Tecnoflon FKM and FFKM portfolio: an overview on …

1 Tecnoflon FKM and ffkm . portfolio : an overview on standard grades and specialties R. Villa Utrecht, 12-02-2009. Introduction History of FKM- ffkm . 1892: Development of fluroalkanes (Swarts reaction). 1955: Elastomeric copolymer VDF-CTFE ( Kellogg Army). 1956: Copolymer VDF-HFP (Dupont) improved heat stability 1960: Terpolymer VDF-HFP-TFE (Dupont) better chemical resistance 1960s: Perfluoroelastomers - copolymers TFE/PMVE (Dupont). 1960s: Copolymers TFE-P (Dupont, Asahi Glass). 1960: Copo and terpolymers using 1 HPFP instead of HFP (Montecatini-Edison SpA). 1970: Bisphenol curing chemistry (Dupont and 3M). 1970s: Terpolymers VDF/TFE/PMVE improved low T performance Late 1970s: Peroxide curing chemistry Br as CSM (Dupont) I as CSM (Daikin). SOLVAY SOLEXIS 2009, SOLVAY Solvay Solexis: FKM and ffkm portfolio Presentation overview Tecnoflon . Solvay Solexis tradename for Fluoroelastomers (FKM) and perfluoroelastomers ( ffkm ).

2 1. Introduction Fluoroelastomers key benefits 2. Fluoroelastomers classification/performances 3. Tecnoflon grades portfolio : fluoroelastomers 4. Perfluoroelastomers classification/performances 5. Tecnoflon PFR grades portfolio : perfluoroelastomers SOLVAY SOLEXIS 2009, SOLVAY Fluorine plus Typical properties of fluoroelastomers are: Excellent chemical resistance Excellent thermal resistance Very low permeability Very good weather, O2 and O3 resistance + Fluorine SOLVAY SOLEXIS 2009, SOLVAY Fluorine plus ASTM D2000/SAE J200 Spec. System 350. FKM and ffkm . ffkm 300 are at the top of the range! Heat Resistance ( C). FKM 250. FVMQ 200. EA. ACM. 150. CSM ECO. CR NBR 100. 50. 180 160 140 120 100 80 60 40 20 0. Swelling in IRM 903 oil (%). SOLVAY SOLEXIS 2009, SOLVAY Fluoroelastomers applications Automotive industry Aerospace industry Chemical & Processing industry Oil field / Mining Semicon industry SOLVAY SOLEXIS 2009, SOLVAY Fluoroelastomers classification FKMs are classified according to monomer composition and ratio FKMs are manufactured by polymerization of a limited number of monomers: Vinylidene Fluoride (VF2) CH2=CF2.

3 Hexafluoropropylene (HFP) CF2=CF-CF3. Tetrafluoroethylene (TFE) CF2=CF2. Perfluoroalkylvinylether (PAVE) CF2=CF-OCF3 (main monomer MVE when Rf = CF3). Ethylene (E) CH2=CH2. Propylene (P) CH2=CH-CH3. FKMs can be further differentiated by curing chemistry Two main cure systems: Bisphenol Peroxide SOLVAY SOLEXIS 2009, SOLVAY Chemical composition Fluoroelastomers (FKM) are classified according to monomer composition (ASTM D1418): Type 1. VF2, HFP (Bisphenol). Example: Tecnoflon FOR 80HS. Type 2. VF2, HFP, TFE (Bisphenol or Peroxide). Example: Tecnoflon FOR 4391 (Bisphenol). Example: Tecnoflon P 959 (Peroxide). Type 3. VF2, TFE, PMVE (Bisphenol or Peroxide). Example: Tecnoflon PL 855 (Peroxide). Type 4. TFE, P, VF2 (Bisphenol). Type 5. TFE, HFP, VF2, E, PMVE (Peroxide). Example: Tecnoflon BR 9151 (Peroxide). Perfluoroelastomers ( ffkm ) are usually TFE / PAVE (MVE) copolymers SOLVAY SOLEXIS 2009, SOLVAY !

