Non-Phthalate Based on Synthetic and Renewable Chemistries

Stephen O’Rourke November 11, 2015

1 Agenda

• Raw Material Chemistry

• Ester Fundamentals

• Non-phthalates esters for NBR

• Renewable esters

• Summary

2 PLASTICIZERS CRUDE PETROLEUM SEMI-LINEAR ALCOHOLS ETHYLENE OIL REFINERY C7C9C11 ZIEGLER ALCOHOLS PHTHALATES DOP, BBP, DBP, NATURAL CHEMICAL C C C PROPYLENE 6 8 10 DIDP, 810P, GAS PROCESSING N-BUTANOL, DTDP, 711P, DINP GLYCOL 2-ETHYLHEXANOL INTERMEDIATES OXO C8C9C10C13 POLYESTERS Adipates Azelates ETHYLENE, PROPYLENE Sebacates NAPTHENICS PHTHALIC ANHY BUTYLENE GLYCOLS AND MALEIC ANHY Glutarates AROMATICS TRIMELLITIC ADIPATES CYCLOHEXANE DOA, DIDA NYLON PLANT ADIPIC ACID

GLUTARIC ACID GLUTARATES DIDG VEGETABLE SALAD OIL, , OILS; CASTOR, SHORTENING, C6-C18 FATTY ACIDS, STEARIC, ETC. SEBACIC OLEATES TALL COCONUT & ACID DOS, DBS OIL, ETC. ALKYD PLANTS STEARATES Butyl Stearate ANIMAL FATS, SHORTENING OLEIC ACID TALLOW, ETC & FATTY ACID C6-C18 FATTY ACIDS, STEARIC, ETC. PLANTS AZELATES DOZ, DBZ

3 HYDROXYLIC COMPOUNDS

Alcohols Glycols

Ethylene glycol butyl ether Propylenene glycol Diethylene glycol butyl ether Dipropylene glycol Propyl Butylene glycol Butyl Triethylene glycol Hexyl Tetraethylene glycol Heptyl Neopentyl glycol Allyl 1,6 Hexylene diol n-Octyl 1,5 Pentanediol 2-Ethyl hexyl 1,4 Cyclohexanedimethanol Iso Octyl Nonyl Octanol-2 Polyols Isononyl Decyl Glycerine Isodecyl Trimethylolpropane Undecyl, Iso- Sorbitol Tridecyl Pentaerythritol Benzyl

4 RAW MATERIALS-CARBOXYLIC ACIDS

Monobasic Acids Dibasic Acids Tribasic Acids

Oleic Acid Succinic Trimellitate Linoleic Acid Maleic Anhydride Citric Acid Glutarate Phosphoric Heptanoic Acid Adipic Pelargonic Acid Azelaic Sebacic Dodecandioic Caprylate Acid Dimer Acids Short Chain Acids Phthalaic Anhydride

5 Recycled Waste

Methanol

Raw Reactor Post Process Steps Filtration Packaging Materials >180°C •Drying •Washing •Deodorization •Decolorization Alcohol, Glycol, Premix H2O Monobasic Acids, Dibasic acids Waste Stream Catalysts

6 Ester Classification • Monoesters – Excellent efficiency

• Diesters – Excellent low temperature

• Triesters – Excellent high temperature

• Polyesters(polymerics) – Excellent extraction resistance – Excellent low volatility – Excellent migration resistance ( )n

8 Ester Classification

• Aliphatic • Aromatic – Examples: Adipate, Sebecate, – Examples: Phthalate/Cyclohexane, Glutarate, Succinate, Azelate, etc. Benzoate • Benefits • Benefits – Efficiency at reducing viscosity – Low Cost – Low Temperature flexibility – Good balance of properties – Volatility Resistance – Ability to be blended with higher – Range of compatibility performing esters • BLEND: Aliphatic / Aromatic • Benefits – Reduce cost – Optimized performance 9 Ester Selection

