DOCSLIB.ORG

The Nordic Expert Group for Criteria Documentation of Health Risks from Chemicals and the Dutch Expert Committee on Occupational Standards 129

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
The Nordic Expert Group for Criteria Documentation of Health Risks from Chemicals and the Dutch Expert Committee on Occupational Standards 129 nr 2002:2 The Nordic Expert Group for Criteria Documentation of Health Risks from Chemicals and The Dutch Expert Committee on Occupational Standards 129. Chlorotrimethylsilane Hans Stouten, Fons Rutten, Iris van de Gevel and Flora de Vrijer Nordic Council of Ministers arbete och hälsa | vetenskaplig skriftserie isbn 91-7045-630-5 issn 0346-7821 http://www.niwl.se/ National Institute for Working Life The National Institute for Working Life is Sweden’s national centre for work life research, development and training. The labour market, occupational safety and health, and work organi- sation are our main fields of activity. The creation and use of knowledge through learning, information and documentation are important to the Institute, as is international co-operation. The Institute is collaborating with interested parties in various develop- ment projects. The areas in which the Institute is active include: • labour market and labour law, • work organisation, • musculoskeletal disorders, • chemical substances and allergens, noise and electromagnetic fields, • the psychosocial problems and strain-related disorders in modern working life. ARBETE OCH HÄLSA Editor-in-chief: Staffan Marklund Co-editors: Mikael Bergenheim, Anders Kjellberg, Birgitta Meding, Bo Melin, Gunnar Rosén and Ewa Wigaeus Tornqvist © National Institut for Working Life & authors 2002 National Institute for Working Life S-112 79 Stockholm Sweden ISBN 91–7045–630–5 ISSN 0346–7821 http://www.niwl.se/ Printed at Elanders Gotab, Stockholm Preface An agreement has been signed by the Dutch Expert Committee on Occupational Standards (DECOS) of the Health Council of the Netherlands and the Nordic Expert Group for Criteria Documentation of Health Risks from Chemicals (NEG). The purpose of the agreement is to write joint scientific criteria documents which could be used by the national regulatory authorities in both the Netherlands and in the Nordic countries. The document on health effects of chlorotrimethylsilane was written by Hans Stouten, Fons Rutten, Iris van de Gevel, and Flora de Vrijer from the Toxicology Division of the TNO Nutrition and Food Research Institute, Zeist, the Netherlands and has been reviewed by DECOS as well as by NEG. The document has been adapted to the different formats used by DECOS and NEG. G.J. Mulder G. Johanson Chairman Chairman DECOS NEG Abbreviations ACGIH American Conference of Governmental Industrial Hygienists CI confidence interval EC European Commission IUCLID International Uniform Chemical Information Data base LC50 lethal concentration for 50% of the exposed animals at single administration LD50 lethal dose for 50% of the exposed animals at single administration LDLo lowest observed lethal dose MTD maximum tolerated dose SCE sister chromatid exchange Contents Preface Abbreviations 1. Introduction 1 2. Identity, properties, and monitoring 1 2.1 Identity 1 2.1.1 Structure 1 2.1.2 Chemical names and synonyms/registry numbers 1 2.2 Physical and chemical properties 2 2.3 Validated analytical methods 2 3. Sources 3 3.1 Natural occurrence 3 3.2 Man-made sources 3 3.2.1 Production 3 3.2.2 Uses 3 4. Exposure 3 4.1 General population 3 4.2 Working population 3 5. Toxicokinetics 4 5.1 Introduction 4 5.2 Absorption 4 5.3 Distribution 4 5.4 Biotransformation 4 5.5 Excretion 4 5.6 Biological monitoring 4 6. Effects 5 6.1 Observations in man 5 6.1.1 Irritation and sensitisation 5 6.1.2 Toxicity due to experimental or occupational exposure 5 6.2 Animal experiments 5 6.2.1 Irritation and sensitisation 5 6.2.2 Acute toxicity 5 6.2.3 Repeated dose and carcinogenicity studies 7 6.2.4 Mutagenic and genotoxic activity 7 6.2.5 Effects on reproduction 9 6.3 Summary 9 7. Existing guidelines, standards, and evaluations 10 7.1 General population 10 7.2 Working population 10 7.3 Evaluations 10 8. Hazard assessment 10 8.1 Assessment of health hazard 10 8.2 Groups at extra risk 11 8.3 Scientific basis for an occupational exposure limit 11 8.4 Additional considerations 11 9. Recommendations for research 11 10. Summary 12 10. Summary in Swedish 13 11. References 14 12. Data bases used in the search for literature 15 Appendix 1. 