related costs anticipated to total ''''''''' ''''#G''''''''' by the EDC Sunset Date in November 2017.

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 92

Despite these continued efforts, as concluded within this AoA, it is not possible to remove EDC within the current sulphonation process when technical, economic, risk reduction and long-term sustainability constraints are considered. The use of EDC is required to achieve cost-effective processing, high quality resins and the appropriate (and approved) performance level for a wide variety of SAC ER markets and applications on the global scale.

The applicants’ ideal goal is to replace EDC via the identification and development of an alternative that will attain technical performance (and associated economic viability) at a level at least equivalent to EDC. Results of the recent R&D effort looking at >1000 potential alternative solvents demonstrates that this goal is extremely challenging. Bearing in mind the highly competitive nature of the IER market, the applicants have no plans to (and cannot) implement an inferior solvent or technique. Doing so would place their SAC ER production activities at a distinct disadvantage to non- EU competitors who could continue using EDC. In this respect, an obligation to implement an inferior alternative would also make the relocation of the applicants’ current SAC ER activities to non- EU plants a more attractive option for Dow.

Similar considerations and Dow’s corporate strategy must also be taken into account when the scale of the applicants’ future R&D operations are explored i.e. local and global cost competitive positions must be maintained for SAC ERs.

Disregarding the above uncertainties, if the applicants are able to obtain a sufficient review period and the required R&D funding, efforts are likely to focus on two areas:

 Continued research into the identification and implementation of a technically feasible, economically feasible, available and sustainable alternative to EDC: New alternative solvents can be screened via a similar methodology associated with the applicants’ current efforts (i.e. a four-step process involving the initial identification of potential alternatives, an assessment of swelling efficiency, an assessment of stability and recyclability under sulphonation conditions and a preliminary hazard assessment). If a potential alternative progresses from the initial screening, a tailored R&D plan for its implementation can then be formulated, under which more extensive testing will be undertaken to confirm whether the alternative can be considered a fully feasible option.  '''''''''''''''''''' ''''''''''' ''''' '''''''''''' ''' '''''''''''''''''' '''''''' ''''''''''''''''''''''''''' '''''''''''' ''''''''''''''''''''''''' '''''''' '''''''' '''''''''''' '''''''''''''''''''''''''' '''''''''''''''' ''''''''''''' '''''' '''''''''''''''''''''' '''''''''''''' '''''''''''''''''''' '''''' '''''''''''''''''''''' '''''''' ''''''' '''''''''''''''' ''''''''''' '''' ''''''''''' '''' '''''''''''''''''#G ' '''''''''''''' '''''''''''''''''''''''''' '''''''' '''''''''' ''''''' '''''''''''' '''' ''''''''' '''''''''''''' ''''''' ''''''''''''' '''''''''''''''''''''''''' '''''''' ''''' ''''''''''''' '''''''''''''''''''' '''''''''''''''''' '''' ''''''''' ''''''''''''' '''''''' '''''''''''''''''''' ''''''''''''''''''''''''''''' ''''''''''' ''''''''''''''''''''''''' '''''''''''''''' '''' ''''''''''''' ''''''''''''''''''''''''''' '''' '''''''' '''''' ''''''' ''''' ''''''''''''''''''''''''

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 93

7 Annex 1: Risk evaluation of alternative substances

7.1 Methodological approach

Article 60 (5) of REACH requires the applicants to investigate whether the use of an alternative substance “would result in reduced overall risks to human health and the environment” (as compared to the Annex XIV substance EDC).

A first hazard screening was carried out to deselect from an initial list of potential alternatives those substances which are not eligible due to a critical hazard profile (CMR substances or substances with a similar level of concern) (see Section 4.2.1).

From the remaining substances those candidates were selected which provide the highest chances for substituting EDC from a technical and economical perspective. In conclusion, two substances were selected for in-depth analysis (see Section 5)27:

 DCM (CAS no: 75-09-2)  1,2,4-trifluorobenzene (CAS no: 367-23-7).

In order to comply with the REACH requirements, in this section the hazard profiles of these substances are presented and suitable reference values for a quantitative comparison (DNELs for human health assessment, PNECs for an assessment of environmental toxicity) are either identified or (if no such reliable basis could be found in the public domain) derived (see Section 7.2).

Literature searches (up to September 2014) for the alternative substances selected for in-depth evaluation were performed in additional bibliographic and other databases as appropriate (after consultation of existing assessments) and assessments available from eChemPortal and other sources were screened.

In detail, the following sources and search steps were used to retrieve relevant information:

 ECHA CHEM database (http://echa.europa.eu/search-chemicals)  eChemPortal (http://www.echemportal.org/echemportal/), with all related sources  bibliographic database Pubmed (http://www.ncbi.nlm.nih.gov/pubmed/)  the US NLM portal TOXNET (http://toxnet.nlm.nih.gov/ including the bibliographic database Toxline and other databases  ECOTOX database (http://cfpub.epa.gov/ecotox/)  the aquatic toxicity database CHRIP of the Japanese Ministry of Environment (http://www.safe.nite.go.jp/english/db.html).

As not only a comparison of hazard profiles is required but a comparison of substance properties on a risk basis, a human health and environmental exposure scenario is developed (Section 7.3). Exposure within this scenario is estimated using the Tier I tool ECETOC TRA v.3.1. This approach is different to that used in the CSR, as it should be applicable in a similar way for all alternative substances assessed and therefore is of a more generic nature, which does not rely on specific data

27 As the third alternative, ‘solventless sulphonation’, removes the need for a solvent altogether it has been assumed to result in a reduced risk to human health and the environment, and no detailed assessment has been carried out in this Annex.

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(e.g. measured data). The outcome of the exposure assessment should not be considered a realistic estimate of exposures, but is expected to describe relative exposure intensities.

Section 7.4 finally presents the comparative risk characterisation and the overall conclusions on risks from using the alternative substances. 7.2 Reference values (DNELs, PNECs) for EDC and alternative substances

7.2.1 Introduction

In the following sections DNELs and PNECs are discussed, which can be used for a comparative assessment. Available monographs, data from registration dossiers as available at ECHA-CHEM (ECHA, 2015a) as well as published data (in case of inconsistencies or data gaps) are used for this purpose.

In case no DNELs/PNECs or similar reference values are available, which are compliant with requirements according to ECHA Guidance (ECHA, 2008; 2012) (or if there is not enough information available on the rationales for deriving the values, which is often the case with the values reported in ECHA CHEM), then based on available data tentative DNELs/PNECs are derived to be used in this comparative assessment, this way giving emphasis to a harmonised approach for all substances. The tentative values should not be considered as a final evaluation of the effects of the substances. These values are used for this comparative assessment only and are not intended to represent a full assessment of the substances concerned.

For human health considerations DNELlong-term inhalation workers and DNELlong-term dermal workers for all alternative substances are used. For EDC the inhalation concentration associated with a risk level of 10-5 (DMEL) is used for comparison with the alternative substances.

For the environmental assessment PNECfreshwater will be used as reference values for the comparative assessment. In case of organic substances and in absence of compartment-specific toxicity data reference values for other compartments (sediment, soil) are often calculated with the equilibrium partitioning method (EPM). As the EPM method is also used for calculating exposure levels (“predicted environmental concentrations”, PEC), risk characterisation ratios calculated this way are the same as for the freshwater compartment. Therefore, RCRs calculated for freshwater are taken as indicative for risks for all environmental compartments.

7.2.2 EDC (CAS: 107-06-2)

Classification

Classification information for EDC is provided in the following figure.

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Figure 7-1: EDC classification information Source: http://echa.europa.eu/web/guest/home (accessed on 6 August 2014)

Human Health

A reference value for long-term, inhalation exposure of workers of 16.7 µg/m3 (equivalent to 4 ppb) associated with a risk level of 1 x 10-5 is used for the comparative assessment with the alternative substances here. This value is based on the exposure-risk relationship presented by RAC (ECHA, 2015b).

This reference value is used for the RCR calculations in the tables in Section 7.4.

RAC (ECHA, 2015b) also proposed an exposure-risk relationship for dermal exposure. As this exposure route is considered to be negligible compared to inhalation exposure, due to the substance’s high volatility, no DMEL for dermal exposure is set here and this exposure route is not considered for this comparative assessment.

Ecotoxicity

Existing reference values

Table 7-1: PNECs for EDC – values from ECHA-CHEM compared to other assessments Reference value ECHA-CHEM28 OECD SIDS (2002) CEPA (Canadian Environmental Protection Act, 1994)

PNECfreshwater (assessment 1100 µg/L (10) 1100 µg/L (10) 130 µg/L (20) factor)

PNECmarine-water 110 µg/L (100) - -

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Table 7-1: PNECs for EDC – values from ECHA-CHEM compared to other assessments Reference value ECHA-CHEM28 OECD SIDS (2002) CEPA (Canadian Environmental Protection Act, 1994) (assessment factor)

PNECintermittent-releases 1360 µg/L (100) - - (assessment factor) PNECSTP (assessment 27800 mg/L (100) - - factor) PNECsediment freshwater 11.1 mg/kg sed. dw. - - (EPM)

PNECsoil 1.8 mg/kg soil dw. (EPM) - -

Discussion of suitability of reference values for comparative assessment

Basis for PNECfreshwater derived in ECHA CHEM and OECD SIDS (2002):

Acute and long-term aquatic toxicity data for species from three trophic levels. Lowest NOAEC of 11 mg/L from daphnia magna life cycle toxicity study. Assesment factor 10.

Basis for PNECfreshwater derived by CEPA (Canadian Environmental Protection Act, 1994):

Study of effects on larval survival of northwestern salamander (Ambystoma gracile), with LC50 2.54 mg/L (Black et al., 1982, unpublished). Assessment factor 20.

