CN101065440A - Thermoplastic polymer composition and process for production thereof - Google Patents
Thermoplastic polymer composition and process for production thereof Download PDFInfo
- Publication number
- CN101065440A CN101065440A CN200580040551.XA CN200580040551A CN101065440A CN 101065440 A CN101065440 A CN 101065440A CN 200580040551 A CN200580040551 A CN 200580040551A CN 101065440 A CN101065440 A CN 101065440A
- Authority
- CN
- China
- Prior art keywords
- polymer composition
- thermoplastic polymer
- resin
- fluoro
- weight
- Prior art date
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- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 106
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 85
- 238000000034 method Methods 0.000 title description 30
- 238000004519 manufacturing process Methods 0.000 title description 13
- 230000008569 process Effects 0.000 title description 13
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 59
- 239000000126 substance Substances 0.000 claims abstract description 58
- 239000011737 fluorine Substances 0.000 claims abstract description 52
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000004132 cross linking Methods 0.000 claims abstract description 43
- 229920002725 thermoplastic elastomer Polymers 0.000 claims abstract description 42
- 229920001973 fluoroelastomer Polymers 0.000 claims abstract description 38
- 238000000465 moulding Methods 0.000 claims abstract description 23
- 238000002844 melting Methods 0.000 claims abstract description 15
- 230000008018 melting Effects 0.000 claims abstract description 15
- 239000000446 fuel Substances 0.000 claims description 64
- 229920002449 FKM Polymers 0.000 claims description 57
- 239000011347 resin Substances 0.000 claims description 55
- 229920005989 resin Polymers 0.000 claims description 55
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 50
- 239000003795 chemical substances by application Substances 0.000 claims description 45
- -1 poly(vinylidene fluoride) Polymers 0.000 claims description 38
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 claims description 37
- 239000010410 layer Substances 0.000 claims description 35
- 150000001875 compounds Chemical class 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 25
- 239000003566 sealing material Substances 0.000 claims description 24
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 22
- 229920005862 polyol Polymers 0.000 claims description 14
- 150000003077 polyols Chemical class 0.000 claims description 14
- 229920005992 thermoplastic resin Polymers 0.000 claims description 12
- 239000000155 melt Substances 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 229920000768 polyamine Polymers 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 239000005977 Ethylene Substances 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 5
- 239000011342 resin composition Substances 0.000 claims description 5
- 239000002356 single layer Substances 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 abstract description 47
- 229920001971 elastomer Polymers 0.000 description 42
- 239000005060 rubber Substances 0.000 description 40
- 238000007789 sealing Methods 0.000 description 37
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 32
- 239000000178 monomer Substances 0.000 description 30
- 239000011248 coating agent Substances 0.000 description 19
- 239000002245 particle Substances 0.000 description 19
- 238000000576 coating method Methods 0.000 description 17
- 229920001577 copolymer Polymers 0.000 description 17
- 229910052740 iodine Inorganic materials 0.000 description 17
- 230000006835 compression Effects 0.000 description 15
- 238000007906 compression Methods 0.000 description 15
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert-Butyl hydroperoxide Substances CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 14
- 230000004888 barrier function Effects 0.000 description 13
- 239000011630 iodine Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 11
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 10
- 125000001153 fluoro group Chemical group F* 0.000 description 10
- 230000009467 reduction Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 229920000459 Nitrile rubber Polymers 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 229920005673 polypropylene based resin Polymers 0.000 description 7
- 229920006169 Perfluoroelastomer Polymers 0.000 description 6
- 125000001246 bromo group Chemical group Br* 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229920002313 fluoropolymer Polymers 0.000 description 6
- 239000004811 fluoropolymer Substances 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 5
- 239000003995 emulsifying agent Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 229920000915 polyvinyl chloride Polymers 0.000 description 5
- 239000004800 polyvinyl chloride Substances 0.000 description 5
- 238000007639 printing Methods 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 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 description 4
- LQNYBXQRMCHSHV-UHFFFAOYSA-M P.[Cl-].C(C1=CC=CC=C1)[P+](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound P.[Cl-].C(C1=CC=CC=C1)[P+](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1 LQNYBXQRMCHSHV-UHFFFAOYSA-M 0.000 description 4
- 150000001491 aromatic compounds Chemical class 0.000 description 4
- 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 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 238000009434 installation Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- QYSGYZVSCZSLHT-UHFFFAOYSA-N octafluoropropane Chemical compound FC(F)(F)C(F)(F)C(F)(F)F QYSGYZVSCZSLHT-UHFFFAOYSA-N 0.000 description 4
- 229960004065 perflutren Drugs 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N perisophthalic acid Natural products OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 150000004714 phosphonium salts Chemical class 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 3
- 239000004160 Ammonium persulphate Substances 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 229920002943 EPDM rubber Polymers 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003905 agrochemical Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 3
- 235000019395 ammonium persulphate Nutrition 0.000 description 3
- 229920005601 base polymer Polymers 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000002093 peripheral effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 235000012431 wafers Nutrition 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- FDMFUZHCIRHGRG-UHFFFAOYSA-N 3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C=C FDMFUZHCIRHGRG-UHFFFAOYSA-N 0.000 description 2
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- 229920001817 Agar Polymers 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- QBTUCBKAWGUMMK-UHFFFAOYSA-N C=CC.[F] Chemical group C=CC.[F] QBTUCBKAWGUMMK-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 2
- 229920000800 acrylic rubber Polymers 0.000 description 2
- 239000008272 agar Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000001118 alkylidene group Chemical group 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000012661 block copolymerization Methods 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000010227 cup method (microbiological evaluation) Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
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- 150000002221 fluorine Chemical class 0.000 description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Natural products OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
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- 239000010453 quartz Substances 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
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- PEGQMHNLNMIEQD-UHFFFAOYSA-N 1,1-difluorohexane Chemical class CCCCCC(F)F PEGQMHNLNMIEQD-UHFFFAOYSA-N 0.000 description 1
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 1
- AAAXMNYUNVCMCJ-UHFFFAOYSA-N 1,3-diiodopropane Chemical compound ICCCI AAAXMNYUNVCMCJ-UHFFFAOYSA-N 0.000 description 1
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 description 1
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 1
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 1
- XSQHUYDRSDBCHN-UHFFFAOYSA-N 2,3-dimethyl-2-propan-2-ylbutanenitrile Chemical compound CC(C)C(C)(C#N)C(C)C XSQHUYDRSDBCHN-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- FEVVTKCAZXCXEQ-UHFFFAOYSA-N 2-(4-hydroxyphenyl)pentanoic acid Chemical compound CCCC(C(O)=O)C1=CC=C(O)C=C1 FEVVTKCAZXCXEQ-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
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- CYYZDBDROVLTJU-UHFFFAOYSA-N 4-n-Butylphenol Chemical compound CCCCC1=CC=C(O)C=C1 CYYZDBDROVLTJU-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- RAKHOPMAIJNICX-UHFFFAOYSA-N C1=CC(=CC=C1C(C(C(F)(F)Cl)(F)Cl)F)O Chemical compound C1=CC(=CC=C1C(C(C(F)(F)Cl)(F)Cl)F)O RAKHOPMAIJNICX-UHFFFAOYSA-N 0.000 description 1
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- NSFGOWGWLHAJPC-UHFFFAOYSA-N COCOC.C(C=C)(=O)O Chemical class COCOC.C(C=C)(=O)O NSFGOWGWLHAJPC-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- VHOQXEIFYTTXJU-UHFFFAOYSA-N Isobutylene-isoprene copolymer Chemical group CC(C)=C.CC(=C)C=C VHOQXEIFYTTXJU-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- KYPYTERUKNKOLP-UHFFFAOYSA-N Tetrachlorobisphenol A Chemical compound C=1C(Cl)=C(O)C(Cl)=CC=1C(C)(C)C1=CC(Cl)=C(O)C(Cl)=C1 KYPYTERUKNKOLP-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- YCLAMANSVUJYPT-UHFFFAOYSA-L aluminum chloride hydroxide hydrate Chemical compound O.[OH-].[Al+3].[Cl-] YCLAMANSVUJYPT-UHFFFAOYSA-L 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- ZUNYPSAHNPANBJ-UHFFFAOYSA-N benzene;2-hydroperoxy-2-methylpropane Chemical compound CC(C)(C)OO.C1=CC=CC=C1 ZUNYPSAHNPANBJ-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- WCHPXAFAEZGCMB-UHFFFAOYSA-M benzyl(tributyl)phosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CC1=CC=CC=C1 WCHPXAFAEZGCMB-UHFFFAOYSA-M 0.000 description 1