16 Current limit values 16 Toxicity data on hydrogen chloride and hexamethyldisiloxane 16 Hydrogen chloride 16 Hexamethyldisiloxane 16 Trimethylsilanol 18 1. Introduction Chlorotrimethylsilane is a colourless liquid with a sharp hydrogen chloride-like odour. The vapour of chlorotrimethylsilane is heavier than air, travels along surfaces, and the liquid substance can be ignited from distance. At elevated temperatures or during combustion, the substance decomposes producing corrosive and toxic vapours. It violently reacts with water producing hydrogen chloride causing a fire and explosion hazard. Hydrogen chloride is also released upon contact with surface moisture. Chlorotrimethylsilane is used as an intermediate in the production of silicone fluids, as a silylating agent, and as a catalyst for propylene oxide production. Because of the high reactivity, chlorotrimethylsilane is manufactured, stored, and used in airtight, highly specialised installations. 2. Identity, properties, and monitoring 2.1 Identity 2.1.1 Structure CH3 Cl Si CH3 CH3 2.1.2 Chemical names and synonyms/registry numbers Chemical name: chlorotrimethylsilane CAS registry no: 75-77-4 Synonyms: trimethylchlorosilane, monochlorotrimethylsilicone, chlorotrimethylsilicane, trimethylsilyl chloride EINECS no: 200-900-5 RTECS no: VV2710000 1 2.2 Physical and chemical properties (3, 4, 17) Molecular formula: C3H9SiCl Molecular weight: 108.66 Boiling point (101.3 kPa): 58.0°C Melting point (101.3 kPa): -57.7°C Relative density (water=1): 0.9 Vapour density (air=1): 3.75 Vapour pressure (20°C; 101.3 kPa): 25.3 kPa Relative density of saturated vapour/air mixture (air=1; 20°C): 1.7 Flashpoint: -18.0°C Auto-ignition temperature: 417.0°C Explosive limits (%, in air): 1.8-6.0 Solubility in water: vigorous hydrolysis Solubility in organic solvents: soluble in benzene, ether, perchloroethylene Log Poctanol/water: 3.00 Physical form: colourless liquid Odour: sharp hydrogen chloride-like odour Conversion factors (20°C; 101.3 kPa ): 1 ppm = 4.5 mg/m3 1 mg/m3 = 0.22 ppm The chlorotrimethylsilane vapour is heavier than air, travels along surfaces, and the liquid substance can be ignited from distance. It violently reacts with water producing hydrogen chloride causing a fire and explosion hazard. Hydrogen chloride is also released upon contact with surface moisture, and will corrode most metals and form flammable hydrogen gas. Generally, chlorotrimethylsilane hydrolyses very rapidly to hydrogen chloride and trimethylsilanol, which condenses rapidly to form hexa- dimethyldisiloxane and water. The committees are of the opinion that the presence of hydrogen chloride in air might indicate the presence of accidentally released chloro- trimethylsilane. At elevated temperatures or combustion, it decomposes producing corrosive and toxic vapours (silicium dioxide, phosgene, hydrogen chloride). It violently reacts with acids, amines, alcohols, and oxidising agents. 2.3 Validated analytical methods No validated method was found which can be used for the direct determination of chlorotrimethylsilane in air or biological samples. The rapid hydrolysis of chlorotri- methylsilane will complicate its determination. 2 3. Sources 3.1 Natural occurrence Chlorotrimethylsilane does not occur naturally. 