The study by Black et al. investigated also toxicity of EDC to fish in several species. LC50 values obtained were consistently and substantially lower than those from other fish toxicity studies with the substance. The Black et al. study was criticised in OECD SIDS and was considered not reliable enough to be used for PNEC derivation, due to the non-reproducibility in other studies.

Conclusions: PNECs for comparative assessment

The PNECfreshwater as derived in the registration dossier (ECHA CHEM) and by OECD SIDS (1100 µg/L) is used for the comparative assessment.

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7.2.3 DCM (methylene chloride, CAS: 75-09-2)

Classification

Classification information for DCM is provided in the following figure.

Figure 7-2: DCM classification information Source: http://echa.europa.eu/web/guest/home (accessed on 22 September 2014)

In addition, classification for the following endpoints is proposed in the substance’s registration dossier:

- H315 (Skin irrit 2) - H319 (Eye irrit 2) - H336 (STOT SE 3).

Human Health

Existing reference values

Table 7-2: DNELs (or DMELs) for DCM from ECHA-CHEM29 ECHA-CHEM ECHA-CHEM Reference value (joint submission) (individual submission) DNEL long-term workers inhalation 353 mg/m³ * 132.14 mg/m³ (DMEL for short- term exposure) ** DNEL long-term workers dermal 12 mg/kg bw/day - DNEL long-term general 88.3 mg/m³ * 5 mg/m³ (DMEL for short-term population inhalation exposure) ** DNEL long-term general 5.82 mg/kg bw/day - population dermal DNEL long-term general 0.06 mg/kg bw/day - population oral * based on SCOEL assessment ** given as inhalative DMEL, short-term exposure, derived from NOAEC by using assessment factors; no further information available

29 http://echa.europa.eu/web/guest/home, assessed on 22 September 2014 Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 98

As shown above, in the EU DCM is classified as suspected carcinogen (Cat 2, H351). Similarly, US EPA classified the substance as “likely to be carcinogenic in humans”30. IARC recently upgraded its classification of DCM to Group 2A “probably carcinogenic to humans” (Benbrahim-Tallaa et al., 2014) in comparison to its previous classification (Group 2B, possibly carcinogenic to humans) (IARC, 1999). This new classification is based on limited evidence that the substance causes biliary-tract cancer and non-Hodgkin lymphoma in humans.

DCM was tested in several oral and inhalation carcinogenicity studies with rats and mice. Only the mouse inhalation studies showed clear evidence of carcinogenicity. Lung and liver tumours were observed in these studies. Benign fibroadenomas of the mammary gland were found in inhalation studies with rats of both sexes (IARC, 1999).

DCM was consistently positive in in vitro mutagenicity assays with microorganisms and induced chromosomal aberrations in human cells in vitro. Inconclusive or negative results were obtained for gene mutations in mammalian cells (IARC, 1999). In general, DCM did not induce chromosome aberrations, micronuclei (TG 474) or DNA damage in rats in vivo after oral or inhalation exposure. The increase in chromosomal damage (aberrations and micronuclei), seen only in B6C3F1 mice, is thought to be related to this species’ high rate of metabolism of dichloromethane by glutathione transferase. Dichloromethane tested negative for genotoxicity in standard in vivo studies in rats and mice. Overall, the data indicate that DCM is not genotoxic in vivo (based on data from registration dossier31).

Metabolism via a glutathione S-transferase-dependant pathway was linked to metabolites considered responsible for the carcinogenic action of the substance in mice. The fact that this enzymatic activity is expressed to a greater extent in mouse tissues compared to rats or humans might explain the differences in the study outcome in mice and rat studies (IARC, 1999). In its recent evaluation IARC considered the fact that this metabolism pathway, which is associated with the genotoxicity of DCM, is active in humans (Benbrahim-Tallaa et al., 2014).

In 2009 the Scientific Committee on Occupational Exposure Limits (SCOEL) evaluated the substance and concluded that based on the current knowledge of activation pathways and the experimental and human data available DCM had a “practical threshold” and probably poses a small risk “under conditions of current occupational exposures”. (SCOEL, 2009). In consequence, SCOEL assigned DCM to the group C and assumed a “practical” threshold with the consequence that an OEL was derived based on non-cancer endpoints. SCOEL recommended an 8 hour TWA OEL of 100 ppm (353 mg/m3), which was mainly based on experiences in the workplace, where no adverse effects were observed at this concentrations (SCOEL, 2009).

30 US EPA: http://cfpub.epa.gov/ncea/iris/index.cfm?fuseaction=iris.showQuickView&substance_nmbr=0070 (Integrated Risk Information System, IRIS) 31 http://echa.europa.eu/web/guest/home

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Discussion of suitability of reference values for comparative assessment

Some uncertainties exist regarding the mode of action of the carcinogenic activity of DCM. In the registration dossier DCM is considered non-genotoxic and a DNEL of 353 mg/m3 was set. SCOEL considered the substance as a weak carcinogen at most and derived an OEL based on other, non- carcinogenic endpoints.

Conclusion

For the comparative assessment the DNEL of 353 mg/m3, identical to the OEL proposed by SCOEL, is used for the comparative assessment.

As the dermal exposure route is considered to be negligible compared to inhalation exposure, due to the substance’s high volatility, no DNEL for dermal exposure is set here and this exposure route is not considered for this comparative assessment.

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Ecotoxicity

Existing reference values

Table 7-3: PNECs for DCM – values from ECHA-CHEM compared to other assessments ECHA-CHEM ECHA-CHEM Reference value (joint submission) (individual submission)

PNECfreshwater (assessment 310 µg/L (20) 130 µg/L (100) factor)

PNECmarine-water (assessment 31 µg/L (200) 130 µg/L (100) factor)

PNECintermittent-releases 270 µg/L (100) - (assessment factor) PNECSTP (assessment factor) 26 mg/L (100) - PNECsediment freshwater 2.57 mg/kg sed. dw. (EPM) 0.163 mg/kg sed. dw. (--) PNECsoil 0.33 mg/kg soil dw. (EPM) 0.173 mg/kg soil dw. (AF 1000)

Basis for PNECfreshwater derived in ECHA CHEM:

All data regarding the individual submission by ECHA-CHEM are based on QSAR, only. Because of this, the resulting PNEC is regarded as being not reliable and consequently will not be discussed any further.

Relevant data from ECHA-CHEM used for PNECfreshwater derivation in case of the joint submission are as follows:

Aquatic invertebrates, acute toxicity: LC50 (48h, Daphnia magna, mort) = 27 mg/L (nom.)

Aquatic invertebrates, chronic toxicity: NOEC by QSAR: 6.2 – 13.3 mg/L (different approaches)

Aquatic plants / algae: no reliable studies, WOE toxicity threshold (8d, blue algae): 550 g/L (Bringmann and Kühn, 1978).

Fish, acute toxicity:

 Key study 1 (fresh water): LC50 (96h; Pimephales promelas; flow through; meas.) = 193 mg/L;  Key study 2 (salt water): LC50 (96h; Fundulus heteroclitus - mummichog; static; meas) = 97 mg/L.

Fish, chronic toxicity:

Key study: NOEC (28d; growth rate; Pimephales prom; flow through; meas.): 83 mg/L

Obviously, PNECfreshwater according to ECHA-CHEM was derived interpreting the QSAR-result for aquatic invertebrates as information on chronic exposure in addition to chronic data on fish and algae. According to R.10, an AF of 10 would result. Presumably to account for limited reliability regarding the studies on algae and / or imponderabilities concerning the value for aquatic invertebrates (QSAR), the factor of 20 was selected and used on the most sensitive trophic level (NOEC of 6.2 mg/L for Daphnids derived by QSAR).

Further studies are available from the literature, which are not reported in the dossier published in ECHA CHEM: Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 101

Aquatic plants / algae:

According to Brack and Rottler (1994), the published data on algae by Bringmann and Kühn (1978) are not reliable for volatile solvents, because no measures were taken to prevent evaporation, which may have led to high effect concentrations.

Brack and Rottler (1994) reported effects of DCM on Chlamydomonas reinhardtii (green alga) Algae were grown in sealed test vessels including a CO2 source (carbonate / bicarbonate buffer) connected via the gas phase to the growth chamber. Actual concentrations were measured at the end of the test (2 replicates for each test item concentration, 3 replicates for controls). Growth of controls was logarithmic throughout the exposure phase, and multiplication during 72 hours was at least by a factor of 100. For DCM the following effect concentrations reduction of biomass were derived:

EC10 (72h, measured, biomass) = 115 mg/L (95% C.I.: 79.1 – 146)

EC50 (72h, measured, biomass) = 242 mg/L (95% C.I.: 202 – 286)

The data determined by Brack and Rottler (1994) on Chlamydomonas reinhardtii (green alga) growth inhibition by DCM provide reliable information on the effect of DCM on algae. However, as they report the effects on a biomass basis (and did not report effects on algal growth rate) the reported EC10 and EC50 values are considered conservative (biomass based effect concentrations in general are more sensitive than growth rate based values).