- TXXACRDXEHKXKD-UHFFFAOYSA-M benzyl(trimethyl)phosphanium;chloride Chemical compound [Cl-].C[P+](C)(C)CC1=CC=CC=C1 TXXACRDXEHKXKD-UHFFFAOYSA-M 0.000 description 1
- XCVBOIFCQHWRDY-UHFFFAOYSA-N benzyl-(dimethylamino)-phenylphosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[PH+](N(C)C)CC1=CC=CC=C1 XCVBOIFCQHWRDY-UHFFFAOYSA-N 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- HZTNYDWTDTYXQC-UHFFFAOYSA-N bis(prop-2-ynyl) benzene-1,4-dicarboxylate Chemical compound C#CCOC(=O)C1=CC=C(C(=O)OCC#C)C=C1 HZTNYDWTDTYXQC-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- PZAIVXOIUQBUAI-UHFFFAOYSA-N carbamic acid;1-methylcyclohexan-1-amine Chemical compound NC(O)=O.CC1(N)CCCCC1 PZAIVXOIUQBUAI-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
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- 238000006356 dehydrogenation reaction Methods 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
- 150000001993 dienes Chemical class 0.000 description 1
- 150000007520 diprotic acids Chemical class 0.000 description 1
- 238000005108 dry cleaning Methods 0.000 description 1
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- 230000005684 electric field Effects 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 229920005558 epichlorohydrin rubber Polymers 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
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- 239000003063 flame retardant Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical group C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
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- 239000003112 inhibitor Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
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- 150000002497 iodine compounds Chemical class 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- WRIRWRKPLXCTFD-UHFFFAOYSA-N malonamide Chemical compound NC(=O)CC(N)=O WRIRWRKPLXCTFD-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- JPQBRSQJGWOTGC-UHFFFAOYSA-N methyl(silyloxysilyloxy)silane Chemical class C[SiH2]O[SiH2]O[SiH3] JPQBRSQJGWOTGC-UHFFFAOYSA-N 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 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 description 1
- ATPFMBHTMKBVLS-UHFFFAOYSA-N n-[6-(cinnamylideneamino)hexyl]-3-phenylprop-2-en-1-imine Chemical compound C=1C=CC=CC=1C=CC=NCCCCCCN=CC=CC1=CC=CC=C1 ATPFMBHTMKBVLS-UHFFFAOYSA-N 0.000 description 1
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229960004692 perflenapent Drugs 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000004978 peroxycarbonates Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- NAYYNDKKHOIIOD-UHFFFAOYSA-N phthalamide Chemical compound NC(=O)C1=CC=CC=C1C(N)=O NAYYNDKKHOIIOD-UHFFFAOYSA-N 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
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- 238000010010 raising Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 1
- IBWGNZVCJVLSHB-UHFFFAOYSA-M tetrabutylphosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CCCC IBWGNZVCJVLSHB-UHFFFAOYSA-M 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- UDRBACREFJVZDG-UHFFFAOYSA-M tributyl(2-methoxypropyl)phosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CC(C)OC UDRBACREFJVZDG-UHFFFAOYSA-M 0.000 description 1
- GRPURDFRFHUDSP-UHFFFAOYSA-N tris(prop-2-enyl) benzene-1,2,4-tricarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C(C(=O)OCC=C)=C1 GRPURDFRFHUDSP-UHFFFAOYSA-N 0.000 description 1
- KJWHEZXBZQXVSA-UHFFFAOYSA-N tris(prop-2-enyl) phosphite Chemical compound C=CCOP(OCC=C)OCC=C KJWHEZXBZQXVSA-UHFFFAOYSA-N 0.000 description 1
- SANRKQGLYCLAFE-UHFFFAOYSA-H uranium hexafluoride Chemical compound F[U](F)(F)(F)(F)F SANRKQGLYCLAFE-UHFFFAOYSA-H 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明的目的在于提供一种热塑性聚合物组合物，其兼具优异的耐热性－耐化学性－耐油性、具有柔软性、且成型加工性优异。本发明的热塑性聚合物组合物含有10重量％～95重量％氟树脂(A)和90重量％～5重量％交联氟橡胶(B)，其中，所述氟树脂(A)含有熔点为120℃～330℃的含氟乙烯性聚合物(a)，所述交联氟橡胶(B)是在氟树脂(A)和交联剂(C)的存在下，使至少1种的氟橡胶(b－1)或含氟热塑性弹性体(b－2)在熔融条件下进行动态交联处理而成的。An object of the present invention is to provide a thermoplastic polymer composition having excellent heat resistance-chemical resistance-oil resistance, flexibility, and excellent molding processability. The thermoplastic polymer composition of the present invention contains 10% by weight to 95% by weight of fluororesin (A) and 90% by weight to 5% by weight of cross-linked fluororubber (B), wherein the fluororesin (A) contains ℃～330℃ fluorine-containing ethylenic polymer (a), the crosslinked fluororubber (B) is at least one kind of fluororubber ( b-1) or fluorine-containing thermoplastic elastomer (b-2) undergoes dynamic cross-linking treatment under melting conditions.
Description
Technical field
The present invention relates to contain the thermoplastic polymer composition of fluoro-resin and crosslinked fluororubber, also relate to the moulding product, sealing material, fuel periphery part, fuel hose, the fuel container that contain this thermoplastic polymer composition.
Background technology
Cross-linked rubber is used in the fields such as vehicle part, tame electrical accessory, electric wire coating, medical part owing to have excellent thermotolerance, chemical resistant properties, flexibility more.But, when using cross-linked rubber to make the moulding product, generally to pass through complicated step, this operation for example is: (1) uses pressurization or baker to carry out crosslinked step etc. uncrosslinked rubber and linking agent, the step, (3) that are subjected to common mixing step, (2) such as sour agent, weighting agent to use forcing machine or injection moulding machine to carry out moulding, thereby will obtain the essential time of length of moulding product.In addition, because cross-linked rubber not fusion after crosslinked, thereby post-treatment such as can not fuse, the problem that existence can not recirculation.
In order to address the above problem, to have developed thermoplastic resins such as making polypropylene-based resin and uncrosslinked bridging property rubber and in forcing machine, carried out melting mixing and carry out crosslinked so-called dynamic crosslinking technology simultaneously with linking agent.
According to this technology, can obtain the cross-linked rubber particle is dispersed in the thermoplastic resin composition who forms in the thermoplastic resins such as polypropylene-based resin, this thermoplastic resin composition is thermoplastic, can carry out melt molding or recirculation, and can show the performance that is similar to cross-linked rubber.As this dynamic crosslinking rubber (TPV), for example have and dynamic crosslinking rubber that crosslinked ethylene-propylene-dience rubber (EPDM) is scattered in the structure in the polypropylene-based resin to have taken place (for example, with reference to the spy open flat 6-287368 communique, the spy opens flat 6-256571 communique or the spy opens flat 11-228750 communique) etc. rubber obtained extensive studies, a part wherein is practical.
But for the above-mentioned TPV that contains polypropylene-based resin and crosslinked EPDM, because its matrix is polypropylene-based resin, thereby in fact it does not have thermotolerance when the fusing point of polypropylene-based resin is above, and chemical resistant properties is also relatively poor in addition.
In order to develop the TPV of thermotolerance and chemical resistant properties excellence, for example known have use polyester resin or 4-methyl-1-pentene resinoid as matrix come the decentralized crosslinking rubber structure TPV (for example, with reference to the spy open flat 10-212392 communique, the spy opens flat 11-269330 communique).But, compare with the TPV that contains polypropylene-based resin and crosslinked EPDM, though these TPV are also insufficient in that some raisings are arranged aspect thermotolerance and the chemical resistant properties, there is the relatively poor problem of flexibility or mechanical property in addition.
And then, carried out studying to having the TPV that has disperseed to take place the structure of crosslinked viton (this crosslinked viton has taken place as cross-linked rubber) as matrix with fluoro-resin (for example, with reference to the spy open clear 61-57641 communique, the spy opens flat 5-140401 communique or the spy opens flat 6-228397 communique).Though this TPV has by thermotolerance and chemical resistant properties as the excellence that fluoro-resin brought of matrix, because the dispersion heterogeneity of crosslinked fluororubber, thereby rerum naturas such as its flexibility or compression set are relatively poor, forming process is also insufficient in addition.
Summary of the invention
The object of the present invention is to provide a kind of thermoplastic polymer composition, this thermoplastic polymer composition has excellent thermotolerance-chemical resistant properties-oil-proofness-fuel shielding concurrently, has flexibility and forming process excellence.
Promptly, the present invention relates to a kind of thermoplastic polymer composition, this thermoplastic polymer composition contains 10 weight %～95 weight % fluoro-resin (A) and 90 weight %～5 weight % crosslinked fluororubbers (B), wherein, described fluoro-resin (A) contain fusing point be 120 ℃～330 ℃ contain vinyl fluoride polymkeric substance (a), described crosslinked fluororubber (B) is in the presence of fluoro-resin (A) and linking agent (C), makes at least a kind viton (b-1) or fluorine-containing thermoplastic elastomer (b-2) carry out dynamic crosslinking under melting condition and handles and to form.
The fusing point that contains vinyl fluoride polymkeric substance (a) is preferably 150 ℃～310 ℃.