3.2 Man-made sources 3.2.1 Production Chlorotrimethylsilane is produced by a Grignard reaction of silicon tetrachloride with methyl-magnesium chloride. Furthermore, chlorotrimethylsilane can be formed in a reaction of silicon metal with methyl chloride at elevated temperature using copper as a catalyst. Thereafter, chlorotrimethylsilane is separated from mixed methylchloro- silanes by fractional crystallisation (13). According to the International Uniform Chemical Information Data base (IUCLID) Data Sheet (see also Section 7.3), there are five production sites in Europe (excluding the former Soviet Union), three in the USA, and three in Japan. The annual produc- tion per European facility through the years 1990-1994 was stated to be in the range of 1-5 kilotonnes, the worldwide production in the range of 15-40 kilotonnes (4). 3.2.2 Uses Chlorotrimethylsilane is used as an intermediate by the production of silicone fluids (as a chain terminating agent), as a silylating agent, and as a catalyst for the pro- duction of propylene oxide (3, 13). According to the IUCLID Data Sheet, the entire European production is used for the manufacture of organosilicic derivatives, mainly polysiloxanes (4). Because of the high reactivity, chlorotrimethylsilane must be manufactured, stored, and used in airtight, highly specialised installations (4). 4. Exposure 4.1 General population No quantitative data were found. However, environmental levels are expected to be negligible. Chlorotrimethylsilane is not a naturally occurring compound, and is produced and used in closed systems at the same facility. When accidentally released into the environment, it will hydrolyse very rapidly to hydrogen chloride and trimethylsilanol, which condenses rapidly to form hexamethyldisiloxane and water (4, 13). 4.2 Working population No quantitative data were found. As stated before, because of its high reactivity, chlorotrimethylsilane is used in closed systems, and exposure levels may therefore be 3 negligible. Moreover, because of this high reactivity, in case of exposure, this may be to hydrogen chloride and hexamethyldisiloxane. No serious industrial
Load more

Recommended publications
  • Chlorotrimethylsilane
    Chlorotrimethylsilane Health-based recommended occupational exposure limit Gezondheidsraad Voorzitter Health Council of the Netherlands Aan de Staatssecretaris van Sociale Zaken en Werkgelegenheid Onderwerp : Aanbieding adviezen over Chloortrimethylsilaan en Butylacetaten Uw kenmerk : DGV/MBO/U-932542 Ons kenmerk : U 2173/AvdB/tvdk/459-D35 Bijlagen : 2 Datum : 15 november 2001 Mijnheer de Staatssecretaris, Bij brief van 3 december 1993, nr. DGV/BMO-U-932542, verzocht de Staatssecretaris van Welzijn, Volksgezondheid en Cultuur namens de Minister van Sociale Zaken en Werkgelegenheid om gezondheidskundige advieswaarden af te leiden ten behoeve van de bescherming van beroepsmatig aan stoffen blootgestelde personen. Per 1 januari 1994 heeft mijn voorganger daartoe een commissie ingesteld die de werkzaamheden voortzet van de Werkgroep van Deskundigen (WGD). De WGD was een door de genoemde Minister ingestelde adviescommissie. Hierbij bied ik u - gehoord de Beraadsgroep Gezondheid en Omgeving - twee publicaties aan van de commissie over chloortrimethylsilaan en butylacetaten. Deze publicaties heb ik heden ter kennisname aan de Minister van Volksgezondheid, Welzijn en Sport en aan de Minister van Volkshuisvesting, Ruimtelijke Ordening en Milieubeheer gestuurd. Hoogachtend, w.g. prof. dr JA Knottnerus Bezoekadres Postadres Parnassusplein 5 Postbus 16052 2511 VX Den Haag 2500 BB Den Haag Telefoon (070) 340 75 20 Telefax (070) 340 75 23 Chlorotrimethylsilane Health-based recommended occupational exposure limit report of the Dutch Expert Committee on Occupational Standards, a committee of the Health Council of The Netherlands to the Minister and State Secretary of Social Affairs and Employment No. 2001/05OSH, The Hague, 15 November 2001 The Health Council of the Netherlands, established in 1902, is an independent scientific advisory body.