Chronic toxicity data on aquatic vertebrates (fish and frog larvae):

Black et al. (1982) published reliable data (flow through, analytical verification of test item concentrations, closed tanks to prevent evaporation of volatile solvents, detailed reporting of material and methods as well as results) on toxicity of DCM to embryo-larval stages of fish and amphibians (partial life cycle tests: exposure initiated within 30 minutes of fertilization through embryogenesis to 4 days post-hatch). For DCM, most sensitive species were Rainbow trout (Oncorhynchus mykiss, reported as Salmo gairdneri) and European common frog (Rana temoraria). For evaluation of results, teratic organisms were counted as dead. The following results are reported:

1) Rainbow trout

 LC50 (27 d) = 13.16 (95% CI: 10.95-15.32) mg/L  LOEL for teratogenic effects (23 d) = 5.55 mg/L (+/- 1.06)

 Approximated (from reported single data points, not reported) LC10 (27 d): 0.13 mg/L 2) Rana temporaria

 LC50 (9 d) = 16.93 (95% CI: 10.95-29.04) mg/L  LOEL for teratogenic effects (5 d) = 18.9 mg/L (+/- 1.8)

 reported LC10 (9d) = 0.8224 (95% CI: 0.2526-1.643) mg/L 3) Fathead minnow (Pimephales promelas)

 Approximate LC50 (9 d, i.e. 5 days till hatching plus 4 days post-hatch): 34 mg/L

 Approximate EC10 (concentration level showing 10% lethality): 0.11 mg/L (+/- 0.02). This disagrees pronouncedly with the NOEC (28d; growth rate; Pimephales prom; flow through; meas.) of 83 mg/L in the fish study reported in ECHA CHEM.

Further toxicity data are available for the free living nematode Panagrellus redivivus (Samoiloff et al., 1980). The testing method is well described (see also Samoiloff, 1990) and implies closed vials for testing. 54% and 85% inhibition of transition from L4 to adult molt were observed at 0.85 µg/L and 84.9 µg/L, respectively. The corresponding increase of frequency of X-chromosomal lethal mutations Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 102 per locus compared to the background of control animals was 27 and 46-fold at these concentrations.

Discussion of suitability of reference values for comparative assessment

The effect concentrations determined by Black et al. (1982) for aquatic vertebrates are consistently lower than those reported by ECHA-CHEM, especially with regard to low effect concentrations (LC10- values). While no methodological deficits become obvious from the original publication, data on fish for EDC tested in the same publication by Black et al. (1982) were criticized in OECD SIDS on EDC (OECD, 2002) to be consistently and substantially lower than those from other fish toxicity studies with the substance. In the SIDS report, the study was considered not reliable enough to be used for PNEC derivation, due to the non-reproducibility in other studies. Therefore, data from this study on the toxicity of DCM are not used for derivation of a tentative PNECfreshwater.

While the study on the nematode Panagrellus redivivus was regarded as relevant within the Canadian assessment report on DCM (Canadian Environmental Protection Act, 1993), it is a non- standard test, and while potentially mutagenic effects were observed, it is difficult to interpret these effects on a population level. The results on Panagrellus redivivus are therefore not included into the data for derivation of a tentative PNECfreshwater.

In conclusion, the following data are regarded as relevant and used for tentative PNECfreshwater derivation:

 fish, (sub)chronic: NOEC (28d; growth rate; Pimephales prom; flow through; meas.): 83 mg/L  algae, chronic: EC10 (72h; Chlamydomonas reinhardtii; measured; biomass) = 115 mg/L

 invertebrates, acute: LC50 (48h, Daphnia magna, mort) = 27 mg/L (nom.)

While chronic data are available for two trophic levels, these do not cover the acutely most sensitive trophic level aquatic invertebrates. Because the acute LC50 for aquatic invertebrates is lower than the lowest long-term result, the tentative PNECfreshwater is derived from the acute LC50 for Daphnia magna with an assessment factor of 100 according to REACH guidance document R.10 (ECHA, 2008):

PNECfreshwater = 270 µg/L

Conclusions: Tentative PNECs for comparative assessment

The PNECfreshwater from ECHA-CHEM based on the individual submission is considered not to be reliable (based on QSAR, only). With regard to PNECfreshwater based on the joint submission (ECHA- CHEM), methodology for derivation is unknown. To be equivalent with PNECfreshwater derived for other compounds being part of the alternatives assessment, the tentative PNECfreshwater derived above will be used for comparative assessment:

PNECfreshwater = 270 µg/L.

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7.2.4 1,2,4-Trifluorobenzene (CAS 367-23-7)

Classification

Classification information for DCM is provided in the following figure.

Figure 7-3: 1,2,4-trifluorobenzene classification information Source: http://echa.europa.eu/web/guest/home (accessed on 13 October 2014)

Human Health

Existing reference values

The substance is not registered under REACH, consequently no reference values are available from ECHA-Chem. No other reference values could be found.

Virtually no toxicity data could be identified. Safety data sheets most often give the classifications as shown above from notifications, but without presenting the data leading to the classifications.

Discussion of suitability of reference values for comparative assessment

No data are available to assess the toxicity of 1,2,4-trifluorobenzene. The substance is preregistered and therefore it can be assumed that a basic set of data will become available until 2018. Currently the suitability of the substance as an alternative cannot be evaluated.

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Conclusion

There are no data to derive tentative DNELs for 1,2,4-trifluorobenzene. Currently the suitability of the substance as an alternative cannot be assessed.

Ecotoxicity

Existing reference values

The substance is not registered under REACH, consequently no reference values are available from ECHA-Chem. Also, no EU-RAR was prepared for this compound. No other reference values could be found.

Discussion of suitability of reference values for comparative assessment

No reference values exist. No experimental data on ecotoxicity could be retrieved for the substance itself. In comparison, the corresponding 1,2,4-trichlorobenzene (CAS: 120-82-1) is data-rich and therefore, a comparative profiling using OECD QSAR toolbox v. 3.2.0.103 was performed. Profiling results were similar, with the following deviations of possible relevance:

 Ultimate biodegradation time frame predicted by BIOWIN 3 is months and longer for the fluoro- isomer compared to weeks to months for the chlorinated benzene.  Protein binding alerts for skin sensitization by OASIS v1.2: No alert for the chlorinated benzene, but the following alert for 1,2,4-trifluorobenzene: SNAr|SNAr >> Nucleophilic aromatic substitution on activated aryl and heteroaryl compounds|SNAr >> Nucleophilic aromatic substitution on activated aryl and heteroaryl compounds >> Activated aryl and heteroaryl compound

According to US-EPA ECOSAR, both compounds are assigned to the neutral organics class. Predictions for 1,2,4-trichlorobenzene are within the range of experimental values reported in EU RAR (ECB, 2003). Predicted values for 1,2,4-trifluorobenzene are considerably higher (around a factor of 10), i.e. ECOSAR predicts the compound to be of lower toxicity than the chlorinated derivative.

Therefore, given the lack of data for 1,2,4-trifluorobenzene, data on aquatic toxicity for 1,2,4- trichlorobenzene may be taken as indicative for the fluorinated isomer. No PNECs are available for 1,2,4-trichlorobenzene, which is registered as an intermediate only, and thus the EU-RAR is used as a reference for ecotoxicity. According to this, the NOEC for aquatic invertebrates (Daphnia, 21 days) and fish (Brachydanio rerio, 21 days) is 60 µg/L and 40 µg/L, respectively. Based on chronic data for three trophic levels, a PNECfreshwater of 4 µg/L was derived.

Bioaccumulation potential:

From the PhysProp-database (available via US-EPA EPI Suite KOWWIN module), an experimental log

KOW value of 2.52 is reported with reference to Sangster (1993). The same value is retrieved using OECD QSAR Toolbox. This log KOW of 2.52 indicates a low to moderate potential for bio-accumulation. In conclusion, despite the presumed persistence it is unclear whether PBT/vPvB-properties are of concern for this substance.

Conclusions: Tentative PNECs for comparative assessment

An assessment and derivation of a tentative PNEC is not possible.

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7.3 Exposure Assessment

7.3.1 Exposure scenario

EDC is used in a closed system as process chemical (solvent) in the production of SAC ERs. The following use descriptors are assigned to this use:

Exposure scenario: Use in the production of ion exchange resins.

ERC: Industrial use of processing aids in processes and products, not becoming part of articles (ERC 4)

PROC: Use in closed process, no likelihood of exposure (PROC 1)

Transfer of substance or preparation (charging/discharging) from/to vessels/large containers at dedicated facilities (PROC 8b)

(i.e. unloading of road tankers - maintenance and cleaning activities, which is an additional activity, to which PROC8b was assigned is not considered here)

This scenario was used for performing a comparative exposure assessment and risk characterisation. Exposure modelling was done using ECETOC TRA, version 3.1.32

The following DNELs/DMELs and PNECs are used for the comparative risk characterisation (for details see Section 7.2).

Table 7-4: DNELs/DMELs and PNECs used for EDC and alternative substances for the comparative risk characterisation Substance D(M)NELlong-term inhalation D(M)NELlong-term dermal PNECfreshwater w workers workers EDC 16.7 µg/m3 NA* 1100 µg/L DCM 353 µg/m3 NA* 270 µg/L 1,2,4-trifluorobenzene - - - * Not available

Evaluation of 1,2,4-trifluorobenzene for environmental and for human health risks is currently not possible due to the unavailability of hazard data.

Dermal exposure from both EDC and from DCM are considered negligible for the following reasons:

- under conditions of PROC 1 no dermal exposure is expected as the substances are handled in closed systems only - under PROC8b operators wear protective clothing and gloves; occasional small splashes may occur at most and these are expected to evaporate rapidly from gloves; direct contact but also contact via contaminated gloves when taking them off are not possible; therefore, for the purpose of this comparative assessment inhalation exposure is considered the only relevant pathway for these two substances.

32 http://www.ecetoc.org/tra

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7.3.2 Input data for exposure modelling

The following data are used for the exposure modelling in the standardised exposure scenario:

Table 7-5: Physico-chemical and environmental fate properties data of alternative substances taken from ECHA-CHEM (if not stated otherwise; ECHA 2015a); data for EDC are from OECD (2002)

Substance Molecular Vapour Log PO/W Chemical Biodegradability Water weight pressure Class for Koc solubility (g/Mol) (Pa) QSAR [mg/L] EDC 98.96 81300 1.45 Predominantly Not ready 8490-9000 (20°C) hydrophobics biodegradable (20 °C)

DCM 84.93 58400 1.25 Predominantly Ready 13200 (25°C) hydrophobics biodegradable * (25°C) *In the OECD SIDS report it was concluded that the substance is not readily biodegradable under non-adapted conditions, based on results from several non-standard biodegradation studies. A new OECD 301 D (closed bottle test) study is reported in the registration dossier in ECHA CHEM33, which showed ready biodegradability of the substance

No definite information on the efficiency of DCM compared to EDC is available. Therefore, for this assessment it is assumed that the same amount of solvent per production unit (on a weight basis) is required for both substances.

