US20010000343A1 - Fluoroelastomer composition having excellent processability and low temperature properties - Google Patents
Fluoroelastomer composition having excellent processability and low temperature properties Download PDFInfo
- Publication number
- US20010000343A1 US20010000343A1 US09/727,793 US72779300A US2001000343A1 US 20010000343 A1 US20010000343 A1 US 20010000343A1 US 72779300 A US72779300 A US 72779300A US 2001000343 A1 US2001000343 A1 US 2001000343A1
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- United States
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- composition
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- dimethyl
- salts
- Prior art date
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- 229920001973 fluoroelastomer Polymers 0.000 title claims abstract description 27
- 239000000203 mixture Substances 0.000 title claims description 68
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical group FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims abstract description 40
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 16
- 150000001451 organic peroxides Chemical class 0.000 claims abstract description 15
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 9
- 229930185605 Bisphenol Natural products 0.000 claims description 22
- 229920001577 copolymer Polymers 0.000 claims description 17
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000003431 cross linking reagent Substances 0.000 claims description 10
- 239000002808 molecular sieve Substances 0.000 claims description 10
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 10
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 9
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 9
- 239000012764 mineral filler Substances 0.000 claims description 9
- 150000004756 silanes Chemical class 0.000 claims description 9
- 239000011630 iodine Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 150000004714 phosphonium salts Chemical class 0.000 claims description 7
- 229910052882 wollastonite Inorganic materials 0.000 claims description 7
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 6
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 6
- 239000010456 wollastonite Substances 0.000 claims description 6
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 239000010457 zeolite Substances 0.000 claims description 5
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 4
- 150000004692 metal hydroxides Chemical class 0.000 claims description 4
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium group Chemical group [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 claims description 4
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 claims description 3
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 claims description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 239000007983 Tris buffer Substances 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- DMSZORWOGDLWGN-UHFFFAOYSA-N ctk1a3526 Chemical compound NP(N)(N)=O DMSZORWOGDLWGN-UHFFFAOYSA-N 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- WRIRWRKPLXCTFD-UHFFFAOYSA-N malonamide Chemical compound NC(=O)CC(N)=O WRIRWRKPLXCTFD-UHFFFAOYSA-N 0.000 claims description 3
- JPQBRSQJGWOTGC-UHFFFAOYSA-N methyl(silyloxysilyloxy)silane Chemical compound C[SiH2]O[SiH2]O[SiH3] JPQBRSQJGWOTGC-UHFFFAOYSA-N 0.000 claims description 3
- BLYOHBPLFYXHQA-UHFFFAOYSA-N n,n-bis(prop-2-enyl)prop-2-enamide Chemical compound C=CCN(CC=C)C(=O)C=C BLYOHBPLFYXHQA-UHFFFAOYSA-N 0.000 claims description 3
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 claims description 3
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 3
- KJWHEZXBZQXVSA-UHFFFAOYSA-N tris(prop-2-enyl) phosphite Chemical compound C=CCOP(OCC=C)OCC=C KJWHEZXBZQXVSA-UHFFFAOYSA-N 0.000 claims description 3
- VERMEZLHWFHDLK-UHFFFAOYSA-N benzene-1,2,3,4-tetrol Chemical class OC1=CC=C(O)C(O)=C1O VERMEZLHWFHDLK-UHFFFAOYSA-N 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 31
- 230000009977 dual effect Effects 0.000 abstract 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 23
- 239000000178 monomer Substances 0.000 description 20
- -1 alkyl vinyl ether Chemical compound 0.000 description 19
- BLTXWCKMNMYXEA-UHFFFAOYSA-N 1,1,2-trifluoro-2-(trifluoromethoxy)ethene Chemical compound FC(F)=C(F)OC(F)(F)F BLTXWCKMNMYXEA-UHFFFAOYSA-N 0.000 description 18
- 239000000654 additive Substances 0.000 description 11
- 150000002978 peroxides Chemical class 0.000 description 11
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 10
- 150000002170 ethers Chemical class 0.000 description 10
- 238000007906 compression Methods 0.000 description 9
- 230000006835 compression Effects 0.000 description 9
- 229920002313 fluoropolymer Polymers 0.000 description 7
- 229920006029 tetra-polymer Polymers 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- 239000004816 latex Substances 0.000 description 6
- 229920000126 latex Polymers 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 229920001897 terpolymer Polymers 0.000 description 6
- 239000004811 fluoropolymer Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 229920006169 Perfluoroelastomer Polymers 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QAERDLQYXMEHEB-UHFFFAOYSA-N 1,1,3,3,3-pentafluoroprop-1-ene Chemical compound FC(F)=CC(F)(F)F QAERDLQYXMEHEB-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 3
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- QDWJJTJNXAKQKD-UHFFFAOYSA-N trihexyphenidyl hydrochloride Chemical compound Cl.C1CCCCC1C(C=1C=CC=CC=1)(O)CCN1CCCCC1 QDWJJTJNXAKQKD-UHFFFAOYSA-N 0.000 description 3
- SRDQTCUHAMDAMG-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-hexadecafluoro-1,8-diiodooctane Chemical compound FC(F)(I)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)I SRDQTCUHAMDAMG-UHFFFAOYSA-N 0.000 description 2
- JOQDDLBOAIKFQX-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluoro-1,6-diiodohexane Chemical compound FC(F)(I)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)I JOQDDLBOAIKFQX-UHFFFAOYSA-N 0.000 description 2
- JILAKKYYZPDQBE-UHFFFAOYSA-N 1,1,2,2,3,3,4,4-octafluoro-1,4-diiodobutane Chemical compound FC(F)(I)C(F)(F)C(F)(F)C(F)(F)I JILAKKYYZPDQBE-UHFFFAOYSA-N 0.000 description 2
- DTWJXPCPIBEZFG-UHFFFAOYSA-N CC.CC.c1ccc(Cc2ccccc2)cc1 Chemical compound CC.CC.c1ccc(Cc2ccccc2)cc1 DTWJXPCPIBEZFG-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical class CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- YOALFLHFSFEMLP-UHFFFAOYSA-N azane;2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoic acid Chemical compound [NH4+].[O-]C(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YOALFLHFSFEMLP-UHFFFAOYSA-N 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 238000005796 dehydrofluorination reaction Methods 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- PYLIXCKOHOHGKQ-UHFFFAOYSA-L disodium;hydrogen phosphate;heptahydrate Chemical compound O.O.O.O.O.O.O.[Na+].[Na+].OP([O-])([O-])=O PYLIXCKOHOHGKQ-UHFFFAOYSA-L 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- OIPPWFOQEKKFEE-UHFFFAOYSA-N orcinol Chemical compound CC1=CC(O)=CC(O)=C1 OIPPWFOQEKKFEE-UHFFFAOYSA-N 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- SHFJWMWCIHQNCP-UHFFFAOYSA-M tetrabutylammoniumhydrogensulfate Substances OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- DBGVGMSCBYYSLD-UHFFFAOYSA-N tributylstannane Chemical compound CCCC[SnH](CCCC)CCCC DBGVGMSCBYYSLD-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 1
- AHUMDLIBMIYQMU-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7-pentadecafluoro-7-iodoheptane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)I AHUMDLIBMIYQMU-UHFFFAOYSA-N 0.000 description 1
- BBZVTTKMXRPMHZ-UHFFFAOYSA-N 1,1,1,2,3,3,3-heptafluoro-2-iodopropane Chemical compound FC(F)(F)C(F)(I)C(F)(F)F BBZVTTKMXRPMHZ-UHFFFAOYSA-N 0.000 description 1
- QBEWJJSQJWLVAI-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-icosafluoro-1,10-diiododecane Chemical compound FC(F)(I)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)I QBEWJJSQJWLVAI-UHFFFAOYSA-N 0.000 description 1
- WIEYKFZUVTYEIY-UHFFFAOYSA-N 1,1,2,2,3,3-hexafluoro-1,3-diiodopropane Chemical compound FC(F)(I)C(F)(F)C(F)(F)I WIEYKFZUVTYEIY-UHFFFAOYSA-N 0.000 description 1
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 1
- BZPCMSSQHRAJCC-UHFFFAOYSA-N 1,2,3,3,4,4,5,5,5-nonafluoro-1-(1,2,3,3,4,4,5,5,5-nonafluoropent-1-enoxy)pent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)=C(F)OC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)F BZPCMSSQHRAJCC-UHFFFAOYSA-N 0.000 description 1
- 125000004955 1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:1])C([H])([H])C([H])([H])C1([H])[*:2] 0.000 description 1
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-dioxonaphthalene Natural products C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 1
- 125000004958 1,4-naphthylene group Chemical group 0.000 description 1
- BOKGTLAJQHTOKE-UHFFFAOYSA-N 1,5-dihydroxynaphthalene Chemical compound C1=CC=C2C(O)=CC=CC2=C1O BOKGTLAJQHTOKE-UHFFFAOYSA-N 0.000 description 1
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- GPASWZHHWPVSRG-UHFFFAOYSA-N 2,5-dimethylbenzene-1,4-diol Chemical compound CC1=CC(O)=C(C)C=C1O GPASWZHHWPVSRG-UHFFFAOYSA-N 0.000 description 1
- 125000004959 2,6-naphthylene group Chemical group [H]C1=C([H])C2=C([H])C([*:1])=C([H])C([H])=C2C([H])=C1[*:2] 0.000 description 1
- QUWAJPZDCZDTJS-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfonylphenol Chemical compound OC1=CC=CC=C1S(=O)(=O)C1=CC=CC=C1O QUWAJPZDCZDTJS-UHFFFAOYSA-N 0.000 description 1