4 "#. CF3. ( PR4)+ -O O-( PR4)+. CF3. CH2-CH=CH2. $# N. O=C C=O. CH2=CH-CH2-N N-CH2-CH=CH2. C. O. SOLVAY SOLEXIS 2009, SOLVAY ). & *. !$#. &'( ) &#. "%. ). * + ) ",-../- !#. ". (. ". %. '&&. !!#. &". !" !"". * &. , +". ). *. ". - . % &. #. ". SOLVAY SOLEXIS 2009, SOLVAY Tecnoflon Bisphenol Curable A full range of products for all kinds of items and processing technologies (compression, injection, transfer, extrusion). Tailor made materials for special requirements New copolymers with improved performances (HS grades manufactured in US plant). For bisphenol curable FKM, Solvay Solexis supplies: Raw gum Cure incorporated materials (rubber + bisphenol +. accelerator + possibly processing aids). Cure incorporated materials for rubber-metal bonding SOLVAY SOLEXIS 2009, SOLVAY Tecnoflon Bisphenol Curable portfolio 4. 7 6. # ) ", 5. &. /01/20/'"230 5601 56("230 56'" 0. &0 11 &$.

5 /4"23 56#"&230 56#+&! 0. 0. 1 /#" 0 5601 56 0 56$+(" 0. ) &0 123, &+ 7$. #+(0 4+( 56#+(& 564+(#. 56 '+'0. '+'0 '+'7. 8 &4. / 6) 1-#. -11 56#+'&. 8'+'08'+'8 !&. SOLVAY SOLEXIS 2009, SOLVAY Tecnoflon Peroxide Curable A full range of products both for compression and injection moulding (high low Mooney viscosity). Very fast curing rate Excellent mechanical properties Very low compression set Very low post-curing times (1 2 h). Excellent processability For Peroxide curable FKM, Solvay Solexis supplies: Raw gum SOLVAY SOLEXIS 2009, SOLVAY Tecnoflon Peroxide Curable portfolio 7 78 6. ) ", 5. 8 13 "9. 3 -*#$0-$#$ &#. ) & 0 3, "9. $ -*#40-4#4 $. 1: "9. 2 -8*##0-8(## +". /6) 11 "9. 1 -8##$ !4. 11 "9. $ -8*#(0- 4#( !*. 119. 2 ,- 9-8(#$+":9-8*#$+". "9 +". < 0/ 6 ) 1-9. " "9. ;- 9-8*##+# +#. 1-9. " "1 9-8(##*"09-8###*". "9 *". 3" ,9. $- - 64& 4. SOLVAY SOLEXIS 2009, SOLVAY Tecnoflon PTFE nanocomposites FKMs Main features / Applications: NFT 7030.))))

6 P757/30M. Good processability P959/30M. Excellent mechanical properties Permeation reduction: automotive industry (low emissions). Friction reduction: automotive industry (shaft seals, valve stem seals). Good chemical resistance: oil industry High purity: semicon / food industry SOLVAY SOLEXIS 2009, SOLVAY Solexis FFKMs: Tecnoflon PFR. SOLVAY SOLEXIS 2009, SOLVAY ffkm : Chemical structure F F F F F F. - C - C - - - - C -C - - - - C -C - F F F F. n O m X z CF3 Cure site TFE MVE monomer Perfluoroelastomers ( ffkm ) are basically TFE / MVE (PAVE) copolymers + CSM. SOLVAY SOLEXIS 2009, SOLVAY ffkm : Thermal resistance ffkm 320 C. Their thermal resistance is the highest one among rubbers ! SOLVAY SOLEXIS 2009, SOLVAY ffkm : Chemical resistance Fluid type Typical example FFKMa FKMb Fluorine Content 66%. Aliphatic hydrocarbon Propane Excellent Excellent Aromatic hydrocarbons Benzene Excellent Excellent Organic acids Acetic acid Excellent Fair-good Inorganic acids Sulfuric acid Excellent Excellent Alcohols Methanol Excellent Fair-excellent Inorganic base Sodium hydroxide Excellent Poor-fair Organic base Aniline Excellent Fair Ethers MTBE Excellent Fair-poor Ketones Acetone Excellent Poor Nitrous oxidizers Ammonium nitrate Excellent Good Halogen oxidizers Chlorine Excellent Excellent Heat transfer fluids Ethylene glycol Excellent Excellent Oils & greases Halogenated refrigerants Mineral oil HFC-134a Excellent Fair-good Excellent Poor-fair Chemical resistance Polar solvents Water Excellent Excellent is by far improved with respect to FKM !