• Branched vs. Linear • Increased Carbon to Oxygen – Poorer low-temperature – Reduced compatibility performance – Poorer processing – Increasing volatility – Higher oil solubility – Lower stability to oxidation – Reduced volatility – Higher electrical volume resistivity – Reduced water solubility in compound – Better low-temperature flexibility – Migration resistance – Improved oil & fuel extraction resistance

10 PLASTHALL® PR-SERIES AND HALLGREEN® PHTHALATE REPLACEMENTS

PLASTHALL® PR-series: Synthetic-based, monomeric and polymeric phthalate replacements – PR-A126: good low and high temperature properties – PR-A200: superior cold flex properties – PR-A217: good overall balance of performance requirements – PR-LCOA: excellent permanence and heat aging

100% renewable, plant-derived monomeric phthalate replacement – PR-A610: excellent heat-aging, compatible with PVC formulations HALLGREEN ® : 100% renewable-based polymeric phthalate replacements – R-3040: excellent permanence, extraction, and migration – R-3050: similar to R-3040 but has a lower molecular weight – R-8010: excellent hydrocarbon resistance

11 Non-Phthalate esters in NBR

12 Non-Phthalate esters in NBR

13 Non-Phthalate esters in NBR

14 Non-Phthalate esters in NBR

15 Low-Temperature Esters

NBR,Compound: 34% [-C≡N] 20 pphr plasticizer (10.2% of compound).

Triethylene Glycol Caprate Monomerics DOP DOA DBEA DBEEA DBES Caprylates

As molded -33 -42 -43 -40 -39 -42

After air oven, 70h/125°C -25 -23 -27 -31 -34 -30

Avg. molec. wt. 391 373 346 494 505 430

16 NBR- Monomeric Esters-TP Products

PLASTICIZER TP-95™ TP-90B™ Original Physical Properties Tensile Ultimate, MPa 13.8 14.2 Tensile, Ultimate, psi 1995 2065 Elongation @ Break, % 495 490 Hardness Duro A, pts. 60 61 Low Temperature Brittleness, °C -42 -46 Tg, °C -44.8 -49.2 Aged Vulcanizate Properties Air Oven Aging, 70h @ 125°C Weight Change, % -3.5 -11 Fluid Resistance IRM 901 Oil, 70h @ 125°C Volume Change, % -11.3 -12.1 Weight Change, % -10.5 -10.9 IRM 903 Oil, 70h @ 125°C Volume Change, % 0.5 0.5 Weight Change, % -0.8 -0.5 Distilled Water, 70h @ 100°C Volume Change, % 5.5 6.4 4.8 5.7 17 Weight Change, % POLYMERIC DIOPLEX® PARAPLEX® NBR-Polymeric Esters 430 A-8000 A-8600 Original Physical Properties Tg by DSC, °C -26.3 -35.0 -33.0

Aged Vulcanizate Properties Air Oven Aging, 70h @ 125°C Weight Change, % -1.0 -1.3 -0.6

Fluid Resistance IRM 901 Oil, 70h @ 125°C Volume Change, % -0.6 -4.1 -1.8 Weight Change, % -1.3 -4.1 -2.4

IRM 903 Oil, 70h @ 125°C Volume Change, % 13.0 7.6 14.0 Weight Change, % 9.4 4.6 9.1

ASTM Fuel C Dry Out 22h @ 70°C Volume Change, % -2.4 -11.0 -5.8 Weight Change, % -3.4 -10.0 -6.0

18 1 RENEWABLE ESTERS

• Several monomeric and polymeric esters based on renewable raw materials have been developed

• Biopolymer modification-initial development PLA, PHA, PSM

• Traditional polymers also can utilize this technology Thermoplastics and Elastomers

19 SHADES OF GREEN

and Bio- degradable degradable Phthalate Adipate Petro-based Bio- 100% Renewable Cost and Performance Rubber Plasthall® PR-series Bio Polymer - Green PVC Focus PLA HallGreen® R-series Renewable PHA HallGreen® B-series