- ZTMADXFOCUXMJE-UHFFFAOYSA-N 2-methylbenzene-1,3-diol Chemical compound CC1=C(O)C=CC=C1O ZTMADXFOCUXMJE-UHFFFAOYSA-N 0.000 description 1
- FDMFUZHCIRHGRG-UHFFFAOYSA-N 3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C=C FDMFUZHCIRHGRG-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-BKFZFHPZSA-N Calcium-45 Chemical compound [45Ca] OYPRJOBELJOOCE-BKFZFHPZSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000001454 anthracenes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- VJGNLOIQCWLBJR-UHFFFAOYSA-M benzyl(tributyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 VJGNLOIQCWLBJR-UHFFFAOYSA-M 0.000 description 1
- BNQRPLGZFADFGA-UHFFFAOYSA-N benzyl(triphenyl)phosphanium Chemical class C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 BNQRPLGZFADFGA-UHFFFAOYSA-N 0.000 description 1
- USFRYJRPHFMVBZ-UHFFFAOYSA-M benzyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 USFRYJRPHFMVBZ-UHFFFAOYSA-M 0.000 description 1
- YFZFPCHXUXSTTM-UHFFFAOYSA-M benzyl-tris(dimethylamino)phosphanium;chloride Chemical compound [Cl-].CN(C)[P+](N(C)C)(N(C)C)CC1=CC=CC=C1 YFZFPCHXUXSTTM-UHFFFAOYSA-M 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 235000012241 calcium silicate Nutrition 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical class [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000004977 cycloheptylene group Chemical group 0.000 description 1
- 125000004979 cyclopentylene group Chemical group 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 150000005205 dihydroxybenzenes Chemical class 0.000 description 1
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- KCIDZIIHRGYJAE-YGFYJFDDSA-L dipotassium;[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] phosphate Chemical class [K+].[K+].OC[C@H]1O[C@H](OP([O-])([O-])=O)[C@H](O)[C@@H](O)[C@H]1O KCIDZIIHRGYJAE-YGFYJFDDSA-L 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- RGMABBBBPOTQIQ-UHFFFAOYSA-M hydrogen sulfate;tributyl(methyl)azanium Chemical compound OS([O-])(=O)=O.CCCC[N+](C)(CCCC)CCCC RGMABBBBPOTQIQ-UHFFFAOYSA-M 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical class COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- UJMWVICAENGCRF-UHFFFAOYSA-N oxygen difluoride Chemical group FOF UJMWVICAENGCRF-UHFFFAOYSA-N 0.000 description 1
- 125000006551 perfluoro alkylene group Chemical group 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 210000002966 serum Anatomy 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- KXCAEQNNTZANTK-UHFFFAOYSA-N stannane Chemical compound [SnH4] KXCAEQNNTZANTK-UHFFFAOYSA-N 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910000083 tin tetrahydride Inorganic materials 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- KSMYREBPTSSZDR-UHFFFAOYSA-M tributyl(prop-2-enyl)phosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CC=C KSMYREBPTSSZDR-UHFFFAOYSA-M 0.000 description 1
- VPAYJEUHKVESSD-UHFFFAOYSA-N trifluoroiodomethane Chemical compound FC(F)(F)I VPAYJEUHKVESSD-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/22—Vinylidene fluoride
- C08F214/222—Vinylidene fluoride with fluorinated vinyl ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
- C08F216/1408—Monomers containing halogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
Definitions
- This invention relates to fluoroelastomers that are capable of being crosslinked with both polyhydroxy compounds and organic peroxides to produce cured compositions having excellent processability and low temperature properties.
- Elastomeric fluoropolymers exhibit excellent resistance to the effects of heat, weather, oil, solvents and chemicals. Such materials are commercially available and are most commonly either dipolymers of vinylidene fluoride (VF 2 ) with hexafluoropropylene (HFP) or terpolymers of VF 2 , HFP, and tetrafluoroethylene (TFE). While these di- and terpolymers have many desirable properties, including low compression set and excellent processability, their low temperature flexibility is not adequate for all applications.
- VF 2 vinylidene fluoride
- HFP hexafluoropropylene
- TFE tetrafluoroethylene
- Kruger in U.S. Pat. No. 5,696,216, discloses PMVE-containing fluoroelastomers that are similar to those disclosed by Carlson. Those disclosed by Kruger contain copolymerized units of VF 2 ; at least one fluorinated propene and or fluorinated methyl vinyl ether; TFE; at least one perfluoro(polyoxyalkyl vinyl) ether, and a crosslinking site.
- compositions of Carlson and Kruger are most effectively crosslinked through use of peroxide cure systems. However, when compression molding equipment is used with peroxide curable VF 2 /PMVE copolymers the compositions generally exhibit a tendency to stick to and foul the mold.
- Tetrapolymers of VF 2 , HFP, TFE and perfluoro(alkyl vinyl) ethers (PAVE) other than PMVE are also known to exhibit improved low temperature properties compared to terpolymers of VF 2 , HFP and TFE.
- Arcella, et al. in U.S. Pat. No. 5,260,393 disclose a tetrapolymer comprising copolymerized units of 48-65 wt. % VF 2 , 21-36 wt. % HFP, 3-9 wt. % PAVE, and 0-17 wt. % TFE.
- compositions can be cured using a bisphenol curing system and do not exhibit the mold fouling problems associated with peroxide cures of VF 2 /PMVE copolymers.
- British Patent 1,296,084 discloses fluoroelastomeric tetrapolymers containing copolymerized units of 48-65 wt. % VF 2 , 8-23 wt. % HFP, 4-15 wt. % TFE, and 17-30 wt. % PAVE.
- Such compositions have good low temperature properties and are curable with bisphenols or amines. Although these tetrapolymers exhibit good low temperature properties, many applications require improved low temperature and processability performance.
- the dehydrofluorinated polymers are easily crosslinked by bisphenols. Furthermore, as discussed by W. W. Schmiegel, in Angewandte Makromolekulare Chemie, 76/77, 39 (1979), completely eliminating HFP to form VF 2 /TFE/PMVE terpolymers results in formation of monomer sequences consisting of TFE/VF 2 /TFE; TFE/VF 2 /PMVE; PMVE/VF 2 /PMVE; and PMVE/VF 2 /TFE. Although such sites readily undergo elimination of HF or HOCF 3 in the presence of base, the double bonds thus formed are not easily crosslinked by bisphenols or any other traditional crosslinking agents.
- the present invention is directed to a curable composition
- a curable composition comprising
- a fluoroelastomer copolymer consisting essentially of copolymerized units of 23-65 weight percent vinylidene fluoride, 25-75 weight percent perfluoro(alkyl vinyl) ether, 0-30 weight percent tetrafluoroethylene, and 0.3-5 weight percent 2-hydropentafluoropropene; said fluoroelastomer copolymer having between 0.05 and 1 weight percent iodine chemically bound at copolymer chain ends;
- an acid acceptor selected from the group consisting of metal oxides, metal hydroxides, and mixtures thereof,
- a preferred embodiment of the curable compositions of the invention additionally comprises a modified silane coated mineral filler.
- a further preferred embodiment of the curable compositions of the invention additionally comprises a molecular sieve.
- copolymers employed in the compositions of the present invention are capable of undergoing crosslinking reactions with both polyhydroxy compounds and organic peroxides to form elastomeric compositions that exhibit unusually good low temperature properties and low mold sticking characteristics.
- the polymer backbones of the copolymers consist essentially of copolymerized units of VF 2 , PAVE, 2-hydropentafluoropropene (i.e. 1,1,3,3,3-pentafluoropropene, referred to herein as HPFP), and, optionally, TFE. That is, each of the first three monomers (and optionally TFE) must be present in the polymer chain, but higher order polymers, i.e. those containing other additional monomer units, the addition of which does not affect the basic and novel characteristics of the polymer, are also within the scope of the present invention.
- the tetrapolymer VF 2 /PAVE/TFE/HPFP can contain other copolymerized vinyl or olefin monomers such as vinyl fluoride, trifluoroethylene, trifluoropropene, chlorotrifluoroethylene, alkyl vinyl ether, vinyl acetate, vinyl chloride, ethylene, and propylene, generally in quantities of up to about 5 wt. %.
- the fluoroelastomer copolymers used in this invention contain between 0.05 and 1 wt. % (preferably between 0.08 and 0.3 wt. %) iodine which is bound to copolymer chain ends, the iodine being introduced via use of an iodine-containing chain transfer agent during polymerization.
- the fluoroelastomers employed in the curable compositions of the invention contain between 23-65 wt. % copolymerized vinylidene fluoride units, preferably between 33-55 wt. % of such units. If less than 23 wt. % vinylidene fluoride units are present, the polymerization rate is very slow. In addition, good low temperature flexibility cannot be achieved. Vinylidene fluoride levels above 65 wt. % result in polymers that contain crystalline domains and are characterized by poor low temperature compression set resistance and reduced fluids resistance.
- Perfluoro(alkyl vinyl) ethers (PAVE) suitable for use as comonomers include those of the formula
- R f and R f′′ are different linear or branched perfluoroalkylene groups of 2-6 carbon atoms, m and n are independently 0-10, and R f is a perfluoroalkyl group of 1-6 carbon atoms.
- a preferred class of perfluoro(alkyl vinyl) ethers includes compositions of the formula
- X is F or CF 3
- n is 0-5
- R f is a perfluoroalkyl group of 1-6 carbon atoms.