    [Show full text]
  • Advances in the Understanding of Low Molecular Weight Silicon Formation and Implications for Control by Amc Filters
    APPLICATION NOTE ADVANCES IN THE UNDERSTANDING OF LOW MOLECULAR WEIGHT SILICON FORMATION AND IMPLICATIONS FOR CONTROL BY AMC FILTERS Authors: Jürgen M. Lobert, Philip W. Cate, David J. Ruede, Joseph R. Wildgoose, Charles M. Miller and John C. Gaudreau Abstract Introduction Trimethylsilanol (TMS) is a low molecular Silicon containing hydrocarbons are a class of weight / low boiling point silicon-containing, AMC causing persistent degradation of UV exposure airborne contaminant that has received increased tool optical surfaces.1,2,3 Organic silicon compounds interest over the past few years as an important are efficiently split into components by 193 nm UV cause for contamination of optical surfaces in light, commonly used in photolithography appli- lithography equipment. cations. The resulting, reactive silicon atoms can recombine with oxygen to create a layer of amor- TMS is not captured well by carbon-based filters, phous silicon dioxide on optical surfaces such as and hexamethyldisiloxane (HMDSO), even though exposure tool lenses.3,4 This haze layer can be captured well, can be converted to TMS when using difficult to remove and may require lens exchange acidic filter media commonly used for ammonia and polishing, potentially destroying optical coatings removal. TMS and HMDSO coexist in a chemical and creating substantial tool downtime and cost. equilibrium, which is affected by the acidity and The importance of TMS and related refractory moisture of their environment. species in optical degradation is one reason for This publication shows that HMDSO is converted the low level of allowable refractory compounds to TMS by acidic media at concentrations typically (100 ppt) specified in the International Technology found in cleanroom environments.
    [Show full text]
  • Rubber Composition, Method For
    (19) TZZ _T (11) EP 2 674 456 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.: of the grant of the patent: C08L 15/00 (2006.01) B60C 1/00 (2006.01) 01.11.2017 Bulletin 2017/44 C08C 19/25 (2006.01) C08J 3/20 (2006.01) C08K 3/36 (2006.01) C08K 5/098 (2006.01) (2006.01) (2006.01) (21) Application number: 12744729.0 C08L 9/06 C08C 19/44 C08L 25/10 (2006.01) (22) Date of filing: 09.02.2012 (86) International application number: PCT/JP2012/052928 (87) International publication number: WO 2012/108488 (16.08.2012 Gazette 2012/33) (54) RUBBER COMPOSITION, METHOD FOR PRODUCING SAME, AND TIRE KAUTSCHUKZUSAMMENSETZUNG, VERFAHREN ZU IHRER HERSTELLUNG UND REIFEN COMPOSITION DE CAOUTCHOUC, SON PROCÉDÉ DE PRODUCTION, ET PNEUMATIQUE (84) Designated Contracting States: • OKADA, Koji AL AT BE BG CH CY CZ DE DK EE ES FI FR GB Tokyo 105-8640 (JP) GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR (74) Representative: TBK Bavariaring 4-6 (30) Priority: 09.02.2011 JP 2011026042 80336 München (DE) (43) Date of publication of application: (56) References cited: 18.12.2013 Bulletin 2013/51 EP-A1- 1 505 087 EP-A1- 1 577 341 EP-A2- 2 009 048 DE-A1-102005 044 998 (73) Proprietor: JSR Corporation JP-A- 2005 008 870 US-A1- 2002 082 333 Tokyo 105-8640 (JP) US-A1- 2010 130 663 US-A1- 2011 003 932 (72) Inventors: • SHIBATA, Masahiro Tokyo 105-8640 (JP) Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the Implementing Regulations.