7 SOLVAY SOLEXIS 2009, SOLVAY ffkm : Classification Differences in perfluoroelastomer performance are due to the different weak points nature ( curing chemistry). Curing point: Phenoxy groups F. o X-linking agent: Bisphenol AF. F3C-C-CF3. o F. SOLVAY SOLEXIS 2009, SOLVAY ffkm : Classification Differences in perfluoroelastomer performance are due to the different weak points nature ( curing chemistry). -CH2CH-CH2- Curing point: Halogen atoms (Br/I). X-linking agent: TAIC. X. 0 N 0. - N N -CH X. X -C H 2 2 CH. - CH. CH 2- H 2. -C. 0. SOLVAY SOLEXIS 2009, SOLVAY ffkm : Classification Differences in perfluoroelastomer performance are due to the different weak points nature ( curing chemistry). CN. Curing point: Nitrile CN groups R4Sn X-linking reaction: Triazine formation Curing catalyst: R4Sn, etc. N N. N. SOLVAY SOLEXIS 2009, SOLVAY Performances comparison 8. ) = ! ;"15. & !

8 $2,5. * ! $;,5. )0& & 3, > $,,5. * ! "-7. ) = ! ;-7. & ! -,7. * ! % 6 ? %. ) = ! & 6 ? %. Tecnoflon PFR grades are peroxide curable SOLVAY SOLEXIS 2009, SOLVAY Performances comparison Chemical resistance * < - + ; < - 8 6 @ ; < - ; ; ;. ( ; ; ;. @ ; ; ;. + < - ;. SOLVAY SOLEXIS 2009, SOLVAY Tecnoflon PFR grades portfolio Grade Cross-linker Feature Max T ( C). PFR 91 TAIC Not a true ffkm - Chemical Resistance 230. PFR 94 TAIC Chemical Resistance 230. All are PFR 06HC TAIC. peroxi Very high chemical resistance (strong amines) 230. de cur PFR 95HT Incorporated able ! Very high thermal resistance 320. PFR 5910M Incorporated High purity - low hardness 320. PFR 5920M Incorporated High purity - medium hardness 320. SOLVAY SOLEXIS 2009, SOLVAY Next Generation of Low Temperature Fluoroelastomers overview History of Low Temperature Fluoroelastomers MOVE - new Low Temperature Monomer Technology Tecnoflon VPL - a New Series of Low Temperature Grades Testing Data on VPL versus standard LT FKM.

9 Applications Examples SOLVAY SOLEXIS 2009, SOLVAY The Fluoroelastomer Challenge Could we have good low temperature properties and high chemical resistance as well? TR10 Performance High F wt%. Current grades Low F wt%. Target Chemical resistance SOLVAY SOLEXIS 2009, SOLVAY The Fluoroelastomer Challenge Low temperature performance and chemical resistance are dependent upon polymer composition Fluid Resistance Monomer TR10 Effect Effect VDF. Decrease Decrease CH2=CF2. HFP. Increase Increase CF2=CF-CF3. TFE. Increase Increase CF2=CF2. PMVE. Decrease Slightly Decrease CF2=CF-O-CF3. The only way to improve low temperature performance is to design a new monomer. SOLVAY SOLEXIS 2009, SOLVAY MOVE Monomer Solution HFP PMVE MOVE. Tg = 160 C Tg = -8 C Tg = -39 C. CF2=CF CF2=CF CF2=CF. Fully Fluorinated CF3 O O Monomer CF3 CF2 No weak point ! O. CF3. SOLVAY SOLEXIS 2009, SOLVAY Unique Properties of MOVE monomer 2.

10 Tg of copolymer lower than two homopolymers -30. 1/Tg = wAPAA/TgA + wBPBB/TgB + (wAPAB + wBPBA)/TgAB. -35. Johnston eq. -40 PVDF PMOVE. Tg ( C). -45. -50 TgAB= -55 C. -55. -60. 0 20 40 60 80 100. MOVE3 (mol%). MOVE (mol%). SOLVAY SOLEXIS 2009, SOLVAY Market Needs Automotive Lower Sealing Temperature (cold environments). High pressure generates Tg shift GDI engines require FKM. with lower Tg compared to standard solutions Increased chemical resistance (biofuels) maintaining Low T. performance Aerospace Oil & Gas FKM for low Low T Service combined Drilling in cold with high thermal resistance environments Temperature ED Resistance Low T combined with Fuels and HTS oils compatibility Sealing Chemical Resistance ..with good process-ability as well! SOLVAY SOLEXIS 2009, SOLVAY MOVE Monomer Technology ) A < /! / =3 8= <. VPL 85540 (45 MU) VPL 85730 (45 MU). Tecnoflon . VPL 55540 (25 MU) VPL 45730 (25 MU).