Contain vinyl fluoride polymkeric substance (a) and be preferably at least a polymkeric substance that is selected from by in following (a-1), (a-2), (a-3) and the group (a-4) formed,
Described (a-1) is the multipolymer of tetrafluoroethylene and ethene;
Described (a-2) is the multipolymer of the perfluoro-ethylene unsaturated compound shown in tetrafluoroethylene and the following general formula (1);
Described (a-3) is for containing the unitary multipolymer of perfluoro-ethylene unsaturated compound shown in 19 moles of %～90 mole % tetrafluoroethylene units, 9 moles of %～80 mole % ethylene unit and the 1 mole of following general formula of %～72 mole % (1);
Described (a-4) is poly(vinylidene fluoride);
Described general formula (1) is:
CF
2＝CF-R
f 1 (1)
In the general formula (1), R
f 1Expression-CF
3Or-OR
f 2, R
f 2The expression carbonatoms is 1～5 perfluoroalkyl.
Linking agent (C) is preferably at least a kind of material that is selected from the group of being made up of organo-peroxide, polyamine compounds, polyol.
Described composition is preferably the structure that fluoro-resin (A) forms external phase and crosslinked fluororubber (B) formation disperse phase.
The average mark shot of crosslinked fluororubber (B) directly is preferably 0.01 μ m～30 μ m.
Fluoro-resin (A) is preferably 0.1～1.5 with the ratio of the melt viscosity of viton (b-1) or fluorine-containing thermoplastic elastomer (b-2).
The melt flow rate (MFR) of thermoplastic polymer composition is preferably 1g/10min～30g/10min.
The fuel perviousness of thermoplastic polymer composition is preferably 0.1gmm/m
2My god～20gmm/m
2My god.
In addition, the present invention relates to contain moulding product, sealing material, fuel periphery part, single layer fuel flexible pipe and the single layer fuel container of above-mentioned thermoplastic polymer composition.
The present invention also relates to the multilayer fuel hose or the multilayer fuel container of the layer that contains above-mentioned thermoplastic polymer composition further.
Embodiment
The present invention relates to a kind of thermoplastic polymer composition, this thermoplastic polymer composition contains 10 weight %～95 weight % fluoro-resin (A) and 90 weight %～5 weight % crosslinked fluororubbers (B), wherein, described fluoro-resin (A) contain fusing point be 120 ℃～330 ℃ contain vinyl fluoride polymkeric substance (a), described crosslinked fluororubber (B) is in the presence of fluoro-resin (A) and linking agent (C), makes at least a kind viton (b-1) or fluorine-containing thermoplastic elastomer (b-2) carry out dynamic crosslinking under melting condition and handles and to form.
As fluoro-resin (A), do not limit especially, can be for containing at least a kind the fluoro-resin that contains vinyl fluoride polymkeric substance (a), contain vinyl fluoride polymkeric substance (a) can have derive from least a kind contain the monomeric structural unit of vinyl fluoride.As the above-mentioned vinyl fluoride monomer that contains, for example can enumerate the perfluoroolefines such as perfluoro-ethylene unsaturated compound shown in tetrafluoroethylene, the following general formula (1); The fluoroolefin of the compound shown in chlorotrifluoroethylene, trifluoro-ethylene, hexafluoro-isobutene, vinylidene fluoride, vinyl fluoride, the following general formula (2) etc. etc.;
CF
2＝CF-R
f 1 (1)
In the general formula (1), R
f 1For-CF
3Or-OR
f 2, R
f 2Be that carbonatoms is 1～5 perfluoroalkyl;
CH
2＝CX
1(CF
2)
nX
2 (2)
In the general formula (2), X
1Be hydrogen atom or fluorine atom, X
2Be hydrogen atom, fluorine atom or chlorine atom, n is 1～10 integer.
And, contain vinyl fluoride polymkeric substance (a) can have derive from can with the above-mentioned monomeric structural unit that contains the vinyl fluoride monomer copolymerization, as this monomer, can enumerate the not fluorine-containing ethene monomer except that above-mentioned fluoroolefins, perfluoroolefine.As not fluorine-containing ethene monomer, for example can enumerate ethene, propylene or alkyl vinyl ethers etc.Wherein, alkyl vinyl ether refers to and has the alkyl vinyl ether that carbonatoms is 1～5 alkyl.
Wherein, becoming from the thermotolerance-chemical resistant properties-oil-proofness excellence of resulting thermoplastic polymer composition and forming process is easy to the aspect and considers, fluorine-containing polyvinyls (a) be preferably (a-1), (a-2), (a-3) and (a-4) in any one;
Described (a-1) is for containing the ethylene-tetrafluoroethylene copolymer (ETFE) of tetrafluoroethylene and ethene;
Described (a-2) is for containing tetrafluoroethylene-perfluor (alkyl vinyl ether) multipolymer (PFA) or the tetrafluoraoethylene-hexafluoropropylene copolymer (FEP) of the perfluoro-ethylene unsaturated compound shown in tetrafluoroethylene and the following general formula (1);
Described (a-3) is for containing the ethylene-tetrafluoroethylene-hexafluoropropylene copolymer (Et-TFE-HFP multipolymer) of the perfluoro-ethylene unsaturated compound shown in tetrafluoroethylene, ethene and the following general formula (1);
Described (a-4) is poly(vinylidene fluoride) (PVDF);
Described general formula (1) is:
CF
2＝CF-R
f 1 (1)
In the general formula (1), R
f 1For-CF
3Or-OR
f 2, R
f 2Be that carbonatoms is 1～5 perfluoroalkyl.Then the vinyl fluoride polymkeric substance that preferably contains to (a-1)～(a-4) describes.
(a-1)ETFE
The described vinyl fluoride polymkeric substance (a) that contains is when the ETFE, and it is being preferred aspect low fuel perviousness and the flexibility also except having above-mentioned action effect.The containing mol ratio and be preferably 20: 80 of tetrafluoroethylene units and ethylene unit～90: 10, more preferably 62: 38～90: 10, be preferably 63: 37～80: 20 especially.It can also contain the 3rd composition, as the 3rd composition, so long as can then its kind not limited with the composition of tetrafluoroethylene and ethylene copolymer.As the 3rd composition, use the monomer shown in the following formula usually;
CH
2=CX
3R
f 3, CF
2=CFR
f 3, CF
2=CFOR
f 3, CH
2=C (R
f 3)
2(in the formula, X
3Expression hydrogen atom or fluorine atom, R
f 3The expression fluoro-alkyl), wherein, CH more preferably
2=CX
3R
f 3Shown fluorine-containing vinyl monomer, preferred especially R
f 3Carbonatoms be 1～8 monomer.
As containing the monomeric object lesson of vinyl fluoride shown in the following formula, can enumerate 1,1-dihydro perfluor-1-propylene, 1,1-dihydro perfluor-1-butylene, 1,1,5-three hydrogen perfluor-1-amylene, 1,1,7-three hydrogen perfluor-1-heptene, 1,1,2-three hydrogen perfluor-1-hexene, 1,1,2-three hydrogen perfluor-1-octene, 2,2,3,3,4,4,5,5-octafluoro amyl group vinyl ether, perfluor (methylvinylether), perfluor (propyl vinyl ether), R 1216, perfluor-1-butylene, 3,3,3-three fluoro-2-Trifluoromethyl-1-propylene, 2,3,3,4,4,5,5-seven fluoro-1-amylene (CH
2=CFCF
2CF
2CF
2H).
The content of the 3rd composition is preferably 0.1 mole of %～10 mole % with respect to containing vinyl fluoride polymkeric substance (a), and more preferably 0.1 mole of %～5 mole % is preferably 0.2 mole of %～4 mole % especially.
(a-2) PFA or FEP
Described when containing vinyl fluoride polymkeric substance (a) for PFA or FEP, it has excellent thermotolerance especially in above-mentioned action effect, and except that having above-mentioned action effect, also shows the low fuel perviousness, so is preferred.The described vinyl fluoride polymkeric substance (a) that contains more preferably contains the perfluoro-ethylene unsaturated compound unit shown in 90 moles of %～99 mole % tetrafluoroethylene units and the 1 mole of %～10 mole % general formula (1).In addition, contain containing vinyl fluoride polymkeric substance (a) and also can containing the 3rd composition of the perfluoro-ethylene unsaturated compound shown in tetrafluoroethylene and the general formula (1), as the 3rd composition, so long as can then its kind not limited with the composition of the perfluoro-ethylene unsaturated compound copolymerization shown in tetrafluoroethylene and the general formula (1).
(a-3) Et-TFE-HFP multipolymer
The described vinyl fluoride polymkeric substance (a) that contains is when the Et-TFE-HFP multipolymer, and it is also preferred aspect low fuel perviousness and flexibility except that having above-mentioned action effect.This contains vinyl fluoride polymkeric substance (a) and more preferably contains the perfluoro-ethylene unsaturated compound unit shown in 19 moles of %～90 mole % tetrafluoroethylene units, 9 moles of %～80 mole % ethylene unit and the 1 mole of %～72 mole % general formula (1), further preferably contains the perfluoro-ethylene unsaturated compound unit shown in 20 moles of %～70 mole % tetrafluoroethylene units, 20 moles of %～60 mole % ethylene unit and the 1 mole of %～60 mole % general formula (1).