- a most preferred class of perfluoro(alkyl vinyl) ethers includes those ethers wherein n is 0 or 1 and R f contains 1-3 carbon atoms. Examples of such perfluorinated ethers include perfluoro(methyl vinyl) ether and perfluoro(propyl vinyl) ether. Other useful monomers include compounds of the formula
- R f is a perfluoroalkyl group having 1-6 carbon atoms
- Additional perfluoro(alkyl vinyl) ether monomers include compounds of the formula
- the perfluoro(alkyl vinyl) ether content of the fluoroelastomers of the invention ranges from 25-75 wt. %. If perfluoro(methyl vinyl) ether is used, then the fluoroelastomer preferably contains between 30-44 wt. % copolymerized perfluoroether units. If less than 25 wt. % perfluoro(alkyl vinyl) ether is present, the low temperature properties of the fluoroelastomers are adversely affected.
- Copolymerized units of tetrafluoroethylene may also be present in the fluoroelastomers used in the invention at levels up to 30 wt. %.
- the presence of copolymerized units of TFE is desirable for the purpose of increasing fluorine content without unduly compromising low temperature flexibility. High fluorine content promotes good fluid resistance.
- TFE is present as a comonomer, it is preferably copolymerized in amounts of at least 3 wt. %. Levels of 3 wt. % or greater TFE lead to improved fluid resistance in some end use applications. TFE levels above 30 wt. % result in some polymer crystallinity which affects low temperature compression set and flexibility.
- the fourth copolymerized monomer unit in the copolymers employed in the invention is 2-hydropentafluoropropene (HPFP).
- HPFP 2-hydropentafluoropropene
- a particular characteristic of the HPFP monomer is that it acts as an independent cure site monomer that takes part in crosslinking reactions with polyhydroxylic curing agents.
- Polymers that contain copolymerized HPFP monomer units do not require the presence of copolymerized monomer sequences of VF 2 flanked by perfluoromonomers (e.g. HFP/NVF 2 /HFP) for initiation of dehydrofluorination.
- HFP/NVF 2 /HFP perfluoromonomers
- Introduction of copolymerized HPFP units into the VF 2 /HFP copolymer chain creates sites that exceed the reactivity of HFP/VF 2 /HFP sequences.
- HFP is a perfluorinated monomer and thus contains no hydrogens. It cannot function as an independent cure site monomer because it is incapable of undergoing dehydrofluorination.
- HFP-containing VF 2 copolymers of PMVE must contain at least about 8-10 wt. % HFP in order to provide a sufficient concentration of —CF 2 CF(CF 3 )CH 2 CF 2 CF 2 — sequences for effective cure by polyhydroxylic compounds.
- HPFP/TFE/PMVE terpolymers are disclosed in U.S. Pat. Nos. 5,478,902 and 5,719,245.
- HPFP/TFE/PMVE tetrapolyrners containing not more than about 20 mole percent of an additional monomer are disclosed therein. Compositions containing high levels of VF 2 comonomer are not disclosed.
- U.S. Pat. No. 5,874,506 discloses VF 2 /TFE/HFP/HPFP tetrapolymers.
- the polymers must contain 16-30 mol % HFP.
- Pentapolymers containing up to 5 mol % of additional comonomers are also disclosed therein.
- the tetrapolymers and pentapolymers disclosed in this reference do not exhibit good low temperature properties and have very different fluids resistance from the polymers of the present invention.
- the polymers employed in the present invention require only low levels of HPFP, i.e. 0.3-5 wt. %, to promote efficient polyhydroxylic cures. This permits adjustment of other comonomer levels to maximize particular physical properties.
- the copolymers used in the present invention exhibit excellent cure characteristics with only low levels of HPFP. They maintain the high temperature compression set resistance properties and excellent cure response characteristic of polymers having significant amounts of copolymerized VF 2 . Further, they exhibit a combination of excellent low temperature properties and processability not found in prior art fluoroelastomers.
- levels of HPFP will be between 0.7 and 3.0 wt. %.
- the polymers employed in this invention may be prepared using free radical batch or semi-batch, or continuous free radical emulsion polymerization processes. They may also be prepared by free radical suspension polymerization processes.
- the polymers are generally prepared in a continuous stirred tank reactor.
- Polymerization temperatures may be in the range of 40° to 145° C., preferably 100° to 135° C. at pressures of 2 to 8 MPa. Residence times of 20 to 60 minutes are preferred.
- Free radical generation may be effected through use of a water-soluble initiator such as ammonium persulfate, either by thermal decomposition or by reaction with a reducing agent such as sodium sulfite.
- An inert surface-active agent such as ammonium perfluorooctanoate may be utilized to stabilize the dispersion, usually in conjunction with addition of a base such as sodium hydroxide or a buffer such as disodium phosphate to control pH in the range 3 to 7.
- a base such as sodium hydroxide or a buffer such as disodium phosphate
- Unreacted monomer is removed from the reactor effluent latex by vaporization at reduced pressure.
- Polymer is recovered from the stripped latex by coagulation.
- coagulation may be effected by reducing latex pH to about 3 by addition of acid, then adding a salt solution, such as an aqueous solution of calcium nitrate, magnesium sulfate, or potassium aluminum sulfate, to the acidified latex.
- the polymer is separated from the serum, then washed with water and subsequently dried. After drying, the product may be cured.
- Chain transfer agents may be used in the polymerization in order to control the molecular weight distribution of the resulting polymers.
- chain transfer agents include isopropanol; methyl ethyl ketone; ethyl acetate; diethyl malonate; isopentane;1,3-diiodoperfluoropropane; 1,4-diiodoperfluorobutane; 1,6-diiodoperfluorohexane; 1,8-diiodoperfluorooctane; methylene iodide; trifluoromethyl iodide; perfluoro(isopropyl) iodide; and perfluoro(n-heptyl) iodide.
- An aspect of the present invention is a curable composition that comprises the above-described copolymers, a polyhydroxylic curing agent and an organic peroxide curing agent.
- any of the known polyhydroxylic aromatic crosslinking agents that require accelerators for satisfactory cure rates are suitable for use with the fluoroelastomers of the present invention.
- the crosslinking agent is usually added in amounts of from about 0.5-4 parts by weight per hundred parts by weight fluoroelastomer (phr), usually 1-2.5 phr.
- Preferred crosslinking agents are di- tri-, tetrahydroxybenzenes, naphthalenes, anthracenes and bisphenols of the formula
- A is a stable divalent radical, such as a difunctional aliphatic, cycloaliphatic, or aromatic radical of 1-13 carbon atoms, or a thio, oxy, carbonyl, sulfinyl, or sulfonyl radical; A is optionally substituted with at least one chlorine or fluorine atom; x is 0 or 1; n is 1 or 2 and any aromatic ring of the polyhydroxylic compound is optionally substituted with at least one atom of chlorine, fluorine, or bromine, a —CHO group, or a carboxyl or acyl radical (e.g.
- R is OH or a C 1 -C 8 alkyl, aryl, or cycloalkyl group. It will be understood from the above formula describing bisphenols that the —OH groups can be attached in any position (other than number one) in either ring. Blends of two or more such compounds can also be used.
- A when A is alkylene, it can be, for example, methylene, ethylene, chloroethylene, fluoroethylene, difluoroethylene, 1,3-propylene, 1,2-propylene, tetramethylene, chlorotetramethylene, fluorotetramethylene, trifluorotetramethylene, 2-methyl-1,3-propylene, 2-methyl-1,2-propylene, pentamethylene, and hexamethylene.
- A is alkylidene
- it can be for example ethylidene, dichloroethylidene, difluoroethylidene, propylidene, isopropylidene, trifluoroisopropylidene, hexafluoroisopropylidene, butylidene, heptachlorobutylidene, heptafluorobutylidene, pentylidene, hexylidene, and 1,1-cyclohexylidene.
- A is a cycloalkylene radical
- it can be for example 1,4-cyclohexylene, 2-chloro-1,4-cyclohexylene, 2-fluoro-1,4-cyclohexylene, 1,3-cyclohexylene, cyclopentylene, chlorocyclopentylene, fluorocyclopentylene, and cycloheptylene.
- A can be an arylene radical such as m-phenylene, p-phenylene, 2-chloro-1,4-phenylene, 2-fluoro-1,4-phenylene, o-phenylene, methylphenylene, dimethylphenylene, trimethylphenylene, tetramethylphenylene, 1,4-naphthylene, 3-fluoro-1 ,4-naphthylene, 5-chloro-1,4-naphthylene, 1,5-naphthylene, and 2,6-naphthylene.
- arylene radical such as m-phenylene, p-phenylene, 2-chloro-1,4-phenylene, 2-fluoro-1,4-phenylene, o-phenylene, methylphenylene, dimethylphenylene, trimethylphenylene, tetramethylphenylene, 1,4-naphthylene, 3-fluoro-1 ,4-naphthy
- Bisphenol AF (sometimes referred to as 4,4′-(hexafluoroisopropylidene)diphenol or as 4,4′-(2,2,2-trifluoro-1-(trifluoromethyl)ethylidene)bisphenol) is a preferred polyhydroxylic curing agent.
- crosslinking agents include hydroquinone, dihydroxybenzenes such as catechol, resorcinol, 2-methyl resorcinol, 5-methyl resorcinol, 2-methyl hydroquinone, 2,5-dimethyl hydroquinone; 2-t-butyl hydroquinone; and 1,5-dihydroxynaphthalene.
- Additional polyhydroxy curing agents include alkali metal salts of bisphenol anions, quaternary ammonium salts of bisphenol anions and quaternary phosphonium salts of bisphenol anions.
- the salts of bisphenol A and bisphenol AF include the disodium salt of bisphenol AF, the dipotassium salt of bisphenol AF, the monosodium monopotassium salt of bisphenol AF and the benzyltriphenylphosphonium salt of bisphenol AF.