    [Show full text]
  • Silyl Ketone Chemistry. Preparation and Reactions of Silyl Allenol Ethers. Diels-Alder Reactions of Siloxy Vinylallenes Leading to Sesquiterpenes2
    J. Am. Chem. SOC.1986, 108, 7791-7800 7791 pyrany1oxy)dodecanoic acid, 1.38 1 g (3.15 mmol) of GPC-CdCIz, 0.854 product mixture was then filtered and concentrated under reduced g (7.0 mmol) of 4-(dimethylamino)pyridine, and 1.648 g (8.0 mmol) of pressure. The residue was dissolved in 5 mL of solvent B and passed dicyclohexylcarbodiimide was suspended in 15 mL of dry dichloro- through a 1.2 X 1.5 cm AG MP-50 cation-exchange column in order to methane and stirred under nitrogen in the dark for 40 h. After removal remove 4-(dimethylamino)pyridine. The filtrate was concentrated under of solvent in vacuo, the residue was dissolved in 50 mL of CH30H/H20 reduced pressure, dissolved in a minimum volume of absolute ethanol, (95/5, v/v) and stirred in the presence of 8.0 g of AG MP-50 (23 OC, and then concentrated again. Chromatographic purification of the res- 2 h) to allow for complete deprotection of the hydroxyl groups (monitored idue on a silica gel column (0.9 X 6 cm), eluting first with solvent A and by thin-layer chromatography)." The resin was then removed by fil- then with solvent C (compound 1 elutes on silica as a single yellow band), tration and the solution concentrated under reduced pressure. The crude afforded, after drying [IO h, 22 OC (0.05 mm)], 0.055 g (90%) of 1 as product (2.75 g). obtained after drying [12 h, 23 OC (0.05 mm)], was a yellow solid: R 0.45 (solvent C); IR (KBr) ucz0 1732, uN(cH3)3 970, then subjected to chromatographic purification by using a 30-g (4 X 4 1050, 1090cm-'; I' H NMR (CDCI,) 6 1.25 (s 28 H, CH2), 1.40-2.05 (m, cm) silica gel column, eluting with solvents A and C, to yield 0.990 g 20 H, lipoic-CH,, CH2CH20,CH2CH,C02), 2.3 (t.
    [Show full text]
  • Benzoic Acid
    A Publication of Reliable Methods for the Preparation of Organic Compounds Working with Hazardous Chemicals The procedures in Organic Syntheses are intended for use only by persons with proper training in experimental organic chemistry. All hazardous materials should be handled using the standard procedures for work with chemicals described in references such as "Prudent Practices in the Laboratory" (The National Academies Press, Washington, D.C., 2011; the full text can be accessed free of charge at http://www.nap.edu/catalog.php?record_id=12654). All chemical waste should be disposed of in accordance with local regulations. For general guidelines for the management of chemical waste, see Chapter 8 of Prudent Practices. In some articles in Organic Syntheses, chemical-specific hazards are highlighted in red “Caution Notes” within a procedure. It is important to recognize that the absence of a caution note does not imply that no significant hazards are associated with the chemicals involved in that procedure. Prior to performing a reaction, a thorough risk assessment should be carried out that includes a review of the potential hazards associated with each chemical and experimental operation on the scale that is planned for the procedure. Guidelines for carrying out a risk assessment and for analyzing the hazards associated with chemicals can be found in Chapter 4 of Prudent Practices. The procedures described in Organic Syntheses are provided as published and are conducted at one's own risk. Organic Syntheses, Inc., its Editors, and its Board of Directors do not warrant or guarantee the safety of individuals using these procedures and hereby disclaim any liability for any injuries or damages claimed to have resulted from or related in any way to the procedures herein.