In addition, contain containing vinyl fluoride polymkeric substance (a) and also can containing and append composition of the perfluoro-ethylene unsaturated compound shown in tetrafluoroethylene, ethene and the general formula (1), as appending composition, can enumerate 2,3,3,4,4,5,5-seven fluoro-1-amylene (CH
2=CFCF
2CF
2CF
2H) etc.
The content that appends composition is preferably 0.1 mole of %～3 mole % with respect to containing vinyl fluoride polymkeric substance (a).
(a-4)PVDF
The described vinyl fluoride polymkeric substance (a) that contains is when the PVDF, and it also has flexibility and excellent mechanics rerum natura except that having above-mentioned action effect, therefore preferably.
In addition, the fusing point that contains vinyl fluoride polymkeric substance (a) is 120 ℃～330 ℃, is preferably 150 ℃～310 ℃, more preferably 150 ℃～290 ℃, and more preferably 170 ℃～250 ℃.If the fusing point that contains vinyl fluoride polymkeric substance (a) is less than 120 ℃, then the thermotolerance of resulting thermoplastic polymer composition has the trend of reduction; If above 330 ℃, then when making viton (b-1) or fluorine-containing thermoplastic elastomer (b-2) under melting condition, carry out dynamic crosslinking in the presence of fluoro-resin (A) and the linking agent (C), melt temperature need be set in more than the fusing point that contains vinyl fluoride polymkeric substance (a), but this moment, viton (b-1) or fluorine-containing thermoplastic elastomer (b-2) had the trend of thermal degradation when.
As employed crosslinked fluororubber (B) among the present invention, handle and form so long as make at least a kind viton (b-1) or fluorine-containing thermoplastic elastomer (b-2) under melting condition, carry out dynamic crosslinking, then do not limit especially.
As viton (b-1), for example can enumerate FFKM, non-FFKM etc.
As FFKM, can enumerate tetrafluoroethylene (TFE hereinafter referred to as)/perfluor (alkyl vinyl ether) (PAVE hereinafter referred to as) analog copolymer, TFE/ R 1216 (HFP hereinafter referred to as)/PAVE analog copolymer etc.
As non-FFKM, for example can enumerate, vinylidene fluoride (VdF hereinafter referred to as) base polymer, TFE/ propylene copolymers etc., they can distinguish use separately or arbitrary combination use in the scope of not damaging effect of the present invention.
In addition, the example of enumerating as above-mentioned FFKM or non-FFKM is the structure of its principal monomer, also can use the rubber that above-mentioned principal monomer and crosslinkable monomer or modified monomer etc. is carried out copolymerization and obtain aptly.As crosslinkable monomer or modified monomer, can use the known crosslinkable monomers such as monomer that contain iodine atom, bromine atoms, two keys; Modified monomers such as transfer agent, known ethene unsaturated compound etc.
As above-mentioned VdF base polymer, specifically, can enumerate VdF/HFP analog copolymer, VdF/TFE/HFP analog copolymer, VdF/TFE/ propylene copolymers, VdF/ ethene/HFP analog copolymer, VdF/TFE/PAVE analog copolymer, VdF/PAVE analog copolymer, VdF/ chlorotrifluoroethylene (CTFE hereinafter referred to as) analog copolymer etc.More particularly, described VdF base polymer be preferably the VdF that contains 25 moles of %～85 mole % and 75 moles of %～15 mole % can with at least a kind of other monomeric fluorinated copolymer of VdF copolymerization, more preferably contain the VdF of 50 moles of %～80 mole % and 50 moles of %～20 mole % can with at least a kind of other monomeric fluorinated copolymer of VdF copolymerization.
Wherein, as can with other monomer of at least a kind of VdF copolymerization, for example can enumerate fluorochemical monomers such as TFE, CTFE, trifluoro-ethylene, HFP, trifluoro propene, tetrafluoeopropene, five fluorine propylene, trifluoro butylene, tetrafluoro iso-butylene, PAVE, vinyl fluoride; Ethene, propylene, alkyl vinyl ether etc. are fluorochemical monomer not.They can distinguish use separately or arbitrary combination is used.
In the above-mentioned viton, consider, be preferably and contain the unitary viton of VdF, consider more preferably have the unitary viton of VdF unit and HFP from the aspect of compression set excellence from thermotolerance, compression set, processibility, cost aspect.
In addition, above-mentioned viton is preferably at least a kind of rubber that is selected from the group of being made up of VdF/HFP class viton, VdF/TFE/HFP class viton, TFE/ propylene class viton, more preferably VdF/TFE/HFP class viton.
As fluorine-containing thermoplastic elastomer (b-2), as long as contain at least a kind of elastomerics polymer segment (S1) and at least a kind of inelastic body polymer segment (S2), then do not limit especially, but from considering with the aspect of the consistency excellence of fluoro-resin (A), at least one side in preferred elastomer polymer segment (S1) and the inelastic body polymer segment (S2) is the fluoropolymer segment, more preferably S1 and S2 the two all be the fluoropolymer segment.At this moment, can expect that the forming process of thermoplastic polymer composition of the present invention is improved, and can expect that the moulding product that obtain thus have excellent tensile break strength and tension fracture elongation rate.
The elastomerics polymer segment (S1) give flexibility to polymkeric substance, and its second-order transition temperature is below 25 ℃, is preferably below 0 ℃.As its structural unit, for example can enumerate the perhalogeno alkene such as perfluoroalkyl vinyl ether shown in tetrafluoroethylene, chlorotrifluoroethylene, R 1216, the following general formula (3); Fluorochemical monomers such as vinylidene fluoride, trifluoro-ethylene, trifluoro propene, tetrafluoeopropene, five fluorine propylene, trifluoro butylene, tetrafluoro iso-butylene, vinyl fluoride; Ethene, propylene, alkyl vinyl ether etc. are fluorochemical monomer etc. not;
CF
2＝CFO(CF
2CFX
4O)
p-(CF
2CF
2CF
2O)
q-R
f 4 (3)
In the general formula (3), X
4For fluorine atom or-CF
3, R
f 4Be that carbonatoms is 1～5 perfluoroalkyl, p is 0～5 integer, and q is 0～5 integer.
As the monomer that cross-linking part is provided, for example can enumerate, the monomers shown in the monomer that contains iodine or bromine shown in the following general formula (4), the following general formula (5) etc., these monomers can be distinguished use separately or arbitrary combination is used;
CX
5 2＝CX
5-R
f 5CHR
1X
6 (4)
In the general formula (4), X
5For hydrogen atom, fluorine atom or-CH
3, R
f 5Be fluoro alkylidene group, perfluorinated alkylidene, fluoro polyoxyalkylene or perfluor polyoxyalkylene, R
1For hydrogen atom or-CH
3, X
6Be iodine atom or bromine atoms;
CF
2＝CFO(CF
2CF(CF
3)O)
m(CF
2)
n-X
7 (5)
In the general formula (5), m is 0～5 integer, and n is 1～3 integer, X
7Be cyano group, carboxyl, carbalkoxy, bromine atoms.
Then, as the structural unit of inelastic body polymer segment (S2), can enumerate perhalogeno alkene such as the compound shown in tetrafluoroethylene, chlorotrifluoroethylene, perfluor (alkyl vinyl ether), R 1216, the following general formula (6), perfluor-2-butylene; Compound, CH shown in vinylidene fluoride, vinyl fluoride, trifluoro-ethylene, the following general formula (7)
2=C (CF
3)
2Etc. partially fluorinated alkene; The not fluorochemical monomer of ethene, propylene, vinylchlorid, vinyl ether, vinyl esters of carboxylic acids, vinylformic acid etc. etc.;
CF
2＝CF(CF
2)
rX
8 (6)
In the general formula (6), r is 1～10 integer, X
8Be fluorine atom or chlorine atom;
CH
2＝CX
9-(CF
2)
s-X
9 (7)
In the general formula (7), X
9Be hydrogen atom or fluorine atom, s is 1～10 integer.
In addition, wherein preferred elastomer polymer segment (S1) is a tetrafluoroethylene, the multipolymer of vinylidene fluoride and R 1216 and inelastic body polymer segment (S2) are the fluorine-containing thermoplastic elastomer (b-2) of the multipolymer of tetrafluoroethylene and ethene, and more preferably elastomerics polymer segment (S1) is that tetrafluoroethylene/vinylidene fluoride/R 1216=0 mole %～35 moles %/40 mole %～90 moles %/5 mole %～50 moles % and inelastic body polymer segment (S2) are the fluorine-containing thermoplastic elastomer (b-2) of tetrafluoroethylene/ethylene=20 mole %～80 moles of %/80 mole %～20 moles of %.