The following assumptions were used for modelling:

Workers assessment:

PROC 1: exposure duration 8 h, indoors, no LEV, no PPE

PROC 8b: exposure duration 1-4 h, outdoors, no LEV, respiratory protection (efficiency 95%)

Environmental assessment:

ERC 4: Release factors and the number of emission days according to ESVOC SpERC 1.1v1, '''#B''' used at site, STP available, all other conditions (e.g. STP discharge rate, river flow rate) with identical default values. 7.4 Results of the comparative exposure assessment and risk characterisation

The following tables show the results of the comparative exposure assessment and risk characterisation.

7.4.1 Occupational exposure

Similar exposure concentrations are obtained for EDC and DCM with respect to inhalation exposure of workers. However, RCRs are much lower for the latter.

33 http://echa.europa.eu/web/guest/home, assessed on 13 October 2014

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Table 7-6: Result of the comparative exposure and risk characterisation, workers EDC DCM PROC 1: 0.041 mg/m3 0.035 mg/m3 Exposure concentration, chronic, inhalation PROC 1: RCR 2.47 0.0001 PROC 8b: 13.0 mg/m3 11 mg/m3 Exposure concentration, chronic, inhalation PROC 8b: RCR 778 0.031

7.4.2 Environmental exposure

With regard to the environmental assessment, RCRs for the freshwater compartment are well below 1, if calculated with release factors from ESVOC SpERC 1.1.v1, although the RCR for DCM is higher by a factor of 7. In conclusion, whereas environmental exposures are considered manageable for both substances, DCM is considered to be less favourable, due to a lower PNECfreshwater.

Table 7-7: Result of the comparative exposure and risk characterisation, environment EDC DCM ERC 4 (ESVOC SpERC 1.1v1) – local PEC, freshwater: 0.0086 mg/L 0.0051 mg/L RCR 0.0078 0.019

7.4.3 Conclusions

Based on these quantitative considerations, the alternative substance DCM seems to be advantageous with regard to potential for human health effects.

It appears to lead to slightly higher RCRs for the aquatic environment compared to 1,2- dichloroethane (due to a lower PNECfreshwater, attenuated by better biodegradability).

In conclusion, DCM is considered to lead to reduced risks for humans (and similar risks for the environment), when used as a substitute for EDC.

For 1,2,4-trifluorobenzene, there aren’t sufficient data available to assess the substance quantitatively. Therefore, for the time being, it cannot be stated that the substance leads to reduced risks for humans and the environment, when used as a substitute for EDC.

7.4.4 References for Annex 1

Benbrahim-Tallaa, L.; Lauby-Secretan, B.; Loomis, D.; Guyton, K.Z.; Grosse, Y.; El Ghissassi, F.; Bouvard, V.; Guha, N.; Mattock, H.; Straif, K. (2014) Carcinogenicity of perfluorooctanoic acid, tetrafluoroethylene, dichloromethane, 1,2- dichloropropane, and 1,3-propane sultone The Lancet Oncology, 15, 924-925

Black, J.A.; Birge, W.J.; McDonnell, W.E.; Westerman, A.G.; Ramey, B.A.; Bruser, D.M. (1982) The Aquatic Toxicity of Organic Compounds to Embryo-larval Stages of Fish and Amphibians University of Kentucky Water Resources Research Institute

Brack, W.; Rottler, H. (1994) Toxicity testing of highly volatile chemicals with green algae: a new assay

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Environmental Science and Pollution Research International, 1, 223-228

Bringmann, G.; Kühn, R. (1978) Grenzwerte der Schadwirkung wassergefährdender Stoffe gegen Blaualgen (Microcystis aeruginosa) und Grünalgen (Scenedesmus quadricauda) im Zellvermehrungshemmtest Vom Wasser, 50, 45-60

Canadian Environmental Protection Act (1993) Priority Substances List Assessment Report. Dichloromethane Minister of Supply and Services Canada

Canadian Environmental Protection Act (1994) Priority Substances List Assessment Report. 1,2-Dichloroethane Minister of Supply and Services Canada

ECB, European Chemicals Bureau (2003) European Union Risk Assessment Report: 1,2,4-Trichlorobenzene. 2nd Priority List, Vol. 26 EUR 20540 EN. European Commission. Joint Research Centre

ECHA, European Chemicals Agency (2008) Guidance on information requirements and chemical safety assessment. Chapter R.10: Characterisation of dose [concentration]-response for environment http://guidance.echa.europa.eu/

ECHA, European Chemicals Agency (2012) Guidance on information requirements and chemical safety assessment. Chapter R.8: Characterisation of dose [concentration]-response for human health. Version: 2.1 online: http://echa.europa.eu/documents/10162/17224/information_requirements_r8_en.pdf

ECHA, European Chemicals Agency (2015a) Information on Chemicals - Registered Substances Online: http://echa.europa.eu/web/guest/information-on-chemicals/registered-substances

ECHA, European Chemicals Agency (2015b) Application for Authorisation: Establishing a Reference Dose Response Relationship for Carcinogenicity of 1,2-Dichloroethane. RAC/33/2015/09 Rev1 Final Helsinki, Finland

IARC, International Agency for Research on Cancer (1999) IARC Monographs on the Evaluation of Carcinogenic Risks to Humans. Vol. 71. Re-Evaluation of some Organic Chemicals, Hydrazine and Hydrogen Peroxide (Part 1-3) WHO, World Health Organization, Geneva

Mennear, J.H.; McConnell, E.E.; Huff, J.E.; Renne, R.A.; Giddens, E. (1988) Inhalation toxicology and carcinogenesis studies of methylene chloride in F344/N rats and B6C3F1 mice Annals of the New York Academy of Sciences, 534, 343-351

NTP, National Toxicology Program (1986)

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 109

Toxicology and Carcinogenesis Studies of Dichloromethane (Methylene Chloride) in F344/N Rats and B6C3F1 Mice (Inhalation Studies). TR 306 U.S. Department of Health and Human Services Public Health Service

OECD, Organisation for Economic Co-Operation and Development (2002) SIDS Initial Assessment Report for SIAM 14 (Paris, France, 26-28 March 2002). 1,2-Dichloroethane http://www.chem.unep.ch/irptc/sids/OECDSIDS/indexcasnumb.htm

Samoiloff, M. (1990) Technical methods section. The nematode toxicity assay using Panagrellus redivivus Toxicity Assessment, 5, 309-318

Samoiloff, M.R.; Schulz, S.; Jordan, Y.; Denich, K.; Arnott, E. (1980) A rapid simple long-term toxicity assay for aquatic contaminants using the nematode panagrellus redivivus Canadian Journal of Fisheries and Aquatic Sciences, 37, 1167-1174

SCOEL, Scientific Committee on Occupational Exposure Limits (2009) Recommendation from the Scientific Committee on Occupational Exposure Limits for Methylene chloride (dichloromethane). SCOEL/SUM/130 June 2009 European Commission, Employment, Social Affairs and Inclusion http://ec.europa.eu/social/keyDocuments.jsp?type=0&policyArea=82&subCategory=153&country=0 &year=0&advSearchKey=recommendation&mode=advancedSubmit&langId=en

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 110

8 Annex 2: Dow IER Products

Tables 8-1 to 8-6 provide an extract of the wide range of IER products marketed by Dow Water & Process Solutions. The downstream market for IERs (and SAC ERs, more specifically) is discussed in detail in the corresponding SEA document.

Table 8-1: Industrial water resins Trade name Uses Strong base anion resins AMBERJET™ 4000 Cl Packed bed and standard industrial demineralisation systems AMBERJET™ 4200 Cl Polishing mixed beds for industrial water treatment systems AMBERJET™ 4200 OH Polishing mixed beds for power generation water treatment systems Working mixed beds for ultrapure water production systems AMBERJET™ 4600 Cl Packed bed and standard industrial demineralisation systems Specialty industrial water treatment applications AMBERLITE™ IRA400 Cl Metal plating waste treatment Precious metal recovery from water AMBERLITE™ IRA402 Cl Co-flow industrial water demineralisation AMBERLITE™ IRA405 Cl Co-flow industrial water demineralisation of high organic content waters AMBERLITE™ IRA410 Cl Co-flow industrial water demineralisation AMBERLITE™ IRA458 Cl Co-flow industrial water demineralisation AMBERLITE™ IRA458RF Cl Packed bed industrial water demineralisation AMBERLITE™ IRA478RF Cl Packed bed industrial water demineralisation AMBERLITE™ IRA900 Cl Co-flow industrial water demineralisation AMBERLITE™ IRA900RF Cl Packed bed industrial water demineralisation AMBERLITE™ IRA910 Cl Co-flow industrial water demineralisation AMBERLITE™ IRA958 Cl Organic scavenging in industrial water treatment systems Industrial demineralisation of high organic fouling waters where low silica DOWEX™ MARATHON 11 is desired Industrial Demineralisation DOWEX™ MARATHON A Packed bed systems Polishing mixed beds for industrial water DOWEX™ MARATHON A (OH) Power station make-up water systems Ultrapure water primary demineralisation systems DOWEX™ MARATHON A LB Layered bed industrial water demineralisation systems Industrial Demineralisation DOWEX™ MARATHON A2 Packed bed systems Industrial demineralisation DOWEX™ MARATHON MSA High organic waters Packed bed systems DOWEX™ UPCORE MONO A2- UPCORE packed bed systems 500 Industrial demineralisation UPCORE packed bed systems DOWEX™ UPCORE MONO A-500 Industrial demineralisation UPCORE layered bed systems DOWEX™ UPCORE MONO A-625 Industrial demineralisation DOWEX™ UPCORE MONO MA- UPCORE packed bed systems 600 Industrial demineralisation Weak acid cation resins AMBERLITE™ IRC86 Dealkalisation of industrial waters Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 111