- Quaternary ammonium and phosphonium salts of bisphenol anions and their preparation are discussed in U.S. Pat. Nos. 4,957,975 and 5,648,429.
- derivatized polyhydroxy compounds such as diesters
- examples of such compositions include diesters of phenols, such as the diacetate of bisphenol AF, the diacetate of sulfonyl diphenol, and the diacetate of hydroquinone.
- the curable compositions of the present invention also generally include a cure accelerator.
- the most useful accelerators are quaternary phosphonium salts, quaternary alkylammonium salts, or tertiary sulfonium salts. Particularly preferred accelerators are n-tetrabutylammonium hydrogen sulfate, tributylallylphosphonium chloride, benzyltriphenylphosphonium chloride, methyltributylammonium hydrogen sulfate, and tripropylammonium bromide. Other useful accelerators include those described in U.S. Pat. Nos.
- 5,591,804; 4,912,171; 4,882,390; 4,259,463 and 4,250,278 such as tributylbenzylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, benzyl tris(dimethylamino)phosphonium chloride; 8-benzyl-1,8-diazabicyclo[5,4,0]-7-undecenonium chloride, [(C 6 H 5 ) 2 S + (C 6 H 13 )][Cl] ⁇ , and [(C 6 H 13 ) 2 S(C 6 H 5 )] + [CH 3 CO 2 ] ⁇ .
- about 0.2 phr accelerator is an effective amount, and preferably about 0.35-1.5 phr is used.
- the curable compositions of the invention will also contain an acid acceptor such as a metal compound composed of a divalent metal oxide (e.g. magnesium oxide, zinc oxide, calcium oxide, or lead oxide), or a divalent metal hydroxide; or a mixture of the oxide and/or hydroxide with a metal salt of a weak acid, for example a mixture containing about 1-70 percent by weight of the metal salt.
- a metal compound composed of a divalent metal oxide e.g. magnesium oxide, zinc oxide, calcium oxide, or lead oxide
- a divalent metal hydroxide e.g. magnesium oxide, zinc oxide, calcium oxide, or lead oxide
- a metal salt of a weak acid for example a mixture containing about 1-70 percent by weight of the metal salt.
- useful metal salts of weak acids are barium, sodium, potassium, lead, and calcium stearates, benzoates, carbonates, oxalates, and phosphites.
- the amount of the metal compound added is generally about 1-15 phr, about 2
- compositions of the present invention also contain an organic peroxide curing agent.
- Compositions containing both polyhydroxy and organic peroxide curatives may cure faster than compositions which contain only a polyhydroxy compound or only an organic peroxide.
- the resulting cured article may have better physical properties (e.g. compression set) than articles cured only with a polyhydroxy compound or an organic peroxide.
- Useful organic peroxides are those which generate free radicals at curing temperatures.
- a dialkyl peroxide or a bis(dialkyl peroxide) which decomposes at a temperature above 50° C. is especially preferred.
- a ditertiarybutyl peroxide having a tertiary carbon atom attached to a peroxy oxygen is especially preferred.
- the most useful peroxides of this type are 2,5-dimethyl-2,5-di(tertiarybutylperoxy)hexyne-3 and 2,5-dimethyl-2,5-di(tertiarybutylperoxy)-hexane.
- peroxides can be selected from such compounds as dicumyl peroxide, dibenzoyl peroxide, tertiarybutyl perbenzoate, and di[1,3-dimethyl-3-(t-butylperoxy)butyl]carbonate. Generally, about 1-3 parts of peroxide per 100 parts of fluoroelastomer is used.
- Another material which is contained in the composition of the invention is a coagent composed of a polyunsaturated compound which is capable of cooperating with the peroxide to provide a useful cure.
- These coagents can be added in an amount equal to 0.1 and 10 parts per hundred parts fluoroelastomer, preferably between 2-5 parts per hundred parts fluoroelastomer.
- the coagent may be one or more of the following compounds: triallyl cyanurate; triallyl isocyanurate; tri(methallyl)isocyanurate; tris(diallylamine)-s-triazine; triallyl phosphite; N,N-diallyl acrylamide; hexaallyl phosphoramide; N,N,N′,N′-tetraalkyl tetraphthalamide; N,N,N′,N′-tetraallyl malonamide; trivinyl isocyanurate; 2,4,6-trivinyl methyltrisiloxane; and tri(5-norbornene-2-methylene)cyanurate. Particularly useful is triallyl isocyanurate (TAIC).
- TAIC triallyl isocyanurate
- additives may be compounded into the fluoroelastomer to optimize various physical properties.
- Such additives include carbon black, stabilizers, plasticizers, lubricants, pigments, fillers, and processing aids typically utilized in perfluoroelastomer compounding. Any of these additives can be incorporated into the compositions of the present invention, provided the additive has adequate stability for the intended service conditions.
- Carbon black is used in elastomers as a means to balance modulus, tensile strength, elongation, hardness, abrasion resistance, conductivity, and processability of the compositions. Carbon black is generally useful in amounts of from 5-60 phr.
- fluoropolymer fillers may be present in the composition. Generally from 1 to 50 phr of a fluoropolymer filler is used, and preferably at least about 5 phr is present.
- the fluoropolymer filler can be any finely divided, easily dispersed plastic fluoropolymer that is solid at the highest temperature utilized in fabrication and curing of the perfluoroelastomer composition. By solid, it is meant that the fluoroplastic, if partially crystalline, will have a crystalline melting temperature above the processing temperature(s) of the perfluoroelastomer(s). Such finely divided, easily dispersed fluoroplastics are commonly called micropowders or fluoroadditives. Micropowders are ordinarily partially crystalline polymers.
- a preferred additive class includes molecular sieves, particularly zeolites.
- Molecular sieve zeolites are crystalline aluminosilicates of Group IA and Group IIA elements, such as sodium, potassium, magnesium, and calcium. Chemically, they are represented by the empirical formula: M 2/n O.Al 2 O 3 . ySiO 2 .wH 2 O where y is 2 or greater, n is the cation valence, and w represents the water contained in the voids of the zeolite.
- Commercially available examples of such compositions include Molecular Sieve 3A, Molecular Sieve 4A, Molecular Sieve 5A, and Molecular Sieve 13X, all available from Aldrich Chemical Co., Inc. Milwaukee, Wis.
- Use of this class of additives prevents sponging and improves heat aging of vulcanizates upon press curing in many instances. In general, use of about 1-5 phr is sufficient.
- modified silane coated mineral fillers By “modified silane” is meant that the silane contains at least one reactive functional group such as an amino group, or an epoxy group.
- the mineral fillers used in this invention are preferably somewhat alkaline, such as calcium metasilicates (CaSiO 3 ), especially wollastonite. Wollastonite coated with either an aminosilane or an epoxysilane is especially preferred. These compounds are commercially available from Quartzwerke GmbH of Freschen, Germany as Tremin®283 EST (epoxysilane treated wollastonite) and Tremin®283 AST (aminosilane treated wollastonite).
- modified silane coated mineral fillers prevent sponging of the fluoroelastomer composition during press cure and also accelerate the cure rate.
- about 5 to 80 phr modified silane coated mineral filler is useful in the compositions of this invention, about 10 to 60 phr being preferred.
- Organotin hydrides are another class of additive that may be employed. Tri-n-butyltin hydride (TBTH) is especially preferred. These tin hydride fillers accelerate the cure rate of the compositions of this invention and increase the modulus and improve the compression set resistance of the cured compounds. Generally, about 0.2 to 1.5 phr organotin hydride filler is useful, about 0.4 to 0.8 phr being preferred.
- crosslinking agents are generally incorporated into the polymer by means of an internal mixer or on a rubber mill.
- the resultant composition is then cured, generally by means of heat and pressure, for example by compression transfer or injection molding.
- the curable compositions of the present invention are useful in production of gaskets, tubing, seals and other molded components. Such articles are generally produced by molding a compounded formulation of the curable composition with various additives under pressure, curing the part, and then subjecting it to a post cure cycle.
- the cured compositions have excellent low temperature flexibility and processability as well as excellent thermal stability and chemical resistance. They are particularly useful in applications such as seals and gaskets requiring a good combination of oil resistance, fuel resistance and low temperature flexibility, for example in fuel injection systems, fuel line connector systems and in other seals for high and low temperature automotive uses.
- test specimens that had been press cured at 180° C. for 15 minutes and then post cured in a hot air oven for 24 hours at 232° C. The following physical property parameters were recorded; test methods are in parentheses:
- T B tensile strength in units of MPa (ISO 37)
- TR-10 temperature of retraction (ISO 2921)
- Polymer 1 a polymer of the invention, was prepared by semi-batch emulsion polymerization carried out at 80° C. in a well-stirred reaction vessel.
- a 41.5 liter reactor was charged with 63.25 grams of ammonium perfluorooctanoate and 27436.75 grams of deionized, deoxygenated water. The reactor was heated to 80° C.
- a 16.0 ml aliquot of a mixture of 49.3 mol % 1,4-diiodoperfluorobutane, 34.8 mol % 1,6-diiodoperfluorohexane, 12.6 mol % 1,8-diiodoperfluorooctane, and 3.3 mol % 1,10-diiodoperfluorodecane was added to the reactor and the resulting mixture agitated 15 minutes.
- 50.0 ml of a solution of 1% ammonium persulfate and 5% disodium phosphate heptahydrate were added to the reactor.
- Latex was coagulated with 400 grams of potassium aluminum sulfate, washed with deionized water and then dried at 70° C. for two days.
- the polymer had a copolymerized monomer unit composition of 32.30 wt. % VF 2 , 37.50 wt. % PMVE, 28.90 wt. % TFE, 1.20 wt. % HPFP and 0.13 wt. % iodine.