    [Show full text]
  • A Novel Procedure for Qualifying and Quantifying Mono-, Di-, And
    A Novel Procedure for Qualifying and Quantifying Mono-, Di-, and Trisaccharides by Derivatization and Gas Chromatography A Senior Honors Thesis Presented in Partial Fulfillment of the Requirements for Graduation With Research Distinction in the Undergraduate Colleges of The Ohio State University By Xiaxi Liu The Ohio State University June 2011 Project Advisor: Dr. Christopher Callam, Department of Chemistry Thesis Committee: Dr. David Stetson, Department of Evolution, Ecology, and Organismal Biology. Dr. Gary Means, Department of Biochemistry Dr. Madhura Pradhan, Department of Microbiology Table of Contents Acknowledgements ...................................................................................................... iv Abstract .......................................................................................................................... v Introduction ................................................................................................................... 1 Analysis of Synthetic Mixture of 18 Sugars ......................................................... 9 Rat Urine Analysis .............................................................................................. 14 Cellular Permeability of Hyaluronic Acid Disaccharide ...................................... 20 Results and Discussion .............................................................................................. 22 Analysis of Synthetic Mixture of 18 Sugars ....................................................... 23 Rat Urine Analysis
    [Show full text]
  • Pyrroles and Its Analogues to Conjugated Materials A
    APPLICATIONS OF DITHIENO[3,2-b:2’,3’-d]PYRROLES AND ITS ANALOGUES TO CONJUGATED MATERIALS A Thesis Submitted to the Graduate Faculty of the North Dakota State University of Agriculture and Applied Science By Casey Brian McCausland In Partial Fulfillment of the Requirements for the Degree of MASTER OF SCIENCE Major Department: Chemistry and Biochemistry June 2014 Fargo, North Dakota North Dakota State University Graduate School Title Applications of Dithieno[3,2-b:2',3'-d]pyrroles and its Analogues to Conjugated Materials By Casey Brian McCausland The Supervisory Committee certifies that this disquisition complies with North Dakota State University’s regulations and meets the accepted standards for the degree of MASTER OF SCIENCE SUPERVISORY COMMITTEE: Seth C. Rasmussen Chair Andrew Croll Erika Offerdahl Pinjing Zhao Approved: 6/20/2014 Gregory R. Cook Date Department Chair ABSTRACT The promise of semiconducting materials with tunable electronic and optical properties that share the same mechanical flexibility, low production costs and ease of processing displayed by traditional polymers fuels the intense interest seen in developing devices employing conjugated polymers (CPs). Many examples of -conjugated systems have been studied and reported in the literature, of which Rasmussen and coworkers have advanced the field with their work involving N-alkyl, N-aryl, and N-acyl-dithieno[3,2-b:2',3'-d]pyrroles (DTPs). Using DTP as a template current investigations are targeting two analogues: pyrrolo[3,2-d:4,5-d’]bisthiazole (PBTz) and difuro[3,2-b:2’,3’-d]pyrroles (DFP). In comparison to polymers of DTP, the electron-deficient nature of thiazoles is known to stabilize HOMO levels of PBTz-based polymers.
    [Show full text]
  • Decomposition of Hexamethyldisilazane on Hot Metal Filaments and Its Gas-Phase Chemistry in a Hot-Wire Chemical Vapor Deposition Reactor
    University of Calgary PRISM: University of Calgary's Digital Repository Graduate Studies The Vault: Electronic Theses and Dissertations 2019-09-04 Decomposition of Hexamethyldisilazane on Hot Metal Filaments and its Gas-phase Chemistry in a Hot-wire Chemical Vapor Deposition Reactor Ampong, Eric Ampong, E. (2019). Decomposition of Hexamethyldisilazane on Hot Metal Filaments and its Gas-phase Chemistry in a Hot-wire Chemical Vapor Deposition Reactor (Unpublished master's thesis). University of Calgary, Calgary, AB. http://hdl.handle.net/1880/110892 master thesis University of Calgary graduate students retain copyright ownership and moral rights for their thesis. You may use this material in any way that is permitted by the Copyright Act or through licensing that has been assigned to the document. For uses that are not allowable under copyright legislation or licensing, you are required to seek permission. Downloaded from PRISM: https://prism.ucalgary.ca UNIVERSITY OF CALGARY Decomposition of Hexamethyldisilazane on Hot Metal Filaments and its Gas-phase Chemistry in a Hot-wire Chemical Vapor Deposition Reactor by Eric Ampong A THESIS SUBMITTED TO THE FACULTY OF GRADUATE STUDIES IN PARTIAL FULLFILMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE GRADUATE PROGRAM IN CHEMISTRY CALGARY, ALBERTA SEPTEMBER, 2019 © Eric Ampong 2019 Abstract Hot-wire chemical vapor deposition (HWCVD) has been used to produce silicon- containing thin films, nanomaterials, and functional polymer coatings for applications in microelectronic and photovoltaic devices. Silicon carbonitride (SiCyNz) thin films, deposited by HWCVD, have found a wide range of applications due to their nonstoichiometric component that exhibits unique properties from a combination of SiC and Si3N4 binary compounds.