Table 8-1: Industrial water resins Trade name Uses Reverse osmosis pretreatment Partial water softening Dealkalisation of industrial waters AMBERLITE™ IRC86RF Reverse osmosis pretreatment Partial water softening Dealkalisation of industrial waters AMBERLITE™ IRC86SB Reverse osmosis pretreatment Partial water softening Industrial Dealkalisation DOWEX™ MAC-3 High TDS softening (Na+ cycle) Thermal enhanced oil recovery (tEOR) water treatment UPCORE packed and layered bed systems DOWEX™ UPCORE MAC-3 Industrial demineralisation Pre-mixed, mixed bed resins AMBERLITE™ MB10 General industrial water treatment Industrial demineralisation applications where <15 meg-ohm, water quality is needed AMBERLITE™ MB20 Once-use water treatment cartridges Laboratory cartridges Small industrial demineralisation applications where <10 meg-ohm, water quality is needed AMBERLITE™ MB6113 Once-use water treatment cartridges Laboratory cartridges AMBERLITE™ MB9L Metal electro-errosion systems DOWEX™ MARATHON MR-3 Polishing demineralised water Inert resins AMBERLITE™ RF14 AMBERPACK systems UPCORE packed and layered bed systems DOWEX™ UPCORE IF-62 Industrial demineralisation Strong acid cation resins Packed bed and standard industrial water demineralisation systems AMBERJET™ 1000 H Polishing mixed beds for industrial water and power generation systems Working mixed beds for ultra pure water production systems Packed bed and standard industrial water softening systems AMBERJET™ 1000 Na Packed bed and standard industrial water demineralisation systems Hot lime softening AMBERLITE™ 200C Na Industrial steam condensate treatment AMBERLITE™ 252RF H Packed bed industrial demineralisation systems AMBERLITE™ IR120 H Co-flow industrial water demineralisation Co-flow industrial water softening systems AMBERLITE™ IR120 Na Industrial water demineralisation Industrial Softening DOWEX™ MARATHON C Packed bed systems Industrial demineralisation DOWEX™ MARATHON C (H) Packed bed systems Industrial Softening; DOWEX™ MARATHON C-10 Packed bed systems Industrial demineralisation Polishing mixed beds DOWEX™ MARATHON C-10 (H) Packed bed systems Layered bed systems DOWEX™ MARATHON MSC Industrial Softening

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 112

Table 8-1: Industrial water resins Trade name Uses Packed bed systems Hot lime softening Na+ cycle steam condensate treatment Industrial demineralisation DOWEX™ MARATHON MSC (H) Packed bed systems DOWEX™ UPCORE MONO C-600 UPCORE packed bed systems (H) Industrial demineralisation DOWEX™ UPCORE™ MONO C- UPCORE packed bed systems 600 Industrial demineralisation Weak base anion resins AMBERLITE™ IRA67 Industrial water demineralisation AMBERLITE™ IRA67RF Packed bed Industrial water demineralisation AMBERLITE™ IRA70RF Packed bed Industrial water demineralisation AMBERLITE™ IRA96 Standard (Co-flow) industrial water demineralisation systems AMBERLITE™ IRA96RF Packed bed industrial water demineralisation systems AMBERLITE™ IRA96SB Layered bed industrial water demineralisation systems Industrial demineralisation DOWEX™ MARATHON WBA Layered bed systems DOWEX™ MARATHON WBA-2 Industrial demineralisation UPCORE packed bed systems DOWEX™ UPCORE MONO WB- Layered bed systems 500 Industrial demineralisation Source: Dow Water & Process Solutions Internet Site http://www.dowwaterandprocess.com/en/products/ion_exchange_resins)

Table 8-2: Power generation resins Trade name Uses Mixed bed resins Primary side Chemical Volume Control Systems (CVS) in PWR AMBERLITE™ IRN150 Nuclear power generating facilities Reactor water clean-up and rad waste systems BWR deep bed condensate polishing Reactor water clean-up systems AMBERLITE™ IRN160 PWR Chemical volume control (CVS) systems Radwaste deionisation BWR deep bed condensate polishing Reactor water clean-up systems AMBERLITE™ IRN170 PWR Chemical volume control (CVS) systems Radwaste deionisation Primary water chemistry control in PWR nuclear power AMBERLITE™ IRN217 operations Primary water chemistry control in PWR nuclear power AMBERLITE™ IRN317 operations Primary loop purification (CVCS) in PWR nuclear reactors AMBERLITE™ IRN9687 Rad waste and clean up Primary water chemistry control in PWR nuclear power operations AMBERLITE™IRN9882 Decontamination of radioactive circuits Reactor water cleanup systems Strong base anion exchange resins AMBERJET™ 9000 OH Regenerable, deep bed condensate polishing for PWR nuclear

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 113

Table 8-2: Power generation resins Trade name Uses Power generation facilities Condensate polishing for fossil power plants Regenerable, deep bed condensate polishing for PWR nuclear AMBERJET™ 9800 Cl Power generation facilities Condensate polishing for fossil power plants Primary water chemistry control in PWR nuclear power operations AMBERLITE™ IRN78 Decontamination of radioactive circuits Reactor water cleanup systems Primary water chemistry control in PWR nuclear power operations AMBERLITE™ IRN9766 Decontamination of radioactive circuits Reactor water cleanup systems Condensate polishing mixed beds AMBERSEP™ 900 OH Fossil fuel electrical power generation For condensate polishing; AMBERSEP™ 900 SO4 For mixed bed applications where organic fouling is a risk Industrial demineralisation DOWEX™ MARATHON MSA High organic waters Packed bed systems Nuclear Power, regenerable condensate polishing DOWEX™ MONOSPHERE™ 550A (OH) Fossil power condensate polishing Mixed bed polishing of demineralised water Inert Resins Nuclear Power, regenerable condensate polishing DOWEX™ MONOSPHERE™ 600BB Fossil power condensate polishing Mixed bed polishing of demineralised water Strong acid cation exchange resins PWR condensate polishing regenerable mixed beds AMBERJET™ 1600 H PWR condensate polishing cation pre-beds Power generation condensate polishing systems using alternative anime chemistry AMBERJET™ 2000 H Condensate polishing systems where superior oxidative stability is required AMBERJET™ 2800 H Power generation condensate polishing Primary water chemistry control in PWR nuclear power operations AMBERLITE™ IRN77 Decontamination of radioactive circuits Control of Lithium 7 content of the reactor coolant Primary water chemistry control in PWR nuclear power operations AMBERLITE™ IRN9652 Decontamination of radioactive circuits Reactor water cleanup systems Cation component of BWR Condensate Polishing Mixed Beds Primary water chemistry control in PWR nuclear power AMBERLITE™ IRN97 H operations Decontamination of radioactive circuits Control of Lithium 7 content of the reactor coolant Cation component of BWR Condensate Polishing Mixed Beds Primary water chemistry control in PWR nuclear power AMBERLITE™ IRN99 operations Decontamination of radioactive circuits Control of Lithium 7 content of the reactor coolant Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 114

Table 8-2: Power generation resins Trade name Uses AMBERSEP™ 252 H Condensate polishing mixed beds Industrial demineralisation DOWEX™ MARATHON MSC (H) Packed bed systems Nuclear Power (PWR) condensate polishing DOWEX™ MONOSPHERE™ 1400PC (H) Ethanolamine chemistry Nuclear Power, regenerable condensate polishing DOWEX™ MONOSPHERE™ 650C (H) Fossil power condensate polishing Mixed bed polishing of demineralised water Source: Dow Water & Process Solutions Internet Site (http://www.dowwaterandprocess.com/en/products/ion_exchange_resins)

Table 8-3: Ultrapure water grade resins Trade name Uses Strong acid cation exchange resins Regenerable mixed bed and other polishing units in the production of water for the semi-conductor and AMBERJET™ UP1400 Electronic industries Single bed or mixed bed columns Semiconductors DOWEX™ MONOSPHERE™ 650C UPW (H) Ultrapure water Strong base anion exchange resins Regenerable mixed bed and other polishing units in the production of water for the semi-conductor and AMBERJET™ UP4000 electronic industries Single bed or mixed bed columns Ultrapure water production DOWEX™ MONOSPHERE™ 550A UPW (OH) Semiconductor manufacturing Electronic device production Mixed bed polishing resins Polishing mixed bed resin for semiconductor devices AMBERJET™ UP6040 and other electronics applications Polishing mixed bed resin for display devices and AMBERJET™ UP6150 Other electronic applications Semiconductors DOWEX™ MONOSPHERE™ MR-3 UPW Ultrapure water Semiconductors DOWEX™ MONOSPHERE™ MR-450 UPW Ultrapure water Source: Dow Water & Process Solutions Internet Site (http://www.dowwaterandprocess.com/en/products/ion_exchange_resins)

Table 8-4: Chemical process and mining resins Trade name Uses Strong base anion exchange resins Uranium Recovery in fixed beds AMBERSEP™ 400 HCO3 Uranium recovery from alkaline leach AMBERSEP™ 400 SO4 Uranium Recovery in fixed beds AMBERSEP™ 4400 Cl Uranium recovery in NIMCIX and other CCIX systems AMBERSEP™ 4400 HCO3 Uranium recovery in NIMCIX and other CCIX systems AMBERSEP™ 4550 Cl Uranium recovery in NIMCIX and other CCIX systems AMBERSEP™ 920U Cl Uranium recovery in RIP systems Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 115