- Polymer 1 was compounded on a two-roll rubber mill with the additives shown in Table I.
- Sample 1B is a composition of this invention.
- the other samples are controls of a similar composition cured with i) bisphenol only (1A) and ii) peroxide only (1C). Curing characteristics are reported in Table I.
- Compounds were press molded at 170° C. for 5 minutes and then post cured for 24 hours at 230° C. Physical properties of the cured compositions were measured according to the Test Methods and are also reported in Table I.
Abstract
Fluoroelastomers containing copolymerized units of vinylidene fluoride, perfluoro(alkyl vinyl) ether, 2-hydropentafluoropropene, and, optionally, tetrafluoroethylene, and having an iodine atom present at some polymer chain ends, exhibit excellent low temperature properties and processability when dual cured with both polyhydroxy compounds and organic peroxides.
Description
- 1. This application is a continuation-in-part of U.S. application Ser. No. 09/378,365, filed Aug. 20, 1999 which claims the benefit of U.S. Provisional Application 60/097,387, filed Aug. 21, 1998.
- 2. This invention relates to fluoroelastomers that are capable of being crosslinked with both polyhydroxy compounds and organic peroxides to produce cured compositions having excellent processability and low temperature properties.
- 3. Elastomeric fluoropolymers (i.e. fluoroelastomers) exhibit excellent resistance to the effects of heat, weather, oil, solvents and chemicals. Such materials are commercially available and are most commonly either dipolymers of vinylidene fluoride (VF2) with hexafluoropropylene (HFP) or terpolymers of VF2, HFP, and tetrafluoroethylene (TFE). While these di- and terpolymers have many desirable properties, including low compression set and excellent processability, their low temperature flexibility is not adequate for all applications.
- 4. It is known that incorporation of perfluorinated ether monomer units into vinylidene fluoride elastomers improves low temperature properties. For example, Carlson, in U.S. Pat. No. 5,214,106 discloses that when perfluoro(methyl vinyl) ether (PMVE) is substituted for HFP, the resultant VF2/PMVE/TFE copolymers have glass transition temperature (Tg) values which are 10°-20° C. lower than those of the corresponding VF2/HFP/TFE copolymers. Tg is often used as an indicator of low temperature flexibility because polymers having low glass transition temperatures maintain elastomeric properties at low temperatures.
- 5. Kruger, in U.S. Pat. No. 5,696,216, discloses PMVE-containing fluoroelastomers that are similar to those disclosed by Carlson. Those disclosed by Kruger contain copolymerized units of VF2; at least one fluorinated propene and or fluorinated methyl vinyl ether; TFE; at least one perfluoro(polyoxyalkyl vinyl) ether, and a crosslinking site.
- 6. The compositions of Carlson and Kruger are most effectively crosslinked through use of peroxide cure systems. However, when compression molding equipment is used with peroxide curable VF2/PMVE copolymers the compositions generally exhibit a tendency to stick to and foul the mold.
- 7. Tetrapolymers of VF2, HFP, TFE and perfluoro(alkyl vinyl) ethers (PAVE) other than PMVE are also known to exhibit improved low temperature properties compared to terpolymers of VF2, HFP and TFE. For example, Arcella, et al. in U.S. Pat. No. 5,260,393 disclose a tetrapolymer comprising copolymerized units of 48-65 wt. % VF2, 21-36 wt. % HFP, 3-9 wt. % PAVE, and 0-17 wt. % TFE. The compositions can be cured using a bisphenol curing system and do not exhibit the mold fouling problems associated with peroxide cures of VF2/PMVE copolymers. Similarly, British Patent 1,296,084 discloses fluoroelastomeric tetrapolymers containing copolymerized units of 48-65 wt. % VF2, 8-23 wt. % HFP, 4-15 wt. % TFE, and 17-30 wt. % PAVE. Such compositions have good low temperature properties and are curable with bisphenols or amines. Although these tetrapolymers exhibit good low temperature properties, many applications require improved low temperature and processability performance.
- 8. Merely raising the PAVE content while lowering the HFP content is not a solution to the problem of improving low temperature performance of VF2/HFP/PAVE/TFE terpolymers. This is because polymers wherein the level of HFP is below about 8-10 mole percent do not contain sufficient copolymerized monomer sequences consisting of HFP units flanked by VF2 units to permit efficient crosslinking with bisphenols. As is well known in the art, efficient curing of VF2/HFP-containing fluoroelastomers with a bisphenol/accelerator system is possible only when a —CH2— group in the polymer backbone is flanked by two perfluorinated carbons (e.g. CF2CF(CF3)CH2CF2CF2), rendering the hydrogens acidic enough to be abstracted by base. The dehydrofluorinated polymers are easily crosslinked by bisphenols. Furthermore, as discussed by W. W. Schmiegel, in Angewandte Makromolekulare Chemie, 76/77, 39 (1979), completely eliminating HFP to form VF2/TFE/PMVE terpolymers results in formation of monomer sequences consisting of TFE/VF2/TFE; TFE/VF2/PMVE; PMVE/VF2/PMVE; and PMVE/VF2/TFE. Although such sites readily undergo elimination of HF or HOCF3 in the presence of base, the double bonds thus formed are not easily crosslinked by bisphenols or any other traditional crosslinking agents.
- 9. There thus exists an unfulfilled need in the art for a method of providing copolymers of VF2, TFE, and PAVE that maintain optimum low temperature properties, but which exhibit low mold sticking characteristics, improved processability and are easily curable.
- 10. The present invention is directed to a curable composition comprising
- 11. A. a fluoroelastomer copolymer consisting essentially of copolymerized units of 23-65 weight percent vinylidene fluoride, 25-75 weight percent perfluoro(alkyl vinyl) ether, 0-30 weight percent tetrafluoroethylene, and 0.3-5 weight percent 2-hydropentafluoropropene; said fluoroelastomer copolymer having between 0.05 and 1 weight percent iodine chemically bound at copolymer chain ends;
- 12. B. a polyhydroxy crosslinking agent;
- 13. C. a cure accelerator;
- 14. D. an acid acceptor selected from the group consisting of metal oxides, metal hydroxides, and mixtures thereof,
- 15. E. an organic peroxide; and
- 16. F. a coagent.
- 17. A preferred embodiment of the curable compositions of the invention additionally comprises a modified silane coated mineral filler.
- 18. A further preferred embodiment of the curable compositions of the invention additionally comprises a molecular sieve.
- 19. The copolymers employed in the compositions of the present invention are capable of undergoing crosslinking reactions with both polyhydroxy compounds and organic peroxides to form elastomeric compositions that exhibit unusually good low temperature properties and low mold sticking characteristics.
- 20. The polymer backbones of the copolymers consist essentially of copolymerized units of VF2, PAVE, 2-hydropentafluoropropene (i.e. 1,1,3,3,3-pentafluoropropene, referred to herein as HPFP), and, optionally, TFE. That is, each of the first three monomers (and optionally TFE) must be present in the polymer chain, but higher order polymers, i.e. those containing other additional monomer units, the addition of which does not affect the basic and novel characteristics of the polymer, are also within the scope of the present invention. For example, the tetrapolymer VF2/PAVE/TFE/HPFP can contain other copolymerized vinyl or olefin monomers such as vinyl fluoride, trifluoroethylene, trifluoropropene, chlorotrifluoroethylene, alkyl vinyl ether, vinyl acetate, vinyl chloride, ethylene, and propylene, generally in quantities of up to about 5 wt. %.
- 21. In addition, the fluoroelastomer copolymers used in this invention contain between 0.05 and 1 wt. % (preferably between 0.08 and 0.3 wt. %) iodine which is bound to copolymer chain ends, the iodine being introduced via use of an iodine-containing chain transfer agent during polymerization.
- 22. The fluoroelastomers employed in the curable compositions of the invention contain between 23-65 wt. % copolymerized vinylidene fluoride units, preferably between 33-55 wt. % of such units. If less than 23 wt. % vinylidene fluoride units are present, the polymerization rate is very slow. In addition, good low temperature flexibility cannot be achieved. Vinylidene fluoride levels above 65 wt. % result in polymers that contain crystalline domains and are characterized by poor low temperature compression set resistance and reduced fluids resistance.
- 23. Perfluoro(alkyl vinyl) ethers (PAVE) suitable for use as comonomers include those of the formula
- CF2═CFO(Rf′O)n(Rf″O)mRf (I)
- 24. where Rf and Rf″are different linear or branched perfluoroalkylene groups of 2-6 carbon atoms, m and n are independently 0-10, and Rf is a perfluoroalkyl group of 1-6 carbon atoms.
- 25. A preferred class of perfluoro(alkyl vinyl) ethers includes compositions of the formula
- CF2═CFO(CF2CFXO)nRf (II)
- 26. where X is F or CF3, n is 0-5, and Rf is a perfluoroalkyl group of 1-6 carbon atoms.
- 27. A most preferred class of perfluoro(alkyl vinyl) ethers includes those ethers wherein n is 0 or 1 and Rf contains 1-3 carbon atoms. Examples of such perfluorinated ethers include perfluoro(methyl vinyl) ether and perfluoro(propyl vinyl) ether. Other useful monomers include compounds of the formula
- CF2═CFO[(CF2)mCF2CFZO]nRf (III)
- 28. where Rf is a perfluoroalkyl group having 1-6 carbon atoms,
- 29. m=0 or 1, n=0-5, and Z=F or CF3.
- 30. Preferred members of this class are those in which Rf is C3F7, m=0, and n= 1.