PHB Bio-degradable

20 20 BIOBASED RAW MATERIAL CHEMISTRY

• Several renewable raw materials for ester synthesis have been available for years Sebacic acid (C-10) Caprylic acid and alcohol (C-8) Oleic acid (C-18) Capric acid and alcohol (C10) • New biobased raw materials-have expanded the renewable ester space Succinic acid isosorbide propylene glycol • As new biobased chemistries become available this will create a broader spectrum for polymer solubility

21 Sustainable Esters- Raw Availability

Acids Mono-acids Dibasic acids Hydroxy Acids C C-4 - Succinic Lactic C-6 C-10-Sebacic Citric C-8 C-6 (adipic-2018) C-10 C-8, C-10 C-12 COFA C-18 - Tall Oil C-18 - Oleic C-18 - Stearic C-22- Erucic C-36-Dimer Acid Hydroxyl Functional Mono-alcohols Glycols-Difunctional Trifunctional C-4 1,2 propylene Glycerine C-8 1,4 BDO (2015-16) C-10 Isosorbide C-8, C-10

22 LOW POLARITY POLYMER BUILDING BLOCKS

Sebacic Acid O HO OH O

Oleic Acid H3C OH

O

H C OH 3 O CH3 H H

Dimer Acid H3C O OH O HO 23 MEDIUM-HIGH POLARITY POLYMER BUILDING BLOCKS

Caprylic Acid H3C OH

O O

H3C Lactic Acid OH OH

H3C OH Capric Acid O O OH Succinic Acid HO O

24 POLYMERS STUDIED

• PLA

• PVC

• NBR (nitrile elastomer)

• ECO (Epichlorhydrin)

• SBR (styrene rubber)

25 NBR Evaluation

Hallgreen R-8010 Paraplex G-50 Paraplex A-8200

0.0

-1.0

-2.0

-3.0

-4.0

-5.0

-6.0

-7.0 Gasoline, 22H @ 70C,Weight Oil, 70H@125C, Hardness Heat Aging, 7 days @125C, Loss, % Change, pts. Weight Loss,%

26 ECO Evaluation

Hallgreen R-8010 Paraplex G-50 Paraplex A-8200 4.0

2.0

0.0

-2.0

-4.0

-6.0

-8.0 Air Oven Aging, Oil, 70h @ 125°C, Gasoline 22h @ 7days @ 125°C, Hardness change 70°C,Weight Loss Weight Loss

27 SBR Evaluation

28 PVC Evaluation

PVC-Heat aging, 3 days@121C HallGreen R-3020 HallGreen R-4010 Hallgreen R-9010 DOP 15 10 5 0 -5 -10 -15 -20 -25 Hardness Change, pts. Weight Loss, %

29 Confidential RENEWABLE POLYMERIC ESTERS

Low Temperature HallGreen R-3050 HallGreen R-3040 DEHP Brittle Point, °C -18 -17 -34 T-45,000 psi, °C -12 -27 -37

Air Oven Aging, 3 days @ 136°C Tensile Change, % -11 -1 rigid Elongation Change, % -10 -1 rigid Weight Change, % -.97 0 -28

Immersion/Extraction, Percent Weight Change After: n-Hexane, 24hrs @23°C, DO -.39 -0.2 -31 1% Soapy Water, 7d @90°C, DO -5.3 -3.3 -19 Cottonseed Oil, 24hrs @ 60°C -.08 -2.6 -16 Distilled Water, 24hrs. @ 60°C, D -.28 -0.4 -.79 High Humidity, 9d @ 90°C, DO -.09 -0.2 -.43

30 Summary

• Review of Non-Phthalate Chemistry

• Non-Phthalate Esters can provide equivalent and better performance in NBR and other elastomers

• Renewable esters can be viable alternatives for plasticizing elastomers

31