    [Show full text]
  • (12) United States Patent (10) Patent No.: US 7.455,998 B2 Brandstadt Et Al
    US007455998B2 (12) United States Patent (10) Patent No.: US 7.455,998 B2 Brandstadt et al. (45) Date of Patent: Nov. 25, 2008 (54) METHODS FOR FORMING STRUCTURALLY 2004/OO7781.6 A1 4/2004 Brandstadt et al. DEFINED ORGANIC MOLECULES FOREIGN PATENT DOCUMENTS CA 2422600 * 3f2OO2 (75) Inventors: Kurt Friedrich Brandstadt, WO WO 90,09446 A 8, 1990 Frankenmuth, MI (US); Thomas WO WO 02/22842 A1 3, 2002 Howard Lane, Midland, MI (US); John WO WOO3/O542O5 A2 T 2003 C. Saam, Midland, MI (US); Joseph C. OTHER PUBLICATIONS McAuliffe, Sunnyvale, CA (US) J.N. Cha et al. “Silicatein Filaments and Subunits From a Marine Sponge Direct the Polymerization of Silica and Silcones. In vitro'. (73) Assignees: Dow Corning Corporation, Midland, PNAS 96: 361-365. (Jan. 1999).* MI (US); Genencor International, Inc., 1997 Sigma Catalog, pp. 652-653.* Palo Alto, CA (US) Bassindale et al., Enzyme-catalysed siloxane bond formation, Jour nal of Inorganic Biochemistry, May 21, 2003, pp. 401–406, Elsevier (*) Notice: Subject to any disclaimer, the term of this Inc. patent is extended or adjusted under 35 Fattaklhova et al., Fermentative Hydrolysis of the Silicon-Oxygen Bond, Access Russia, Inc. pp. 100-105. U.S.C. 154(b) by 480 days. Nishino et al., Enzymatic silicon oligomerization catalyzed by a lipid-coated lipase, The Royal Society of Chemistry 2002, pp. 2684 (21) Appl. No.: 10/791.951 2685. Bassindale et al., Biocatalysis of Siloxane Bonds, Polymer Preprints (22) Filed: Mar. 3, 2004 2003, 44(2), pp. 570-571. Bassindale et al: "Siloxane Biocatalysis. Polymer Preprints.” Mid (65) Prior Publication Data Mar.
    [Show full text]
  • United States Patent (10) Patent No.: US 7,118,616 B2 Gillard Et Al
    USOO711 8616B2 (12) United States Patent (10) Patent No.: US 7,118,616 B2 Gillard et al. (45) Date of Patent: Oct. 10, 2006 (54) PAINT COMPOSITIONS COMPRISING 5,382.281 A 1, 1995 Kuo ESTERS OF ROSIN AND PROCESS OF 5,436,284 A 7/1995 Honda et al. PRODUCTION THEREOF 5,545,823. A 8, 1996 Kuo et al. 5,712.275 A 1/1998 Van Gestel (75) Inventors: Michel Gillard, Louvain-la-Neuve 5,767,171 A 6/1998 MatSubara et al. (BE); M Vos, Nivelles (BE) 5,795,374. A * 8/1998 Itoh et al. ..................... 106/16 ; Varcel Vos, IN1Velles 6,069,189 A 5/2000 Kramer et al. 6,110,990 A 8/2000 Nakamura et al. (73) Assignee: Sigma Coatings B.V., Uithoorn (NL) 6,248,806 B1 6/2001 Codolar et al. 6,303,701 B1 10/2001 Isozaki et al. (*) Notice: Subject to any disclaimer, the term of this 6,559,202 B1 5/2003 t al patent is extended or adjusted under 35 6,710, 117 B1 3/2004 Gillard et al. U.S.C. 154(b) by 0 days. 6,828,030 B1* 12/2004 Arimura et al. ............ 428.447 2003,0162924 A1 8, 2003 Vos et al. (21) Appl. No.: 10/492,766 2005/008O159 A1 4/2005 Omoto et al. ............... 523,122 (22) PCT Filed: Oct.e 25,a? a 9 2002 FOREIGN PATENT DOCUMENTS EP OOO1711 * 5, 1979 (86). PCT No.: PCT/EPO2/11957 EP O 131 621 9, 1987 EP O 297 505 1, 1989 S 371 (c)(1), EP O 526 441 2, 1993 (2), (4) Date: Feb.