- 31. Additional perfluoro(alkyl vinyl) ether monomers include compounds of the formula
- CF2═CFO[(CF2CFCF3O)n(CF2CF2CF2O)m(CF2)p]CxF2x+1 (IV)
- 32. where m and n independently=1-10, p=0-3, and x=1-5.
- 33. Preferred members of this class include compounds where n=0-1, m=0-1, and x=1.
- 34. Examples of useful perfluoro(alkoxy vinyl) ethers include
- CF2═CFOCF2CF(CF3)O(CF2O)mCnF2n+1 (V)
- 35. where n=1-5, m=1-3, and where, preferably, n=1.
- 36. Mixtures of perfluoro(alkyl vinyl) ethers and perfluoro(alkoxy vinyl) ethers may also be used.
- 37. The perfluoro(alkyl vinyl) ether content of the fluoroelastomers of the invention ranges from 25-75 wt. %. If perfluoro(methyl vinyl) ether is used, then the fluoroelastomer preferably contains between 30-44 wt. % copolymerized perfluoroether units. If less than 25 wt. % perfluoro(alkyl vinyl) ether is present, the low temperature properties of the fluoroelastomers are adversely affected.
- 38. Copolymerized units of tetrafluoroethylene may also be present in the fluoroelastomers used in the invention at levels up to 30 wt. %. The presence of copolymerized units of TFE is desirable for the purpose of increasing fluorine content without unduly compromising low temperature flexibility. High fluorine content promotes good fluid resistance. If TFE is present as a comonomer, it is preferably copolymerized in amounts of at least 3 wt. %. Levels of 3 wt. % or greater TFE lead to improved fluid resistance in some end use applications. TFE levels above 30 wt. % result in some polymer crystallinity which affects low temperature compression set and flexibility.
- 39. The fourth copolymerized monomer unit in the copolymers employed in the invention is 2-hydropentafluoropropene (HPFP). A particular characteristic of the HPFP monomer is that it acts as an independent cure site monomer that takes part in crosslinking reactions with polyhydroxylic curing agents. Polymers that contain copolymerized HPFP monomer units do not require the presence of copolymerized monomer sequences of VF2 flanked by perfluoromonomers (e.g. HFP/NVF2/HFP) for initiation of dehydrofluorination. Introduction of copolymerized HPFP units into the VF2/HFP copolymer chain creates sites that exceed the reactivity of HFP/VF2/HFP sequences. HFP is a perfluorinated monomer and thus contains no hydrogens. It cannot function as an independent cure site monomer because it is incapable of undergoing dehydrofluorination. In fact, HFP-containing VF2 copolymers of PMVE must contain at least about 8-10 wt. % HFP in order to provide a sufficient concentration of —CF2CF(CF3)CH2CF2CF2— sequences for effective cure by polyhydroxylic compounds.
- 40. HPFP/TFE/PMVE terpolymers are disclosed in U.S. Pat. Nos. 5,478,902 and 5,719,245. In addition, HPFP/TFE/PMVE tetrapolyrners containing not more than about 20 mole percent of an additional monomer are disclosed therein. Compositions containing high levels of VF2 comonomer are not disclosed. In addition, U.S. Pat. No. 5,874,506 discloses VF2/TFE/HFP/HPFP tetrapolymers. The polymers must contain 16-30 mol % HFP. Pentapolymers containing up to 5 mol % of additional comonomers are also disclosed therein. The tetrapolymers and pentapolymers disclosed in this reference do not exhibit good low temperature properties and have very different fluids resistance from the polymers of the present invention.
- 41. Because of the ease of hydrogen abstraction in HPFP-containing VF2 fluoroelastomers, the polymers employed in the present invention require only low levels of HPFP, i.e. 0.3-5 wt. %, to promote efficient polyhydroxylic cures. This permits adjustment of other comonomer levels to maximize particular physical properties. Thus, the copolymers used in the present invention exhibit excellent cure characteristics with only low levels of HPFP. They maintain the high temperature compression set resistance properties and excellent cure response characteristic of polymers having significant amounts of copolymerized VF2. Further, they exhibit a combination of excellent low temperature properties and processability not found in prior art fluoroelastomers. Preferably levels of HPFP will be between 0.7 and 3.0 wt. %.
- 42. The polymers employed in this invention may be prepared using free radical batch or semi-batch, or continuous free radical emulsion polymerization processes. They may also be prepared by free radical suspension polymerization processes.
- 43. For example, if a continuous emulsion process is utilized, the polymers are generally prepared in a continuous stirred tank reactor. Polymerization temperatures may be in the range of 40° to 145° C., preferably 100° to 135° C. at pressures of 2 to 8 MPa. Residence times of 20 to 60 minutes are preferred. Free radical generation may be effected through use of a water-soluble initiator such as ammonium persulfate, either by thermal decomposition or by reaction with a reducing agent such as sodium sulfite. An inert surface-active agent such as ammonium perfluorooctanoate may be utilized to stabilize the dispersion, usually in conjunction with addition of a base such as sodium hydroxide or a buffer such as disodium phosphate to control pH in the range 3 to 7. Unreacted monomer is removed from the reactor effluent latex by vaporization at reduced pressure. Polymer is recovered from the stripped latex by coagulation. For example, coagulation may be effected by reducing latex pH to about 3 by addition of acid, then adding a salt solution, such as an aqueous solution of calcium nitrate, magnesium sulfate, or potassium aluminum sulfate, to the acidified latex. The polymer is separated from the serum, then washed with water and subsequently dried. After drying, the product may be cured.
- 44. Chain transfer agents may be used in the polymerization in order to control the molecular weight distribution of the resulting polymers. Examples of chain transfer agents include isopropanol; methyl ethyl ketone; ethyl acetate; diethyl malonate; isopentane;1,3-diiodoperfluoropropane; 1,4-diiodoperfluorobutane; 1,6-diiodoperfluorohexane; 1,8-diiodoperfluorooctane; methylene iodide; trifluoromethyl iodide; perfluoro(isopropyl) iodide; and perfluoro(n-heptyl) iodide.
- 45. Polymerization in the presence of iodine-containing chain transfer agents results in a copolymer with one or two iodine atoms per fluoroelastomer copolymer chain, bound at the chain ends (see for example U.S. Pat. No. 4,243,770 and U.S. Pat. No. 4,361,678). Such polymers are also curable with an organic peroxide and they may have improved flow and processability compared to polymers made in the absence of a chain transfer agent.
- 46. An aspect of the present invention is a curable composition that comprises the above-described copolymers, a polyhydroxylic curing agent and an organic peroxide curing agent.
- 47. Any of the known polyhydroxylic aromatic crosslinking agents that require accelerators for satisfactory cure rates are suitable for use with the fluoroelastomers of the present invention. The crosslinking agent is usually added in amounts of from about 0.5-4 parts by weight per hundred parts by weight fluoroelastomer (phr), usually 1-2.5 phr. Preferred crosslinking agents are di- tri-, tetrahydroxybenzenes, naphthalenes, anthracenes and bisphenols of the formula
- 48. where A is a stable divalent radical, such as a difunctional aliphatic, cycloaliphatic, or aromatic radical of 1-13 carbon atoms, or a thio, oxy, carbonyl, sulfinyl, or sulfonyl radical; A is optionally substituted with at least one chlorine or fluorine atom; x is 0 or 1; n is 1 or 2 and any aromatic ring of the polyhydroxylic compound is optionally substituted with at least one atom of chlorine, fluorine, or bromine, a —CHO group, or a carboxyl or acyl radical (e.g. a —COR where R is OH or a C1-C8 alkyl, aryl, or cycloalkyl group). It will be understood from the above formula describing bisphenols that the —OH groups can be attached in any position (other than number one) in either ring. Blends of two or more such compounds can also be used.
- 49. Referring to the bisphenol formula shown in the previous paragraph, when A is alkylene, it can be, for example, methylene, ethylene, chloroethylene, fluoroethylene, difluoroethylene, 1,3-propylene, 1,2-propylene, tetramethylene, chlorotetramethylene, fluorotetramethylene, trifluorotetramethylene, 2-methyl-1,3-propylene, 2-methyl-1,2-propylene, pentamethylene, and hexamethylene. When A is alkylidene, it can be for example ethylidene, dichloroethylidene, difluoroethylidene, propylidene, isopropylidene, trifluoroisopropylidene, hexafluoroisopropylidene, butylidene, heptachlorobutylidene, heptafluorobutylidene, pentylidene, hexylidene, and 1,1-cyclohexylidene. When A is a cycloalkylene radical, it can be for example 1,4-cyclohexylene, 2-chloro-1,4-cyclohexylene, 2-fluoro-1,4-cyclohexylene, 1,3-cyclohexylene, cyclopentylene, chlorocyclopentylene, fluorocyclopentylene, and cycloheptylene. Further, A can be an arylene radical such as m-phenylene, p-phenylene, 2-chloro-1,4-phenylene, 2-fluoro-1,4-phenylene, o-phenylene, methylphenylene, dimethylphenylene, trimethylphenylene, tetramethylphenylene, 1,4-naphthylene, 3-fluoro-1 ,4-naphthylene, 5-chloro-1,4-naphthylene, 1,5-naphthylene, and 2,6-naphthylene. Bisphenol AF (sometimes referred to as 4,4′-(hexafluoroisopropylidene)diphenol or as 4,4′-(2,2,2-trifluoro-1-(trifluoromethyl)ethylidene)bisphenol) is a preferred polyhydroxylic curing agent.
- 50. Other useful crosslinking agents include hydroquinone, dihydroxybenzenes such as catechol, resorcinol, 2-methyl resorcinol, 5-methyl resorcinol, 2-methyl hydroquinone, 2,5-dimethyl hydroquinone; 2-t-butyl hydroquinone; and 1,5-dihydroxynaphthalene.