Importantly, fluorine-containing thermoplastic elastomer (b-2) is the fluorine-containing polynary segment fluidized polymer that elastomerics polymer segment (S1) and inelastic body polymer segment (S2) form with block or grafted mode bonding in 1 molecule, and this fluorine-containing thermoplastic elastomer (b-2) more preferably contains:
(1) contain 1 elastomerics polymer segment (S1) and 1 inelastic body polymer segment (S2) and a side wherein for the diblock polymer of fluoropolymer segment and/or
(2) containing 1 elastomerics polymer segment (S1) and 2 inelastic body polymer segments (S2) and at least one side wherein is the triblock polymer of fluoropolymer segment,
This fluorine-containing thermoplastic elastomer (b-2) especially preferably contains:
(1) contain 1 elastomerics polymer segment (S1) and 1 inelastic body polymer segment (S2) and two kinds of segments wherein be the fluoropolymer segment diblock polymer and/or
(2) contain the triblock polymer that 1 elastomerics polymer segment (S1) and 2 inelastic body polymer segments (S2) and described segment are the fluoropolymer segment.
As fluorine-containing thermoplastic elastomer (b-2), for being connected with inelastic body polymer segment (S2) thereby in modes such as block or grafting, elastomerics polymer segment (S1) makes fluorine-containing polynary segment fluidized polymer, can adopt known the whole bag of tricks, but method for making, the spy of the fluorine-containing polynary segment fluidized polymer of disclosed block types such as the special public clear 58-4728 communique of wherein preferred employing open the method for making of the fluorine-containing polynary segment fluidized polymer of disclosed graft type in the clear 62-34324 communique etc.
Particularly segment rate (block rate) is higher from obtaining, the preferred fluorine-containing polynary segment fluidized polymer that adopts the so-called iodine transfer polymerization method of being put down in writing according to the public clear 58-4728 communique of spy, polymer collection of thesis (Vol.49, No.10,1992) to come the synthetic block type is considered in the aspect of the segment fluidized polymer of homogeneous and rule.
As the preferable production process of fluorine-containing thermoplastic elastomer (b-2), can enumerate as the known iodine transfer polymerization method of the manufacture method of viton.Can enumerate for example following method: substantially under the condition of anaerobic, in water medium, at iodine compound, preferably in the presence of diiodo-compound, above-mentioned perfluoroolefine and monomer that cure sites is provided are as required stirred adding to depress, in the presence of radical initiator, carry out letex polymerization simultaneously.As the representation example of employed diiodo-compound, for example can use the compound shown in the general formula (8), can obtain described elastomerics by there being the compound shown in this general formula (8);
R
2I
xBr
y (8)
In the general formula (8), x and y are respectively 0～2 integer and satisfy 1≤x+y≤2, R
2Be that carbonatoms is that 1～16 saturated or undersaturated fluoro alkyl, Chlorofluorocarbons (CFCs) base or carbonatoms are 1～3 alkyl, it can contain Sauerstoffatom.So the performance of iodine that imports or bromine is as the function of cross-linking set.
As the compound shown in the general formula (8), for example can enumerate 1,3-diiodo perfluo propane, 1,3-two iodo-2-chlorine perfluoropropane, 1,4-diiodo perfluo butane, 1,5-two iodo-2,4-dichloro perflenapent, 1,6-diiodo perfluo hexane, 1,8-diiodo perfluo octane, 1,12-diiodo perfluo dodecane, 1,16-diiodo perfluo n-Hexadecane, methylene iodide, 1,2-ethylidene periodide, 1,3-diiodo-n-propane, CF
2Br
2, BrCF
2CF
2Br, CF
3CFBrCF
2Br, CFClBr
2, BrCF
2CFClBr, CFBrClCFClBr, BrCF
2CF
2CF
2Br, BrCF
2CFBrOCF
3, (the 2-iodine ethyl) of the diiodo-list bromine substituent of single iodine list bromine substituent, benzene of 1-bromo-2-iodine R 116,1-bromo-3-iodine perfluoropropane, 1-bromo-4-iodine perfluorinated butane, 2-bromo-3-iodine perfluorinated butane, 3-bromo-4-iodine perfluor-1-butylene, 2-bromo-4-iodine perfluor-1-butylene, benzene and benzene and (2-bromotrifluoromethane) substituent etc., these compounds can use separately or be used in combination mutually.
Wherein, consider, preferably use 1,4-diiodo perfluo butane, methylene iodide etc. from aspects such as polymerisation reactivity, crosslinking reaction, acquisition easiness.
Employed radical polymerization initiator can be identical with the polymeric radical polymerization initiator that is used for fluoroelastomer so far among the present invention.Organic and inorganic peroxide and azo-compound in these initiators.As typical initiator, persulfuric acid salt, peroxycarbonates class, peroxyesters etc. are arranged, as preferred initiator, can enumerate ammonium persulphate (APS).APS can use separately or be used in combination such as reductive agents such as sulfurous esters, sulfites.
As employed emulsifying agent in the letex polymerization, can use the emulsifying agent of relative broad range, but in order to be suppressed at the chain transfer reaction to the emulsifying agent molecule that takes place in the polymerization process, described emulsifying agent is preferably the salt of the carboxylic acid with fluorocarbon chain or fluoro polyether chain.The consumption of emulsifying agent is preferably the about 0.05 weight %～2 weight % of the water that is added, and is preferably 0.2 weight %～1.5 weight % especially.
Polymerization pressure can change in the scope of broad.Be generally the scope of 0.5MPa～5MPa.Because the high more then polymerization velocity of polymerization pressure is fast more, thereby from improving the consideration of productivity aspect, described polymerization pressure is preferably more than the 0.8MPa.
During with the elastomerics polymer segment (S1) of the above-mentioned fluorine-containing thermoplastic elastomer of iodine transfer polymerization manufactured (b-2), from the aspect consideration of giving flexibility to resulting fluorine-containing polynary segment fluidized polymer integral body, giving elasticity, giving mechanical properties, its number-average molecular weight is preferably 3000～750000, and more preferably 5000～300000.
The terminal portions of the elastomerics polymer segment (S1) that so obtains forms the perhalogeno type, has the iodine atom of the initiation point of the block copolymerization that becomes inelastic body polymer segment (S2).
Then, inelastic body polymer segment (S2) is to the block copolymerization of elastomerics polymer segment (S1), and then the letex polymerization of elastomerics polymer segment (S1) is undertaken by the monomer that monomer is transformed to inelastic body polymer segment (S2) usefulness.Consider that from the aspect of giving thermotolerance to thermoplastic polymer composition of the present invention, giving mechanical properties the number-average molecular weight of inelastic body polymer segment (S2) is preferably 1000～1200000, more preferably 3000～600000.
In addition, in the fluorine-containing thermoplastic elastomer (b-2), with respect to the segment in the fluorine-containing thermoplastic elastomer (b-2) and the total amount of polymer molecule, bonding does not have inelastic body polymer segment (S2) and only for the polymer molecule of elastomerics polymer segment (S1) is preferably below the 20 weight %, more preferably below the 10 weight %.
Consider that from using organo-peroxide to carry out crosslinked aspect preferred viton (b-1) or fluorine-containing thermoplastic elastomer (b-2) have iodine atom or bromine atoms in molecule.
The viton (b-1) of fluoro-resin (A) and interpolation to fluoro-resin (A) in or the weight ratio of fluorine-containing thermoplastic elastomer (b-2) are preferably in the scope 10/90～95/5, more preferably in 20/80～80/20 scope.If the viton (b-1) that adds in fluoro-resin (A) or the weight ratio of fluorine-containing thermoplastic elastomer (b-2) are less than 5 weight %, then the flexibility of resulting thermoplastic polymer composition has the trend of reduction; If surpass 90 weight %, the mobile variation of resulting thermoplastic polymer composition then, forming process has the trend of reduction.
Thermoplastic polymer composition of the present invention makes at least a kind viton (b-1) or fluorine-containing thermoplastic elastomer (b-2) carry out dynamic crosslinking in the presence of fluoro-resin (A) and linking agent (C) under melting condition and handles and obtain.Wherein, dynamic crosslinking is handled to refer to and is used Banbury mixer, pressurization kneader, forcing machine etc. that viton (b-1) or fluorine-containing thermoplastic elastomer (b-2) melting mixing are also made its dynamic crosslinking simultaneously.Wherein, consider, preferably use forcing machines such as biaxial extruder from the aspect that can apply high shear force.Handle by carrying out dynamic crosslinking, can control the phase structure of fluoro-resin (A) and crosslinked fluororubber (B).
Linking agent (C) can suitably be selected according to the kind or the melting mixing condition of viton (b-1) or fluorine-containing thermoplastic elastomer (b-2).
When containing crosslinkable groups (sulfide site) in viton (b-1) or the fluorine-containing thermoplastic elastomer (b-2), employed cross-linking system can suitably be selected according to the purposes of the kind of sulfide site or resulting moulding product etc. among the present invention.As cross-linking system, can adopt polyol crosslink system, organo-peroxide cross-linking system and polyamines cross-linking system arbitrarily.
Wherein, crosslinked as if being undertaken by the polyol crosslink system, then cross-linking set has carbon-oxygen bond, compression set is less, formability is excellent, sealing characteristics is excellent, owing to have above-mentioned feature, so preferred.