Table 8-4: Chemical process and mining resins Trade name Uses AMBERSEP™ 920U SO4 Uranium recovery in U-shape/ Higgins loop systems AMBERSEP™ 920UHC SO4 Uranium recovery in RIP systems AMBERSEP™ 920UXL Cl Uranium recovery in RIP systems AMBERSEP™ 920UXL SO4 Uranium recovery in RIP systems Uranium recovery from high chloride or sulfate AMBERSEP™ 940U leachates Gold recovery for cyanide leaches DOWEX™ 21K 16/20 Uranium recovery from low chloride leachates Fixed bed systems Gold recovery Copper recovery DOWEX™ 21K XLT Zinc recovery Uranium recovery Fixed bed systems Uranium Recovery DOWEX™ RPU Low chloride leaches Porter systems DOWEX™ XZ 91419 Gold mining Strong acid cation exchange resins Biodiesel purification Salt removal AMBERLITE™ BD10DRY Soap removal Residual glycerol removal Catalyst recovery AMBERLYST™ 40 Metal removal from organic streams Biodiesel feedstock purification AMBERSEP™ BD19 Esterification catalyst protection Glycerol purification AMBERSEP™ BD50 Biodiesel manufacturing Produced Water treatment DOWEX™ G-26 (H) Coal Seam Gas produced water Higgins Loop systems Weak base anion resin Deacidification AMBERLYST™ A23 Chemical purification Chelating resins Flue gas desulfurization blow-down treatment AMBERLITE™ IRA743 Boron removal from concentrated MgCl2 solutions Irrigation water and waste water Brine softening for chlor-alkali industry AMBERLITE™ IRC747 Metals recovery AMBERLITE™ IRC747UPS Brine softening for chlor-alkali industry Brine softening for chlor-alkali industry AMBERLITE™ IRC748I Metal removal from plating wastes Catalyst recovery Mercury removal from Chloralkali brines streams; AMBERSEP™ GT74 FGD blowdown Oil field produced water DOWEX™ M4195 Mining Copper production and recovery DOWEX™ XUS 43578 Nickel recovery Chromate recovery

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 116

Table 8-4: Chemical process and mining resins Trade name Uses Zinc production Mercury removal DOWEX™ XUS 43600 Thiouronium Platinum group metal recovery Mercury removal from waste water DOWEX™ XUS 43604 Flue gas desulfurization blow down Chloralkali streams for mercury cell electrodes DOWEX™ XUS 43605 Mining Amphoteric resins DOWEX™ Retardion 11A8 Purification of Caustic Soda Source: Dow Water & Process Solutions Internet Site (http://www.dowwaterandprocess.com/en/products/ion_exchange_resins)

Table 8-5: Drinking water grade resins Trade name Uses Arsenic removal ADSORBSIA™ AS600 Drinking water Boron removal from desalinated sea water AMBERLITE™ PWA10 Boron removal from groundwater AMBERLITE™ PWA12 CARIX municipal water treament system AMBERLITE™ PWA15 Nitrate removal in packed bed systems Municipal drinking water systems AMBERLITE™ PWA17 Nitrate removal Uranium removal Nitrate removal from potable water in standard or AMBERLITE™ PWA5 packed bed systems Perchlorate removal Chromate removal from drinking water AMBERLITE™ PWA7 Groundwater remediation Drinking water AMBERLITE™ PWA8 Uranyl removal Natural Organic matter (NOM) removal from drinking AMBERLITE™ PWA9 water THM reduction in drinking water AMBERLITE™ PWC14 Na Municipal water softening systems DOWEX™ PSR-2 Perchlorate removal from drinking water Radium removal from drinking water DOWEX™ RSC Mine effluent applications Removal of NOM from drinking water DOWEX™ TAN-1 Tannin removal, reduction of THM precursors Source: Dow Water & Process Solutions Internet Site (http://www.dowwaterandprocess.com/en/products/ion_exchange_resins)

Table 8-6: Residential and commercial resins Trade name Uses Weak acid cation POU resins Drinking water purification IMAC™ HP333 Carafe and pitcher treatment devices IMAC™ HP335 - Strong base anion exchange resins IMAC™ HP555 Nitrate removal from drinking water Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 117

Table 8-6: Residential and commercial resins Trade name Uses Point-of-use cartridges Strong acid cation softening resins AMBERLITE™ SR1L NA Home water softeners DOWEX™ HCR S/S FF Residential water softeners DOWEX™ HCR-S/S Residential water softeners DOWEX™ MONOSPHERE™ C-350 Compact home water softeners Source: Dow Water & Process Solutions Internet Site (http://www.dowwaterandprocess.com/en/products/ion_exchange_resins)

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 118

9 Annex 3: Substances excluded from further analysis following screening step 2

Table 9-1, below, highlights the 516 potential alternative substances excluded from further consideration by the applicants following the second screening stage (as discussed in Section 4.2). All of these substances were either modelled or demonstrated to have RED values >1. As indicated (and validated) by the applicants’ R&D activities, the use of these solvents would result in poor quality SAC ERs and also affect the applicants’ processing parameters, resulting in smaller yields, longer processing times, and therefore higher costs. Consequently, these substances can be excluded on both economic feasibility and technical feasibility grounds.

Table 9-1: Potential alternative substances excluded from further analysis (RED values >1) Substance CAS No Substance CAS No 1,1,1-Trichloroethane 71-55-6 Ethylene cyanohydrins 109-78-4 1,1,2,2-Tetrabromoethane (R-130b4) 79-27-6 Ethylene dibromide 106-93-4 1,1,2-Trichlorotrifluoroethane (R-113) 76-13-1 Ethylene glycol 107-21-1 1,1-Dimethoxyethane (dimethyl acetal) 110-71-4 Ethylene glycol diacetate (egda) 111-55-7 1,1-Dimethylcyclohexane 590-66-9 Ethylene glycol diethyl ether 629-14-1 1,1-Dimethylhydrazine 88733-28-2 Ethylene glycol dimethyl ether (glyme) 110-71-4 1,2,4-Trichlorobenzene 120-82-1 Ethylene glycol di-n-butyl ether 112-48-1 1,2,4-Trimethylbenzene 95-63-6 Ethylene glycol ethyl ether N/A 1,2-Dichlorotetrafluoroethane (Freon 76-14-2 Ethylene glycol ethyl ether acetate N/A 114) 1,2-Dichlorotetrafluoroethane (R-114) 76-14-2 Ethylene glycol isobutyl ether N/A 1,2-Diethylbenzene 135-01-3 Ethylene glycol isopropyl ether N/A 1,2-Dimethylcyclohexane 583-57-3 Ethylene glycol methyl ether N/A 1,2-Hexanediol N/A Ethylene glycol methyl ether acetate N/A 1,2-Hhda (1,2-Hexanedioldiacrylate) N/A Ethylene glycol methylphenyl ether N/A 1,3,5-Triisopropyl benzene 717-74-8 Ethylene glycol monobenzyl ether N/A 1,3-Butadiene 106-99-0 Ethylene glycol monobutyl ether 111-76-2 1,3-Butanediol 107-88-0 Ethylene glycol monohexyl ether 112-25-4 1,3-Diethylbenzene 141-93-5 Ethylene glycol n-butyl ether acetate N/A 1,3-Diisopropylbenzene 99-62-7 Ethylene glycol n-propyl ether 83855-85-0 1,3-Dimethylcyclohexane 591-21-9 Ethylene glycol t-butyl ether N/A 1,3-Propanediol diacetate 628-66-0 Ethylene oxide 75-21-8 1,3-Propanediol monoacetate 36678-05-4 Ethylenediamine 107-15-3 1,4-Butanediol 110-63-4 Exxate 1000 solvent (decyl acetate) N/A 1,4-Diethylbenzene 105-05-5 Exxate 1300 solvent (tridecyl acetate) 1072-33-9 1,4-Diisopropylbenzene 100-18-5 Exxate 600 solvent (hexyl acetate) N/A 1,4-Dimethylcyclohexane 589-90-2 Exxate 700 solvent (heptyl acetate) N/A 1-Bromonaphthalene 90-11-9 Exxate 800 solvent (octyl acetate) N/A 1-Butene N/A Exxate 900 solvent (nonyl acetate) 143-13-5 1-Chlorobutane 109-69-3 Exxon mineral spirits (varsol 1) N/A 1-Chloropropane 540-54-5 Exxon vm&p naphtha N/A 1-Cyclohexyl ethanol 1193-81-3 Exxsol d110 N/A 1-Decene 872-05-9 Exxsol d130 N/A 1-Dodecene 112-41-4 Exxsol d-60 solvent N/A