- 51. Additional polyhydroxy curing agents include alkali metal salts of bisphenol anions, quaternary ammonium salts of bisphenol anions and quaternary phosphonium salts of bisphenol anions. For example, the salts of bisphenol A and bisphenol AF. Specific examples include the disodium salt of bisphenol AF, the dipotassium salt of bisphenol AF, the monosodium monopotassium salt of bisphenol AF and the benzyltriphenylphosphonium salt of bisphenol AF. Quaternary ammonium and phosphonium salts of bisphenol anions and their preparation are discussed in U.S. Pat. Nos. 4,957,975 and 5,648,429.
- 52. In addition, derivatized polyhydroxy compounds, such as diesters, are useful crosslinking agents. Examples of such compositions include diesters of phenols, such as the diacetate of bisphenol AF, the diacetate of sulfonyl diphenol, and the diacetate of hydroquinone.
- 53. The curable compositions of the present invention also generally include a cure accelerator. The most useful accelerators are quaternary phosphonium salts, quaternary alkylammonium salts, or tertiary sulfonium salts. Particularly preferred accelerators are n-tetrabutylammonium hydrogen sulfate, tributylallylphosphonium chloride, benzyltriphenylphosphonium chloride, methyltributylammonium hydrogen sulfate, and tripropylammonium bromide. Other useful accelerators include those described in U.S. Pat. Nos. 5,591,804; 4,912,171; 4,882,390; 4,259,463 and 4,250,278 such as tributylbenzylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, benzyl tris(dimethylamino)phosphonium chloride; 8-benzyl-1,8-diazabicyclo[5,4,0]-7-undecenonium chloride, [(C6H5)2S+(C6H13)][Cl]−, and [(C6H13)2S(C6H5)]+[CH3CO2]−. In general, about 0.2 phr accelerator is an effective amount, and preferably about 0.35-1.5 phr is used.
- 54. If quaternary ammonium or phosphonium salts of bisphenols are used as curing agents, then addition of a cure accelerator is not necessary.
- 55. The curable compositions of the invention will also contain an acid acceptor such as a metal compound composed of a divalent metal oxide (e.g. magnesium oxide, zinc oxide, calcium oxide, or lead oxide), or a divalent metal hydroxide; or a mixture of the oxide and/or hydroxide with a metal salt of a weak acid, for example a mixture containing about 1-70 percent by weight of the metal salt. Among the useful metal salts of weak acids are barium, sodium, potassium, lead, and calcium stearates, benzoates, carbonates, oxalates, and phosphites. The amount of the metal compound added is generally about 1-15 phr, about 2-10 parts being preferred.
- 56. The compositions of the present invention also contain an organic peroxide curing agent. Compositions containing both polyhydroxy and organic peroxide curatives may cure faster than compositions which contain only a polyhydroxy compound or only an organic peroxide. In addition, the resulting cured article may have better physical properties (e.g. compression set) than articles cured only with a polyhydroxy compound or an organic peroxide.
- 57. Useful organic peroxides are those which generate free radicals at curing temperatures. A dialkyl peroxide or a bis(dialkyl peroxide) which decomposes at a temperature above 50° C. is especially preferred. In many cases it is preferred to use a ditertiarybutyl peroxide having a tertiary carbon atom attached to a peroxy oxygen. Among the most useful peroxides of this type are 2,5-dimethyl-2,5-di(tertiarybutylperoxy)hexyne-3 and 2,5-dimethyl-2,5-di(tertiarybutylperoxy)-hexane. Other peroxides can be selected from such compounds as dicumyl peroxide, dibenzoyl peroxide, tertiarybutyl perbenzoate, and di[1,3-dimethyl-3-(t-butylperoxy)butyl]carbonate. Generally, about 1-3 parts of peroxide per 100 parts of fluoroelastomer is used.
- 58. Another material which is contained in the composition of the invention is a coagent composed of a polyunsaturated compound which is capable of cooperating with the peroxide to provide a useful cure. These coagents can be added in an amount equal to 0.1 and 10 parts per hundred parts fluoroelastomer, preferably between 2-5 parts per hundred parts fluoroelastomer. The coagent may be one or more of the following compounds: triallyl cyanurate; triallyl isocyanurate; tri(methallyl)isocyanurate; tris(diallylamine)-s-triazine; triallyl phosphite; N,N-diallyl acrylamide; hexaallyl phosphoramide; N,N,N′,N′-tetraalkyl tetraphthalamide; N,N,N′,N′-tetraallyl malonamide; trivinyl isocyanurate; 2,4,6-trivinyl methyltrisiloxane; and tri(5-norbornene-2-methylene)cyanurate. Particularly useful is triallyl isocyanurate (TAIC).
- 59. Other additives may be compounded into the fluoroelastomer to optimize various physical properties. Such additives include carbon black, stabilizers, plasticizers, lubricants, pigments, fillers, and processing aids typically utilized in perfluoroelastomer compounding. Any of these additives can be incorporated into the compositions of the present invention, provided the additive has adequate stability for the intended service conditions.
- 60. Carbon black is used in elastomers as a means to balance modulus, tensile strength, elongation, hardness, abrasion resistance, conductivity, and processability of the compositions. Carbon black is generally useful in amounts of from 5-60 phr.
- 61. In addition, or in the alternative, fluoropolymer fillers may be present in the composition. Generally from 1 to 50 phr of a fluoropolymer filler is used, and preferably at least about 5 phr is present. The fluoropolymer filler can be any finely divided, easily dispersed plastic fluoropolymer that is solid at the highest temperature utilized in fabrication and curing of the perfluoroelastomer composition. By solid, it is meant that the fluoroplastic, if partially crystalline, will have a crystalline melting temperature above the processing temperature(s) of the perfluoroelastomer(s). Such finely divided, easily dispersed fluoroplastics are commonly called micropowders or fluoroadditives. Micropowders are ordinarily partially crystalline polymers.
- 62. A preferred additive class includes molecular sieves, particularly zeolites. Molecular sieve zeolites are crystalline aluminosilicates of Group IA and Group IIA elements, such as sodium, potassium, magnesium, and calcium. Chemically, they are represented by the empirical formula: M2/nO.Al2O3. ySiO2.wH2O where y is 2 or greater, n is the cation valence, and w represents the water contained in the voids of the zeolite. Commercially available examples of such compositions include Molecular Sieve 3A, Molecular Sieve 4A, Molecular Sieve 5A, and Molecular Sieve 13X, all available from Aldrich Chemical Co., Inc. Milwaukee, Wis. Use of this class of additives prevents sponging and improves heat aging of vulcanizates upon press curing in many instances. In general, use of about 1-5 phr is sufficient.
- 63. Other preferred additives include modified silane coated mineral fillers. By “modified silane” is meant that the silane contains at least one reactive functional group such as an amino group, or an epoxy group. The mineral fillers used in this invention are preferably somewhat alkaline, such as calcium metasilicates (CaSiO3), especially wollastonite. Wollastonite coated with either an aminosilane or an epoxysilane is especially preferred. These compounds are commercially available from Quartzwerke GmbH of Freschen, Germany as Tremin®283 EST (epoxysilane treated wollastonite) and Tremin®283 AST (aminosilane treated wollastonite). These modified silane coated mineral fillers prevent sponging of the fluoroelastomer composition during press cure and also accelerate the cure rate. Generally, about 5 to 80 phr modified silane coated mineral filler is useful in the compositions of this invention, about 10 to 60 phr being preferred.
- 64. Organotin hydrides are another class of additive that may be employed. Tri-n-butyltin hydride (TBTH) is especially preferred. These tin hydride fillers accelerate the cure rate of the compositions of this invention and increase the modulus and improve the compression set resistance of the cured compounds. Generally, about 0.2 to 1.5 phr organotin hydride filler is useful, about 0.4 to 0.8 phr being preferred.
- 65. The crosslinking agents, coagent, accelerator, metal oxide, and other additives are generally incorporated into the polymer by means of an internal mixer or on a rubber mill. The resultant composition is then cured, generally by means of heat and pressure, for example by compression transfer or injection molding.
- 66. The curable compositions of the present invention are useful in production of gaskets, tubing, seals and other molded components. Such articles are generally produced by molding a compounded formulation of the curable composition with various additives under pressure, curing the part, and then subjecting it to a post cure cycle. The cured compositions have excellent low temperature flexibility and processability as well as excellent thermal stability and chemical resistance. They are particularly useful in applications such as seals and gaskets requiring a good combination of oil resistance, fuel resistance and low temperature flexibility, for example in fuel injection systems, fuel line connector systems and in other seals for high and low temperature automotive uses.
- 67. The invention is now illustrated by certain embodiments wherein all parts and percentages are by weight unless otherwise specified.
- 68. Cure Characteristics
- 69. Unless otherwise noted, cure characteristics were measured using an Alpha Systems model MDR 2000E moving die rheometer (MDR), under the following conditions:
- 70. Moving die frequency: 1.66 Hertz
- 71. Oscillation amplitude: ±0.5°
- 72. Temperature: 180° C.