If undertaken crosslinked by the organo-peroxide cross-linking system, then cross-linking set has C-C, thereby compare with the polyamines cross-linking system with the two keys of carbon-nitrogen with the polyol crosslink system that cross-linking set has a carbon-oxygen bond, have the feature of chemical resistant properties and anti-steam excellence.
If undertaken crosslinkedly by polyamines is crosslinked, then cross-linking set has the two keys of carbon-nitrogen, has the feature of dynamic mechanically excellent.But, to carry out comparing when crosslinked with using polyol crosslink system or organo-peroxide cross-linking system, the compression set rate has the trend of increase.
Therefore, among the present invention, preferably use the linking agent of polyol crosslink system or organo-peroxide cross-linking system, consider from the excellent aspect of stopping property as mentioned above, more preferably use the linking agent of polyol crosslink system.
Linking agent among the present invention can use the linking agent of polyamines system, polyvalent alcohol system, organic peroxide systems.
As the polyamines linking agent, for example can enumerate hexamethylene-diamine carbamate, N, N '-dicinnamylidene-1, polyamine compounds such as 6-hexamethylene-diamine, 4,4 '-two (aminocyclohexyl) methane carbamate.Wherein preferred N, N '-dicinnamylidene-1,6-hexamethylene-diamine.
As the polyol crosslink agent, can use in the past linking agent compound known as viton, for example polyol is considered from the excellent heat resistance aspect, especially preferably uses polyhydroxy aromatic compound.
As above-mentioned polyhydroxy aromatic compound, do not limit especially, for example can enumerate 2,2-two (4-hydroxy phenyl) propane (dihydroxyphenyl propane hereinafter referred to as), 2,2-two (4-hydroxy phenyl) perfluoropropane (bisphenol AF hereinafter referred to as), Resorcinol, 1, the 3-dihydroxy-benzene, 1, the 7-dihydroxy naphthlene, 2, the 7-dihydroxy naphthlene, 1, the 6-dihydroxy naphthlene, 4,4 '-dihydroxybiphenyl, 4,4 '-the dihydroxyl Stilbene, 2, the 6-dihydroxy-anthracene, Resorcinol, pyrocatechol, 2,2-two (4-hydroxy phenyl) butane (bisphenol b hereinafter referred to as), 4,4-two (4-hydroxy phenyl) valeric acid, 2,2-two (4-hydroxy phenyl) tetrafluoro propylene dichloride, 4,4 '-dihydroxy-diphenyl sulfone, 4,4 '-the dihydroxyl diphenylketone, three (4-hydroxy phenyl) methane, 3,3 ', 5,5 '-tetrachlorobisphenol A, 3,3 ', 5,5 '-tetrabromo-bisphenol etc.These polyhydroxy aromatic compounds can be an alkali metal salt, alkaline earth salt etc., but when being to use acid to come the condensation multipolymer, preferably do not use above-mentioned metal-salt.
Linking agent as the organo-peroxide cross-linking system, get final product so long as in the presence of heat or redox system, can easily produce the organo-peroxide of peroxy radical, specifically for example can enumerate, 1,1-two (tert-butyl hydroperoxide)-3,5, the 5-trimethyl-cyclohexane, 2,5-dimethylhexane-2,5-peroxidation dihydro, ditertiary butyl peroxide, tert butyl isopropyl benzene peroxide, the diisopropylbenzyl superoxide, α, α-two (tert-butyl hydroperoxide)-to diisopropyl benzene, 2,5-dimethyl-2,5-two (tert-butyl hydroperoxide) hexane, 2,5-dimethyl-2,5-two (tert-butyl hydroperoxide)-3-hexin, benzoyl peroxide, tert-butyl hydroperoxide benzene, the tert-butyl hydroperoxide toxilic acid, tert-butyl hydroperoxide sec.-propyl carbonic ether etc.Wherein preferred 2,5-dimethyl-2,5-two (tert-butyl hydroperoxide) hexane, 2,5-dimethyl-2,5-two (tert-butyl hydroperoxide)-3-hexin.
Wherein, less from the compression set of resulting moulding product etc., formability is excellent, the excellent aspect of sealing characteristics is considered, is preferably polyol, consider from the aspect of excellent heat resistance, more preferably polyhydroxy aromatic compound, more preferably bisphenol AF.
In addition, in the polyol crosslink system, use crosslinking accelerator usually, this crosslinking accelerator and polyvalent alcohol are linking agent and use.If use crosslinking accelerator, then can promote crosslinking reaction by the formation of the molecule internal double bond in the dehydrogenation fluoric acid reaction that promotes the viton main chain.
As the crosslinking accelerator of polyol crosslink system, use compound usually.Do not limit especially as compound, for example can enumerate, ammonium compounds such as quaternary ammonium salt, season phosphine compound, oxygen compound, sulfonium compound, cyclic amine, 1 functionality amine compound etc. such as phosphonium salt, wherein be preferably quaternary ammonium salt, season phosphonium salt.
Do not limit especially as quaternary ammonium salt, for example can enumerate, the 8-methyl isophthalic acid, 8-diazabicyclo [5,4,0]-7-undecylene muriate, the 8-methyl isophthalic acid, 8-diazabicyclo [5,4,0]-7-undecylene iodide, the 8-methyl isophthalic acid, 8-diazabicyclo [5,4,0]-7-undecylene oxyhydroxide, the 8-methyl isophthalic acid, 8-diazabicyclo [5,4,0]-7-undecylene methyl sulfate, 8-ethyl-1,8-diazabicyclo [5,4,0]-7-undecylene bromide, 8-propyl group-1,8-diazabicyclo [5,4,0]-7-undecylene bromide, 8-dodecyl-1,8-diazabicyclo [5,4,0]-7-undecylene muriate, 8-dodecyl-1,8-diazabicyclo [5,4,0]-7-undecylene oxyhydroxide, 8-eicosyl-1,8-diazabicyclo [5,4,0]-7-undecylene muriate, 8-tetracosyl-1,8-diazabicyclo [5,4,0]-7-undecylene muriate, 8-benzyl-1,8-diazabicyclo [5,4,0]-7-undecylene muriate (DBU-B hereinafter referred to as), 8-benzyl-1,8-diazabicyclo [5,4,0]-7-undecylene oxyhydroxide, 8-styroyl-1,8-diazabicyclo [5,4,0]-7-undecylene muriate, 8-(3-phenyl propyl)-1,8-diazabicyclo [5,4,0]-7-undecylene muriate etc.Wherein, consider, be preferably DBU-B from the rerum natura aspect of bridging property, cross-linking agent.
In addition, as the season phosphonium salt, do not limit especially, for example can enumerate, tetrabutylphosphonium chloride, benzyl triphenyl phosphonium chloride phosphine (BTPPC hereinafter referred to as), benzyl trimethyl phosphonium chloride, benzyl tributyl phosphonium chloride, tributyl allyl group chlorination phosphine, tributyl-2-methoxy-propyl phosphonium chloride, benzyl phenyl (dimethylamino) phosphonium chloride etc., wherein, consider, be preferably benzyl triphenyl phosphonium chloride phosphine (BTPPC) from the rerum natura aspect of bridging property, cross-linking agent.
In addition, as crosslinking accelerator, also can use quaternary ammonium salt, season phosphonium salt and the sosoloid of bisphenol AF; Disclosed no chlorine crosslinking accelerator in the Te Kaiping 11-147891 communique.
As the organo-peroxide crosslinking accelerator, for example can enumerate, triallyl cyanurate, triallyl isocyanurate (TAIC), three vinylformic acid methylals (tracryl formal), triallyl trimellitate, N, N '-metaphenylene dimaleimide, the dipropargyl terephthalate, diallyl phthalate, the tetraallyl terephthalamide, the triallyl phosphoric acid ester, bismaleimides, fluoridize cyanacrylate (1,3,5-three (2,3,3-three fluoro-2-propenyl)-1,3,5-triazine-2,4, the 6-triketone), three (diallyl amine)-S-triazines, triallyl phosphite, N, N-diallyl acrylamide, 1,6-divinyl ten difluoro hexanes, six allyl group phosphamides, N, N, N ', N '-tetraallyl phthalic diamide, N, N, N ', N '-tetraallyl Malonamide, the trivinyl isocyanuric acid ester, 2,4,6-trivinyl methyl trisiloxanes, three (5-norbornylene-2-methylene radical) cyanurate, triallyl phosphorous acid ester etc.Wherein, consider, be preferably triallyl isocyanurate (TAIC) from the rerum natura aspect of bridging property, cross-linking agent.
The use level of linking agent (C) is preferably 0.1 weight part～10 weight parts with respect to 100 weight part viton (b-1) or fluorine-containing thermoplastic elastomer (b-2), more preferably 0.3 weight part～5 weight parts.If linking agent (C) is less than 0.1 weight part, then viton (b-1) or the crosslinked of fluorine-containing thermoplastic elastomer (b-2) carry out insufficiently, the thermotolerance of resulting thermoplastic polymer composition and oil-proofness have the trend of reduction, if surpass 10 weight parts, then the forming process of resulting thermoplastic polymer composition has the trend of reduction.