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 119

Table 9-1: Potential alternative substances excluded from further analysis (RED values >1) Substance CAS No Substance CAS No 1-Heptene 592-76-7 Formamide 75-12-7 1-Hexene 592-41-6 Formic acid 64-18-6 1-Methyl cyclohexene N/A Furan 110-00-9 1-Methylnaphthalene 90-12-0 Furfural 98-01-1 1-Nitropropane 108-03-2 Furfuryl alcohol 98-00-0 1-Octene 111-66-0 Gamma-butyrolactone 96-48-0 1-Pentene 109-67-1 Glycerin 56-81-5 2-(Methylamino)Ethanol 109-83-1 Glycerin trimethyl ether N/A 2,2,4-Trimethylpentane (Isooctane) 540-84-1 Glycidyl lauril ether N/A 2,2-Dimethylbutane 75-83-2 Guaiacol (2-methoxyphenol) 90-05-1 2,2-Dimethylpentane 590-35-2 Heptylglycerol N/A 2,3-Dimethylbutane 79-29-8 Hexafluorobenzene 392-56-3 2,4 Dichloronitrobenzene 611-06-3 Hexafluoroisopropanol N/A 2,6,8-Trimethyl-4-nonanol N/A Hexamethylenediamine N/A 2-Chlorobutane 78-86-4 Hexamethylphosphorotriamide 680-31-9 2-Chloropropyl octanoate N/A Hexyl carbitol glycol ether solvent N/A 2-Decanol 1120-06-5 Hexyl cellosolve glycol ether solvent N/A 2-Ethyl butyl alcohol N/A Hexylbenzene 1077-16-3 2-Ethylhexyl acetate 103-09-3 Hexylene glycol 99210-90-9 2-Ethylhexyl acrylate 103-11-7 Hexylene glycol diacetate 6222-17-9 2-Ethylhexyl alcohol N/A Hydroxyethylmethacrylate 868-77-9 2-Hydroxyethyl-3-ethoxypropionate N/A Hydroxypropylmethacrylate N/A 2-Hydroxypropyl octanoate 68332-79-6 Isoamyl acetate 123-92-2 2-Hydroxypropyl-3-ethoxypropionate N/A Isoamyl alcohol (3-methyl-1-butanol) 123-51-3 2-Methoxy methyl lactate N/A Isobutyl acetate N/A 2-Methyl-1-butanol 34713-94-5 Isobutyl acrylate 106-63-8 2-Methyl-1-butene N/A Isobutyl alcohol N/A 2-Methyl-1-pentene 544-76-3 Isobutyl benzene 538-93-2 2-Methyl-2-butanol (T-Amyl Alcohol) 75-85-4 Isobutyl heptyl ketone 123-18-2 2-Methylpentane 107-83-5 Isobutyl isobutyrate 97-85-8 2-Nitropropane 79-46-9 Iso-butylamine N/A 2-Octanol N/A Isobutylene oxide 558-30-5 2-Pentanol 26184-62-3 Isooctyl alcohol 26952-21-6 2-Pyrrolidone (gamma-butyrolactam) 616-45-5 Isopar e solvent N/A 3,4-Dichlorotoluene 95-75-0 Isopar g solvent N/A 3-Chloro-1-propanol 627-30-5 Isopar h solvent N/A 3-Methoxybutanol 2517-43-3 Isopar k solvent N/A 3-Methoxybutyl acetate 4435-53-4 Isopar l solvent N/A 3-Methyl-3-methoxybutanol 56539-66-3 Isopar m solvent N/A 3-Methyl-3-methoxybutyl acetate 103429-90- Isopar v solvent N/A 9 3-Pentanol (Diethyl carbinol) 584-02-1 Isopentane 78-78-4 4,4-Methylene-bis-phenylisocyanate 58180-53-3 Isopentanoic acid N/A 4-Methylanisole 104-93-8 Isophoronediamine 2855-13-2 4-Methylcyclohexane 108-87-2 Isoprene (2-methyl-1,3-butadiene) 78-79-5 5-Oxohexyl acetate N/A Isopropanolamine 78-96-6 Acetal (1,1-diethoxyethane) N/A Isopropyl acetate 108-21-4 Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 120

Table 9-1: Potential alternative substances excluded from further analysis (RED values >1) Substance CAS No Substance CAS No Acetaldehyde 75-07-0 Isopropyl alcohol 67-63-0 Acetamide 60-35-5 Isopropyl lactate 63697-00-7 Acetic acid 64-19-7 Isopropyl palmitate N/A Acetic anhydride N/A Isopropylamine 75-31-0 Acetone 67-64-1 Isopropylbiphenyl 25640-78-2 Acetonitrile 75-05-8 Isopropylglycerol N/A Acetyl acetone (2,4-pentanedione) 123-54-6 Isopropylhexane N/A Acrylamide 79-06-1 Kerosene 8008-20-6 Acrylic acid 79-10-7 Lactic acid (dl-lactic acid) 50-21-5 Acrylonitrile 107-13-1 M-cresol 108-39-4 Allyl alcohol 107-18-6 M-dichlorobenzene 541-73-1 Aminated dowanol dpnb N/A Mesitylene (1,3,5-trimethylbenzene) 108-67-8 Aminated dowanol dpnp N/A Methacrylamide 79-39-0 Aminated dowanol pm N/A Methacrylic acid 79-41-4 Aminated dowanol pnb N/A Methacrylonitrile 126-98-7 Aminated dowanol pnp N/A Methoxyacetone 5878-19-3 Aminated dowanol tpnb N/A Methoxydiglycol N/A Aminated dowanol tpnp N/A Methyl acetate 79-20-9 Aminated-dowanol-dpm N/A Methyl acrylate 96-33-3 Aminated-dowanol-tpm N/A Methyl alcohol 67-56-1 Amyl alcohol 71-41-0 Methyl amyl acetate 108-84-9 Amylbenzene 74296-33-6 Methyl carbitol glycol ether solvent N/A Aniline 62-53-3 Methyl chloride 74-87-3 Benzene 71-43-2 Methyl formate 107-31-3 Benzophenone 119-61-9 Methyl isoamyl ketone N/A Benzyl acetate 140-11-4 Methyl isobutyl carbinol 108-11-2 Benzyl alcohol 100-51-6 Methyl isobutyl ketone 108-10-1 Beta-propiolactone 57-57-8 Methyl isobutyl ketone 108-10-1 Biphenyl 92-52-4 Methyl isopropyl ketone 563-80-4 Bis(m-phenoxyphenyl) ether 748-30-1 Methyl lactate 27871-49-4 Bromobenzene 108-86-1 Methyl n-butyl ketone 591-78-6 Bromoform 75-25-2 Methyl oleate 112-62-9 Bromotrifluoromethane (r-13b1) 75-63-8 Methyl propionate 554-12-1 Butoxytriglycol N/A Methyl salicylate (wintergreen oil) 119-36-8 Butyl benzoate 136-60-7 Methyl soyate 67784-80-9 Butyl carbitol acetate glycol ether N/A Methylal (dimethoxyethane) 109-87-5 Butyl carbitol glycol ether solvent N/A Methylcyclohexane 108-87-2 Butyl cellosolve acetate glycol ether N/A Methylethylketoxime 96-29-7 Butyl cellosolve glycol ether solvent N/A Methylisocyanate N/A Butyl glycerol N/A Methyl-t-butyl ether (mtbe) 1634-04-4 Butyl stearate 123-95-5 Monoethanolamine 141-43-5 Butyl valerate 591-68-4 Morpholine 110-91-8 Butylamine 109-73-9 M-xylene 108-38-3 Butylcyclohexane 1678-93-9 N propyl benzene 103-65-1 Butylene glycol butyl ether N/A N,n-diethyl formamide 617-84-5 Butylene glycol ethyl ether N/A N,n-dimethylacetamide 127-19-5 Butylene glycol methyl ether N/A N-amyl acetate 628-63-7 Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 121

Table 9-1: Potential alternative substances excluded from further analysis (RED values >1) Substance CAS No Substance CAS No Butyraldehyde 123-72-8 N-butane 106-97-8 Butyronitrile 109-74-0 N-butyl acetate 123-86-4 Carbitol acetate glycol ether N/A N-butyl acrylate 141-32-2 Carbitol glycol ether solvent N/A N-butyl alcohol 71-36-3 Carbon disulfide 75-15-0 N-butyl benzene 104-51-8 Carbon tetrachloride 56-23-5 N-butyl butyrate 109-21-7 Chlorobenzene 108-90-7 N-butyl formate 592-84-7 Chlorodifluoromethane (r-22) 75-45-6 N-butyl lactate 138-22-7 Chloroform 67-66-3 N-butyl methacrylate 97-88-1 Cis-decalin 493-01-6 N-butyl propionate 590-01-2 Cumene 98-82-8 N-butyric acid 107-92-6 Cyclohexane 110-82-7 N-decane N/A Cyclohexanol 108-93-0 N-decanol 112-30-1 Cyclohexene 110-83-8 N-dodecane N/A Cyclohexylamine 108-91-8 N-eicosane 112-95-8 Cyclohexylbenzene 827-52-1 N-heptane 142-82-5 Cyclohexylmethacrylate 101-43-9 N-heptyl alcohol N/A Cyclopentane 287-92-3 N-hexadecane 763-29-1 Dalpad a glycol ether solvent N/A N-hexane 110-54-3 Dalpad c glycol ether solvent N/A N-hexanol 111-27-3 Dalpad d glycol ether solvent N/A N-hexyl amine 111-26-2 Dalpad p glycol ether solvent N/A Nitroethane 79-24-3 Dbe dibasic ester 95481-62-2 Nitromethane 75-52-5 Dbe-2 dibasic ester N/A N-nonane 111-84-2 Dbe-3 dibasic ester N/A N-octane 111-65-9 Dbe-4 dibasic ester N/A N-octyl alcohol 111-87-5 Dbe-5 dibasic ester N/A Nonyl phenol 84852-15-3 Dbe-9 dibasic ester N/A Nonyl phenoxy ethanol N/A Diacetone alcohol 123-42-2 Norpar 12 solvent N/A Dibenzyl ether 103-50-4 Norpar 15 solvent N/A Dibutyl ether 142-96-1 N-pentane 109-66-0 Dichloro fluoromethane (freon21) 75-43-4 N-pentyl propionate 624-54-4 Dichlorodifluoromethane (freon 12) 75-71-8 N-propyl acetate 109-60-4 Dichlorodifluoromethane (r-12) 75-71-8 N-propyl alcohol 71-23-8 Dichlorofluoromethane (r-21) 75-43-4 N-propyl propionate 106-36-5 Dichlorohydrin (1,3-dichloro-2- 26545-73-3 N-propylamine 104810-31- propanol) 3 Dicyclohexyl N/A Octanoic acid 124-07-2 Diethanolamine 111-42-2 Oleic acid 112-80-1 Diethyl carbonate 105-58-8 Oleyl alcohol 143-28-2 Diethyl ether 60-29-7 O-xylene 95-47-6 Diethyl phthalate 84-66-2 P-dichlorobenzene 106-46-7 Diethyl sulfate 64-67-5 P-dioxane 123-91-1 Diethyl sulfide 352-93-2 Pentapropylene glycol methyl ether N/A Diethylamine 109-89-7 Penthachloroethane 76-01-7 Diethylaminoethanol 100-37-8 Pentoxone(4-methoxy-4-methyl-2- N/A pentanone Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 122