    [Show full text]
  • Methyl(Bismethylthio)Sulphonium Salts and Organo-Sulphur Chemistry
    Pure & App!. Chem., Vol. 59, No. 8, pp. 989—992, 1987. Printed in Great Britain. © 1987 IUPAC Methyl(bismethylthio)sulphonium salts and trimethylsilyl-sulphenyl halides as synthons in organo-sulphur chemistry GiuseppeCapozzi Department of Organic Chemistry, University of Florence, 50121 Florence, Italy Abstract —Methyl(bismethylthio)sulfoniumsalts 1 react with nucleophiles like suiphides, alkenes, and alkynes to give respectively methyltiosulphonium, thiiranium, and thiirenium salts. The reaction of 1 with alkenes or alkynes hearing a nucleophilic center inappropriatepositiongives ring closure with formation of heterocyclic compounds whose nature depend on the position of the nucleophile in the unsaturated hydrocarbons. A new one—pot synthesis of thiiranes from alkenes and trimethylsilylsulphenyl bromide is also described. The timethylsilylsulphenyl bromide is also the key intermediate for a new catalytic desulphurization of thiiranes to alkenes by trimethylsi lyl bromide. Several years ago we synthesized some methyl(bismethylthio)sulphonium salts 1 and found that they may act as very efficient synthetic equivalents of the rrethylsulphenylium ion in reactions with nucleophiles of various nature1' +S-Me - + Scheme! Me—S' X Me—S S-Me +,S—Me + A R______ + Me—S—S-Me 2 Me_SSM + S Me—S—-.S( X — SbC1. BF4 1 2 Methyl(bi smethylt hi o) sulphoni um hex a c h lo roan t imona te react s w it h sulphidesto give methylthio—substituted sulphonium salts 2 (Scheme 1). The reactions were carried out with symmetric and asymmetric sulphides as well as with cyclic sulphides. Usually the thio—substituted sulphonium salts are prepared by alkylation of disulphides; however the alkylation of an asymmetric disulphide gives poor regioselectivity and the synthesis of cyclic thio—substituted sulphonium salts is not possible because of the unavailability of the corresponding disulphides.
    [Show full text]
  • Siloxanes in Biogas: Approaches of Sampling Procedure and GC-MS Method Determination
    molecules Article Siloxanes in Biogas: Approaches of Sampling Procedure and GC-MS Method Determination Grzegorz Piechota GP CHEM, Laboratory of Biogas Research and Analysis, Legionów 40a/3, 87-100 Toru´n,Poland; [email protected] Abstract: A new approach of siloxane sampling based on impinger, micro-impinger, adsorption on active carbon, and direct TedlarBag methods followed by gas chromatography-mass spectrometry (GC-MS) was developed for the analysis of three linear (L2–L4) and four cyclic (D3–D5) volatile methyl siloxanes (VMSs). Three kinds of organic liquid-medium characterized by different polarities, namely acetone, methanol, and d-decane as siloxanes trap were arranged in the experiment which is widely discussed below. Thus, the GC-MS equipped with SUPELCOWAX-10 capillary column was employed to perform monitoring of VMS content in the analyzed biogas samples originating from landfill, wastewater treatment plants, and agriculture biogas plants. In all samples that have undergone the analysis, cyclic and linear VMSs were found in quantities exceeding 107.9 and 3.8 mg/m3, respectively. Significant differences between siloxanes concentrations depending on biogas origin were observed. Moreover, the high range of linearity (0.1 to 70.06 mg/m3), low LoD (0.01 mg/m3), low LoQ (0.04 mg/m3), and high recovery (244.1%) indicate that the procedure and can be applied in sensitive analyses of silica biogas contaminants. In addition to the above, the impinger method of sampling performed better than active-carbon Tube and TedlarBag, particularly for quantifying low concentrations of siloxanes. Overall, the evaluation of sampling methods for biogas collection simplified the analytical procedure by reducing the procedural steps, avoiding the Citation: Piechota, G.
    [Show full text]