In addition, referring to fluoro-resin (A), viton (b-1) or fluorine-containing thermoplastic elastomer (b-2) under the melting condition takes place under the fused temperature.The fused temperature takes place according to the difference of the second-order transition temperature of various fluoro-resin (A) and viton (b-1) or fluorine-containing thermoplastic elastomer (b-2) and/or fusing point and difference still is preferably 120 ℃～330 ℃, more preferably 130 ℃～320 ℃.If temperature is lower than 120 ℃, the trend that is dispersed with thickization between fluoro-resin (A) and viton (b-1) or the fluorine-containing thermoplastic elastomer (b-2) then, if above 330 ℃, then viton (b-1) or fluorine-containing thermoplastic elastomer (b-2) have the trend of thermal degradation when.
Resulting thermoplastic polymer composition can have fluoro-resin (A) and form external phase and crosslinked fluororubber (B) and form the structure of disperse phase or have fluoro-resin (A) and crosslinked fluororubber (B) forms successive structure altogether, but wherein preferably has the structure that fluoro-resin (A) forms external phase and crosslinked fluororubber (B) formation disperse phase.
Even viton (b-1) or fluorine-containing thermoplastic elastomer (b-2) are disperseing to form at first matrix, be accompanied by the carrying out of crosslinking reaction, viton (b-1) or fluorine-containing thermoplastic elastomer (b-2) form crosslinked fluororubber (B), melt viscosity also can increase, thereby makes crosslinked fluororubber (B) form the common external phase of disperse phase or formation and fluoro-resin (A).
If form this structure, thermoplastic polymer composition then of the present invention shows excellent thermotolerance, chemical resistant properties and oil-proofness, and has excellent forming process simultaneously.At this moment, the average mark shot of crosslinked fluororubber (B) directly is preferably 0.01 μ m～30 μ m, more preferably 0.1 μ m～10 μ m.If average mark shot footpath is less than the then mobile trend that reduction is arranged of 0.01 μ m, if surpass 30 μ m then the intensity of resulting thermoplastic polymer composition the trend of reduction is arranged.
The average mark shot footpath of the crosslinked fluororubber in the thermoplastic polymer composition of the present invention (B) can be determined by any one mode among use AFM, SEM, the TEM or their array mode.For example, when using AFM, obtain, can carry out 2 systemizations by this shading value being carried out Hue distinguishes by the resulting difference of surface information of the crosslinked fluororubber (B) of the fluoro-resin (A) of external phase and disperse phase form with the different picture of light and shade.By with the position of 2 systemizations as the central horizontal in the Hue distinguishes, can obtain having the picture of clear and definite contrast gradient, can read the cross-linked rubber particle diameter of disperse phase.In addition, when using SEM, by emphasize contrast gradient or to picture implement the adjustment of shading value or carry out above-mentioned two kinds adjust so that the crosslinked fluororubber of disperse phase (B) in the picture that looks like to obtain by reflection electronic for clearly, thereby the cross-linked rubber particle that can similarly read disperse phase with AFM directly.For TEM, also with SEM similarly, contrast gradient by adjusting resulting picture or shading value or picture carried out above-mentioned two kinds of adjustment then can similarly read the cross-linked rubber particle diameter of disperse phase with AFM or SEM.Wherein, for various thermoplastic polymer compositions, can select the method for easier affirmation.
On the other hand, in the thermoplastic polymer composition of the present invention, fluoro-resin (A) is preferably 0.1～1.5 with the ratio ([melt viscosity of resin (A)]/[melt viscosity of rubber (b-1) or elastomerics (b-2)]) of the melt viscosity of viton (b-1) or fluorine-containing thermoplastic elastomer (b-2), more preferably 0.2～1.2, be preferably 0.3～1.1 especially.The ratio of above-mentioned melt viscosity is less than 0.1 or greater than 1.5 o'clock, and the average mark shot of crosslinked fluororubber (B) is thickization directly, is dispersed with the trend of heterogeneityization.By making the fluoro-resin (A) and the melt viscosity ratio of viton (b-1) or fluorine-containing thermoplastic elastomer (b-2) is 0.1～1.5, can make the average mark shot footpath miniaturization of crosslinked fluororubber (B), disperse homogeneous, thereby can obtain the thermoplastic polymer composition of flexibility, compression set and forming process excellence.Wherein, to refer in temperature be 297 ℃, load to melt viscosity is the value of the melt flow rate (MFR) measured under the condition of 5000g.
In addition, for thermoplastic polymer composition of the present invention, in the part of the structure that fluoro-resin (A) formation external phase and crosslinked fluororubber (B) as its optimal way form disperse phase, also can contain the common continuous structure of fluoro-resin (A) and crosslinked fluororubber (B).
Thermoplastic polymer composition of the present invention contains 10 weight %～95 weight % fluoro-resin (A), 90 weight %～5 weight % crosslinked fluororubbers (B), preferably contain 20 weight %～80 weight % fluoro-resin (A), 80 weight %～20 weight % crosslinked fluororubbers (B), more preferably contain 30 weight %～70 weight % fluoro-resin (A), 70 weight %～30 weight % crosslinked fluororubbers (B).If fluoro-resin (A) is less than 10 weight %, the mobile variation of resulting thermoplastic polymer composition then, forming process has the trend of reduction; If surpass 95 weight %, then the flexibility of resulting thermoplastic polymer composition has the trend of reduction.
The melt flow rate (MFR) of thermoplastic polymer composition of the present invention (MFR) is preferably 0.5g/10min～30g/10min, more preferably 1g/10min～25g/10min.If MFR is less than the then mobile variation of 0.5g/10min, forming process has the trend of reduction.Wherein, to be to use the smart mechanism of Japan to make made melt flow rate (MFR) determinator be that 297 ℃, load are measured under the condition of 5000g in temperature to the mensuration of MFR.
In addition, when considering that when thermoplastic polymer composition of the present invention was used for fuel periphery part, the fuel perviousness of described thermoplastic polymer composition was preferably 0.1gmm/m
2My god～20gmm/m
2My god, 0.2gmm/m more preferably
2My god～18gmm/m
2My god.Wherein, the mensuration of fuel perviousness is used CE10 (toluene/octane-iso/ethanol=45vol%/45vol%/10vol%) undertaken by agar diffusion method (Cup method) as analog fuel in the time of 40 ℃.
In addition, in the scope that does not influence effect of the present invention, can in thermoplastic polymer composition of the present invention, add other polymkeric substance such as polyethylene, polypropylene, polymeric amide, polyester, urethane; Inorganic filling materials such as lime carbonate, talcum, clay, titanium oxide, carbon black, barium sulfate; Pigment, fire retardant, lubricant, photostabilizer, weather-proof stablizer, static inhibitor, UV light absorber, antioxidant, releasing agent, whipping agent, spices, oil, tenderizer etc.
Thermoplastic polymer composition of the present invention can use general shaping operation method or shaping and processing device etc. to carry out forming process.As method for processing forming, for example, can adopt arbitrary method such as injection molding, extrusion moulding, compressed moulding, blow molding, calendering formation, vacuum forming, thermoplastic polymer composition of the present invention is shaped to the formed body of arbitrary shape according to application target.
Further, relate to the moulding product that use thermoplastic polymer composition of the present invention and obtain among the present invention, as these moulding product, comprise the formed body of sheet material or film, and comprise the laminated structure body that has the layer that contains thermoplastic polymer composition of the present invention and contain the layer of other material.
One deck at least contain the layer of thermoplastic polymer composition of the present invention and at least one deck contain in other the laminated structure body of layer of material, above-mentioned other material can be according to desired characteristic, the suitable materials of selection such as purposes be scheduled to.As other material, for example can enumerate polyolefine (for example: high density polyethylene(HDPE), medium-density polyethylene, new LDPE (film grade), straight chain shape new LDPE (film grade), ethylene-propylene copolymer, polypropylene etc.), nylon, polyester, vinyl chloride resin (PVC), vinylidene resin thermoplastic polymers such as (PVDC); Cross-linked rubbers such as ethylene-propylene-dience rubber, isoprene-isobutylene rubber, nitrile rubber, silicone rubber, acrylic rubber; Metal; Glass; Timber; Pottery etc.
In having the moulding product of this laminated structure, can and contain between the substrate layer of other material at the layer that contains thermoplastic polymer composition of the present invention and insert binder layer.Engage also integrated securely by inserting this binder layer, can make layer that contains thermoplastic polymer composition of the present invention and the substrate layer that contains other material.As employed tackiness agent in the binder layer, can use the anhydride modified thing of alkadiene polymkeric substance; Polyolefinic anhydride modified thing; Macromolecule polyol is (for example, with diprotic acid polycondensations such as diatomic alcohol compounds such as ethylene glycol, propylene glycol and hexanodioic acids and the polyester polyol that obtains; The part ketonates of the multipolymer of vinyl-acetic ester and vinylchlorid etc.) with polyisocyanate compound (for example, 1, diatomic alcohol compounds and 2 such as 6-hexamethylene glycol, the mol ratio of diisocyanate cpds such as 4-tolylene vulcabond are 1 to 2 reaction product; Trivalent alcohol compounds and 2 such as TriMethylolPropane(TMP), the mol ratio of diisocyanate cpds such as 4-tolylene vulcabond are 1 to 3 reaction product etc.) mixture etc.And, in order to form laminated structure, can use coextrusion, altogether injection, known method such as extrusion coated.