Table 9-1: Potential alternative substances excluded from further analysis (RED values >1) Substance CAS No Substance CAS No Diethylene glycol 111-46-6 Pentyl valerate 2173-56-0 Diethylene glycol diacetate 628-68-2 Perchloroethylene 127-18-4 Diethylene glycol diethyl ether 112-36-7 Perfluoro(dimethylcyclohexane) 3709-71-5 Diethylene glycol dimethyl ether 111-96-6 Perfluoroheptane 335-57-9 Diethylene glycol di-n-butyl ether 112-73-2 Perfluorohexane (pfc 5060) N/A Diethylene glycol distearate N/A Perfluoromethyl cyclohexane 355-02-2 Diethylene glycol ethyl ether N/A Perfluoromethyl cyclohexane 355-02-2 Diethylene glycol ethyl ether acetate N/A Pg methyl ether propionate N/A Diethylene glycol hexyl ether N/A Phenol 108-95-2 Diethylene glycol monobutyl ether 112-34-5 Pinacol dimethyl ether N/A Diethylene glycol monomethyl ether N/A Proglyde dmm glycol diether N/A Diethylene glycol monopropyl ether N/A Propane 74-98-6 Diethylene glycol n-butyl ether acetate N/A Propane 1,2-diyl dioctanoate N/A Diethylene glycol phenyl ether 104-68-7 Propionaldehyde 123-38-6 Diethylenetriamine 111-40-0 Propionamide 79-05-0 Diisobutyl carbinol 108-82-7 Propionic acid 79-09-4 Diisobutyl ketone 108-83-8 Propionitrile 107-12-0 Diisopropyl ether N/A Propyl benzoate 2315-68-6 Dimethyl carbonate 616-38-6 Propyl cellosolve glycol ether solvent N/A Dimethyl formamide 68-12-2 Propyl formate 110-74-7 Dimethyl sulfone 67-71-0 Propylcyclohexane 1678-92-8 Dimethyl sulfoxide 67-68-5 Propylene carbonate 108-32-7 Dimethylamine 124-40-3 Propylene chlorohydrin 78-89-7 Dimethyldioxane N/A Propylene dichloride N/A Dimethylethanolamine 108-01-0 Propylene glycol N/A Di-n-butyl sebacate N/A Propylene glycol butyl ether acetate N/A Di-n-propylamine 142-84-7 Propylene glycol dimethyl ether 7778-85-0 Dipentene (limonene) 5989-27-5 Propylene glycol ethyl ether N/A Diphenyl oxide 101-84-8 Propylene glycol ethyl ether acetate N/A Dipropyl ketone 123-19-3 Propylene glycol isobutyl ether N/A Dipropylene glycol ethyl ether 15764-24-6 Propylene glycol isobutyl ether acetate N/A Dipropylene glycol isopropyl ether N/A Propylene glycol isopropyl ether 110-48-5 Dipropylene glycol methyl allyl ether N/A Propylene glycol isopropyl ether N/A acetate Dipropylene glycol n-hexyl ether N/A Propylene glycol methyl t-butyl ether N/A Dipropylene glycol propyl ether acetate N/A Propylene glycol n-hexyl ether N/A Dipropylene glycol t-butyl ether N/A Propylene glycol t-butyl ether 80763-10-6 Dipropylene glycol2 N/A Propylene oxide 75-56-9 Divinylbenzene hp 1321-74-0 P-xylene 106-42-3 D-limonene 5989-27-5 Resorcinol (1,3-benzenediol) 108-46-3 Dodecanol N/A Sc #28 N/A Dowanol dipph glycol ether N/A Sc #3 N/A Dowanol dpm glycol ether N/A Sec-butyl acetate 105-46-4 Dowanol dpma glycol ether acetate N/A Sec-butyl alcohol N/A Dowanol dpnb glycol ether N/A Shell sol 142ht N/A Dowanol dpnp glycol ether N/A Shellsol d38 N/A Dowanol eph glycol ether N/A Stearic acid 57-11-4 Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 123

Table 9-1: Potential alternative substances excluded from further analysis (RED values >1) Substance CAS No Substance CAS No Dowanol pgda N/A Stoddard solvent (rule 66 min. Spirits) N/A Dowanol pm glycol ether N/A Styrene 100-42-5 Dowanol pma glycol ether acetate 142300-82- Succinic anhydride 108-30-5 1 Dowanol pnb glycol ether N/A Sulfolane 126-33-0 Dowanol pnp glycol ether N/A T-butanol 75-65-0 Dowanol pph glycol ether N/A T-butyl acetate 540-88-5 y Dowanol tpm glycol ether N/A T-butyl amine 75-64-9 Dowanol tpnb glycol ether N/A T-butyl thiol N/A Dowanol tpnp glycol ether N/A Terpineol 8006-39-1 Dowfroth 250 N/A Tetradecane 629-59-4 Dowtherm q N/A Tetrahydrofurfuryl alcohol 97-99-4 Dpnb adipate N/A Tetralin (1,2,3,4- N/A tetrahydronaphthalene) Ecosoft ik N/A Tetramethyl urea 632-22-4 E-fame N/A Tetrapropylene glycol methyl ether N/A Ektapro eep solvent N/A Tetrapropylene glycol monobutyl ether N/A Ektasolve eeh (eg 2-ethylhexyl ether) N/A Texanol solvent N/A Epsilon-caprolactone 80137-66-2 Trans-decalin 493-02-7 Ethanethiol 75-08-1 Trichloroethylene 79-01-6 Ethoxytriglycol N/A Trichlorofluoromethane (r-11) 75-69-4 Ethyl acetate 141-78-6 Tridecyl alcohol N/A (78-93-3 y) Ethyl acrylate 140-88-5 Triethanolamine 102-71-6 Ethyl alcohol 161886-60- Triethyl phosphate 78-40-0 Ethyl alcohol, 95% N/A Triethylamine 121-44-8 Ethyl amyl ketone 541-85-5 Triethylene glycol 112-27-6 Ethyl benzene 100-41-4 Triethylene glycol ethyl ether N/A Ethyl butyl ketone 106-35-4 Triethylene glycol monobutyl ether 143-22-6 Ethyl chloride 19961-13-8 Triethylene glycol monoethyl ether N/A Ethyl chloroformate 541-41-3 Triethylene glycol monomethyl ether 112-35-6 Ethyl formate 109-94-4 Trifluoroethane 27987-06-0 Ethyl iodide 75-03-6 Trimethyl phosphate 512-56-1 Ethyl isocyanate N/A Trimethylbenzene 25551-13-7 Ethyl lactate 97-64-3 Tri-n-octyl amine 1116-76-3 Ethyl methacrylate 97-63-2 Tripropylene glycol dimethyl ether N/A Ethyl octanoate 106-32-1 Tripropylene glycol ethyl ether N/A Ethyl propionate 105-37-3 Tripropylene glycol isopropyl ether N/A Ethyl silicate 9044-80-8 Tripropylene glycol methyl ether N/A acetate Ethyl-2-ethoxypropionate 7737-40-8 Turpentine (alpha-pinene) 8052-14-0 Ethyl-3-ethoxypropionate 763-69-9 Urea 57-13-6 Ethylcylcohexane N/A Velate 262 (isodecyl benzoate) 120657-54- 7 Ethylene carbonate 96-49-1 Vinylidene chloride 75-35-4 Ethylene chlorohydrin (2- 107-07-3 Water 7732-18-5 chloroethanol)

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 124

10 Annex 4: Justifications for confidentiality claims

This document contains confidential business information and so cannot be made public as a whole. In particular, the publication of the submitted document must not cover items which were not made public by the applicants, i.e. financial plans and financial forecasts, sales plans, and other relevant information that may have an impact on the share price of the applicants.

The World Trade Organisation agreement on Trade-Related Aspects of Intellectual Property Rights (TRIPS) requires signatory members (including EU-members) to maintain protection of undisclosed information, including company know-how that has been subject to reasonable steps to keep it secret (under Article 39.2). Much of the information claimed confidential below falls under the protection of TRIPS or Competition Law and therefore its public disclosure must be prevented.

Particular care has been taken to minimise the presence of confidential information in the AoA document and thus the confidentiality claims made by the applicants. However, it is necessary to include some confidential information to provide the rapporteurs and Committees the necessary information to fully evaluate this AfA in more quantitative terms.

The justifications of confidentiality are given in the table below. These can be grouped in three categories:

1. Trade Secrets – Detailed information relating to manufacturing processes, e.g. quantity of EDC used per batch, etc.

2. Business Secrets – Financial Information e.g. project cost estimates, cost of EDC etc.

3. Other Information – E.g. public disclosure of an association between EDC and specific products.

Note: In this public version of the AoA the table of justifications has been removed as they are also considered to be confidential.

Use number: 1 Legal name of the applicants: Dow Italia Srl and Rohm and Haas France S.A.S. 125

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