- 73. Sample size: 7 to 8 g
- 74. Duration: 12 minutes
- 75. The following cure parameters were recorded:
- 76. MH: maximum torque level, in units of dN.m
- 77. ML: minimum torque level, in units of dN.m
- 78. Delta M: difference between maximum and minimum torque, in units of dN.m
- 79. ts2: minutes to a 2.26 dNm rise above ML
- 80. tc50: minutes to 50% of maximum torque
- 81. tc90: minutes to 90% of maximum torque
- 82. Tensile Properties
- 83. Unless otherwise noted, stress/strain properties were measured on test specimens that had been press cured at 180° C. for 15 minutes and then post cured in a hot air oven for 24 hours at 232° C. The following physical property parameters were recorded; test methods are in parentheses:
- 84. M100: modulus at 100% elongation in units of MPa (ISO 37)
- 85. TB: tensile strength in units of MPa (ISO 37)
- 86. TS: tear strength in units of dN/m (ISO 34, Die B)
- 87. EB: elongation at break in units of % (ISO 37)
- 88. TR-10: temperature of retraction (ISO 2921)
- 89. According to the TR test method, a standard test piece of length 50 mm is stretched at room temperature and then cooled in a bath (usually filled with isopropanol) to a temperature of about 10° C. less than the Tg of the polymer. The test piece is then allowed to retract freely while the test temperature is raised at a rate of 1° C. per minute. Readings of the retracted length are taken every 2 minutes until the retraction reaches 75%. TR-10 is the temperature at which a retraction of 10% is achieved.
- 90. Hardness (Shore A, ISO 868)
- 91. Compression set of small pip samples (ISO 815)
- 92. Polymer 1, a polymer of the invention, was prepared by semi-batch emulsion polymerization carried out at 80° C. in a well-stirred reaction vessel. A 41.5 liter reactor was charged with 63.25 grams of ammonium perfluorooctanoate and 27436.75 grams of deionized, deoxygenated water. The reactor was heated to 80° C. and then pressurized with 800 grams of a mixture of 42.3 mol % vinylidene fluoride, 29.1 mol % perfluoro(methyl vinyl ether), 25.6 mol % 1,1,3,3,3-pentafluoropropene (HPFP), and 3.0 mol % tetrafluoroethylene, bringing the reactor pressure to 1.48 MPa. A 16.0 ml aliquot of a mixture of 49.3 mol % 1,4-diiodoperfluorobutane, 34.8 mol % 1,6-diiodoperfluorohexane, 12.6 mol % 1,8-diiodoperfluorooctane, and 3.3 mol % 1,10-diiodoperfluorodecane was added to the reactor and the resulting mixture agitated 15 minutes. Next, 50.0 ml of a solution of 1% ammonium persulfate and 5% disodium phosphate heptahydrate were added to the reactor. As the reactor pressure dropped, a mixture of 51.4 mol % vinylidene fluoride, 22.6 mol % perfluoro(methyl vinyl ether), 1.1 mol % 1,1,3,3,3-pentafluoropropene, and 24.9 mol % tetrafluoroethylene was added to the reactor to maintain a 1.48 MPa pressure. After 155 grams of the 1% ammonium persulfate/5% disodium phosphate heptahydrate mixture had been added to the reactor, corresponding to the use of 9250 grams of monomer and an elapsed time of 24.0 hours, monomer feed to the reactor was halted and pressure reduced to atmospheric. The pH of the resulting latex was reduced to 3.3 with sulfuric acid. Latex was coagulated with 400 grams of potassium aluminum sulfate, washed with deionized water and then dried at 70° C. for two days. The polymer had a copolymerized monomer unit composition of 32.30 wt. % VF2, 37.50 wt. % PMVE, 28.90 wt. % TFE, 1.20 wt. % HPFP and 0.13 wt. % iodine. Mooney viscosity, ML(1+10) at 121° C., was 93.
- 93. Polymer 1 was compounded on a two-roll rubber mill with the additives shown in Table I. Sample 1B is a composition of this invention. The other samples are controls of a similar composition cured with i) bisphenol only (1A) and ii) peroxide only (1C). Curing characteristics are reported in Table I. Compounds were press molded at 170° C. for 5 minutes and then post cured for 24 hours at 230° C. Physical properties of the cured compositions were measured according to the Test Methods and are also reported in Table I.
TABLE I 1A 1B 1C Formulation, phr Polymer 1 100 100 100 MT Black1 2.5 2.5 2.5 Tremin 283 600 EST2 45 45 45 Calcium Oxide VG 6 6 6 Elastomag 1703 1 1 1 Molecular Sieves 13X 3 3 3 Bisphenol AF4 2 1 0 TBAHS5 0.5 0.25 0 VPA #26 1 1 1 Peroxide7 0 1.9 3.75 Coagent8 0 1.35 2.70 Cure Characteristics ML, dNm 2.72 3.15 3.41 MH, dNm 32.75 42.18 34.09 Delta M, dNm 30.03 39.03 30.68 ts2, minutes 0.60 0.32 0.31 tc50, minutes 1.50 0.53 0.44 tc90, minutes 4.21 1.03 0.64 Peak Rate, dNm/min 17.7 98.3 120 Physical Properties TB, MPa 13.40 16.90 16.50 EB, % 144 135 195 M100, MPa 10.4 14.6 11.1 Hardness (Shore A) 75.3 79.1 77.1 Compression Set (70 23.8 19.6 24.9 hours at 200° C.), % TR-10, ° C. −21 −22 −22
Claims (16)
1. A curable composition comprising:
A. a fluoroelastomer copolymer consisting essentially of copolymerized units of 23-65 weight percent vinylidene fluoride, 25-75 weight percent perfluoro(alkyl vinyl) ether, 0-30 weight percent tetrafluoroethylene, and 0.3-5 weight percent 2-hydropentafluoropropene; said fluoroelastomer having between 0.05 and 1 weight percent iodine chemically bound at copolymer chain ends;
B. a polyhydroxy crosslinking agent;
C. a cure accelerator;
D. an acid acceptor selected from the group consisting of metal oxides, metal hydroxides, and mixtures thereof;
E. an organic peroxide; and
F. a coagent.
2. A composition of wherein the polyhydroxy crosslinking agent is selected from the group consisting of i) dihydroxy-, trihydroxy-, and tetrahydroxy- benzenes, -naphthalenes, and -anthracenes; ii) bisphenols of the formula
claim 1
where A is a stable divalent radical; x is 0 or 1; and n is 1 or 2;
iii) dialkali salts of said bisphenols, iv) quaternary ammonium and phosphonium salts of said bisphenols, v) tertiary sulfonium salts of said bisphenols, and vi) esters of phenols.
3. A curable composition of wherein said cure accelerator is chosen from the group consisting of quaternary ammonium salts, tertiary sulfonium salts and quaternary phosphonium salts.
claim 1
4. A curable composition of wherein said organic peroxide is selected from the group consisting of 2,5-dimethyl-2,5-di(tertiarybutylperoxy)hexyne-3; 2,5-dimethyl-2,5-di(tertiarybutylperoxy)-hexane; dicumylperoxide; dibenzoylperoxide; tertiarybutylperbenzoate; and di[1,3-dimethyl-3-(t-butylperoxy)butyl]carbonate.
claim 1
5. A curable composition of wherein said coagent is selected from the group consisting of triallyl cyanurate; triallyl isocyanurate; tri(methallyl)isocyanurate; tris(diallylamine)-s-triazine; triallyl phosphite; N,N-diallyl acrylamide; hexaallyl phosphoramide; N,N,N′,N′-tetraalkyl tetraphthalamide; N,N,N′,N′-tetraallyl malonamide; trivinyl isocyanurate; 2,4,6-trivinyl methyltrisiloxane; and tri(5-norbornene-2-methylene)cyanurate.
claim 1
6. A composition of further comprising a zeolite.
claim 1
7. A composition of further comprising a modified silane coated mineral filler.
claim 1
8. A composition of wherein the modified silane coated mineral filler is selected from the group consisting of epoxysilane coated wollastonites and aminosilane coated wollastonites.
claim 7
9. A composition of further comprising a molecular sieve.
claim 1
10. A curable composition consisting essentially of
A) a fluoroelastomer copolymer consisting essentially of copolymerized units of 23-65 weight percent vinylidene fluoride, 25-75 weight percent perfluoro(alkyl vinyl) ether, 0-30 weight percent tetrafluoroethylene, and 0.3-5 weight percent 2-hydropentafluoropropene; said fluoroelastomer having between 0.05 and 1 weight percent iodine chemically bound to copolymer chain ends; and
B) a compound selected from the group consisting of i) quaternary ammonium salts of a bisphenol, ii) quaternary phosphonium salts of a bisphenol and iii) tertiary sulfonium salts of a bisphenol;
C) an acid acceptor selected from the group consisting of metal oxides, metal hydroxides, and mixtures thereof;
D) an organic peroxide; and
E) a coagent.
11. A curable composition of wherein said organic peroxide is selected from the group consisting of 2,5-dimethyl-2,5-di(tertiarybutylperoxy)hexyne-3; 2,5-dimethyl-2,5-di(tertiarybutylperoxy)-hexane; dicumylperoxide; dibenzoylperoxide; tertiarybutylperbenzoate; and di[1,3-dimethyl-3-(t-butylperoxy)butyl]carbonate.
claim 10
12. A curable composition of wherein said coagent is selected from the group consisting of triallyl cyanurate; triallyl isocyanurate; tri(methallyl)isocyanurate; tris(diallylamine)-s-triazine; triallyl phosphite; N,N-diallyl acrylamide; hexaallyl phosphoramide; N,N,N′,N′-tetraalkyl tetraphthalamide; N,N,N′,N′-tetraallyl malonamide; trivinyl isocyanurate; 2,4,6-trivinyl methyltrisiloxane; and tri(5-norbomene-2-methylene)cyanurate.
claim 10
13. A composition of further comprising a zeolite.
claim 10
14. A composition of further comprising a modified silane coated mineral filler.
claim 10
15. A composition of wherein the modified silane coated mineral filler is selected from the group consisting of epoxysilane coated wollastonite and aminosilane coated wollastonite.
claim 14
16. A composition of further comprising a molecular sieve.
claim 10
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