The fuel hose or the fuel container that comprise the layer that only contains thermoplastic polymer composition of the present invention among the present invention.Purposes to fuel hose does not limit especially, for example can enumerate for motor vehicle weighting material flexible pipe, evaporation flexible pipe (エ バ Port ホ one ス), refrigeration flexible pipe (Block リ one ザ one ホ one ス) etc.In addition, to the qualification especially of purposes of fuel container, for example can enumerate for motor vehicle fuel container, automatic two-wheel vehicle used fuel container, the fuel container of small generator, the fuel container of mower etc.
Also comprise following multilayer fuel hose or multilayer fuel container among the present invention, described multilayer fuel hose or multilayer fuel container have the layer that contains thermoplastic polymer composition of the present invention.As this multilayer fuel hose or multilayer fuel container, contain the layer of thermoplastic polymer composition of the present invention and contain one deck at least of other material, these layers are by binder layer or bonding mutually by binder layer.
And, as the layer that contains other material, can enumerate the layer of the rubber that contains except that thermoplastic polymer composition of the present invention or contain thermoplastic resin layer.
As this rubber, consider from chemical resistant properties or flexibility aspect, preferred its contains at least a kind of rubber that is selected from the group of being made up of mixed rubber, viton, epichloro hydrin rubber and the acrylic rubber of acrylonitrile-butadiene rubber or its hydrogenation rubber, acrylonitrile-butadiene rubber and polyvinyl chloride, and more preferably it contains at least a kind of rubber that is selected from by in the mixed rubber of acrylonitrile-butadiene rubber or its hydrogenation rubber, acrylonitrile-butadiene rubber and polyvinyl chloride, the group that viton is formed.
In addition, as this thermoplastic resin, consider from fuel shielding aspect, preferred its contains at least a kind of thermoplastic resin that is selected from the group of being made up of fluoro-resin, polyamide-based resin, polyolefin resin, polyester resin, polyvinyl alcohol resin, polyvinyl chloride resin, polyphenylene sulfide resinoid, and more preferably it contains at least a kind of thermoplastic resin that is selected from the group of being made up of fluoro-resin, polyamide-based resin, polyvinyl alcohol resin, polyphenylene sulfide resinoid.
As above-mentioned contain thermoplastic polymer composition of the present invention the layer and contain other rubber or contain other thermoplastic resin the layer fuel hose or fuel container, do not limit especially, for example can enumerate fuel hoses such as for motor vehicle weighting material flexible pipe, evaporation flexible pipe, refrigeration flexible pipe; For motor vehicle fuel container, automatic two-wheel vehicle used fuel container, the fuel container of small generator, the fuel containers such as fuel container of mower.
Wherein, as the fuel hose of the layer that contains thermoplastic polymer composition of the present invention with the layer that contains other rubber, consider from showing excellent fuel shielding-flexibility-chemical resistant properties aspect, be preferably that (at this moment, described skin contains acrylonitrile-butadiene rubber or its hydrogenation rubber or contains acrylonitrile-butadiene rubber and the mixed rubber of polyvinyl chloride by outer, middle layer and these 3 layers of fuel hoses that is constituted of internal layer; Thermoplastic polymer composition of the present invention is contained in described middle layer; Described internal layer contains viton) or serve as reasons skin and these 2 layers of fuel hoses that is constituted of internal layer (at this moment, described skin contains acrylonitrile-butadiene rubber or its hydrogenation rubber or contains acrylonitrile-butadiene rubber and the mixed rubber of polyvinyl chloride; Described internal layer contains thermoplastic polymer composition of the present invention).
Thermoplastic polymer composition of the present invention and the moulding product that contain said composition can be used for following field suitably.
In semi-conductor association areas such as semiconductor-fabricating device, liquid crystal panel manufacturing installation, plasma panel manufacturing installation, PALC panel, field emission display board, solar cell substrate, can enumerate, circle (side) shape ring, gasket, sealing material, pipe, roller, coating, lining, liner, barrier film, flexible pipe etc., these can be used for CVD device, dry-etching device, Wet-type etching device, oxide-diffused device, sputter equipment, cineration device, washing device, ion implantation apparatus, gas barrier, reagent pipe arrangement, gas pipe arrangement.Specifically, can be as circular rings, the sealing material of gate valve; The circular rings of quartz window, sealing material; The circular rings of chamber, sealing material; The circular rings of grid, sealing material; The circular rings of bell jar, sealing material; The circular rings of junctor, sealing material; The circular rings of pump, sealing material, barrier film; Semi-conductor circular rings, the sealing material of gas control equipment; The circular rings that resist developing solution, stripping liquid are used, sealing material; The flexible pipe that wafer cleaning solution is used, pipe; The roller that carrying wafers is used; Resist dipper, the lining of peeling off liquid bath, coating; The lining of wafer cleaning solution groove, coating; Or the lining of Wet-type etching groove, coating.Further, can be used as closed material-sealing agent; The coating material of the quartz of optical fiber; With insulation, vibrationproof, waterproof, damp proof be electronic unit, the potting of circuit substrate, coating, the adhesive seal of purpose; The liner that magnetic storage device is used; Sealing materials such as epoxy material modified; Clean room-cleaning apparatus is with sealing agent etc.
In vehicular field, liner, axle envelope, seal valve stem, sealing material and flexible pipe can be used for engine and peripheral device, flexible pipe and sealing material can be used for the AT device, and circle (side) shape ring, pipe, gasket, spool material, flexible pipe, sealing material and barrier film can be used for fuel system and peripheral device.Specifically, can be used as the motor head liner, metal gasket, oil pan gasket, the crank axle sealing, the camshaft envelope, valve stem seal, manifold gasket, shore installation hose, oxygen sensor is with sealing, the ATF flexible pipe, the injector circular rings, the injector gasket, the petrolift circular rings, barrier film, fuel hose, the crank axle sealing, the wheel casing sealing, the power piston gasket, the sealing of steam jacket, the sealing of valve rod, the preceding pump seal of automatic transmission, the sealing of rear axle pinion(gear), the liner of universal joint, the pinion(gear) sealing of velometer, the piston cup of foot-operated moving device, the circular rings of transmission of torque, oil sealing, the sealing of exhausting recombustion device, bearing seal, the EGR pipe, the twin carburettor pipe, the transmitter barrier film of vaporizer, vibration-proof rubber (engine mount, exhaust portion etc.), reignition device flexible pipe, oxygen sensor lining etc.
In field of aircraft, rocket field and ship domain, can enumerate barrier film, circle (side) shape ring, valve, pipe, gasket, flexible pipe, sealing material etc., these can be used for fuel system.Specifically, in field of aircraft, can be used for the jet engine valve stem seal; Fuel feed flexible pipe, liner and circular rings; Rotating shaft sealing; The liner of oil pressure instrument; Fireproof brickwork sealings etc. in ship domain, can be used for the screwshaft stern sealing of screw rod, the suction and discharge valve stem seal of diesel engine, the valve seal of butterfly valve, the axle envelope of butterfly valve etc.
In field of chemicals such as chemical industry equipment, can enumerate lining, valve, gasket, roller, flexible pipe, barrier film, circle (side) shape ring, pipe, sealing material, chemically-resistant with coating etc., these can be used for chemical manufacturing processes such as medicine, agricultural chemicals, coating, resin.Specifically, can be as pharmaceutical chemicals pump, mobile meter; The sealing of pipe arrangement; The sealing of heat exchanger; The glass cools device gasket of sulfuric acid manufacturing installation; The agricultural chemicals spreading machine; The sealing of agricultural chemicals transferpump; The sealing of gas pipe arrangement; Electroplate liquid is with sealing; The gasket of high-temperature vacuum drying machine; Section's sieve envelope material (コ ロ シ one Le) of paper grade (stock) transmission belt; The sealing of fuel cell; The connection sealing of wind-tunnel; Anti-trieline roller (dyeing keratin-fiber is used); Acid proof hose (vitriol oil is used); The gasket of the pipe jointing portion of gas-chromatography, pH meter; Chlorine is carried and is used flexible pipe; Row's rainwater flexible pipe of benzene, toluene storage tank; The sealing of analytical instrument, physics and chemistry instrument, pipe, barrier film, valve member etc.
In medicine fields such as pharmaceuticals, can be used as medicinal lid etc.
In field of coating such as print fields such as shooting field, printing machinery such as visualizer and coating equipment, can enumerate roller etc., it can be used for film development instrument-X line film development instrument, print roller and application roller respectively.Specifically, can be used as the developer roll of film development instrument-X line film development instrument; The gravure roll of print roller, guide roller; The tape of application roller is made gravure roll, the tape of coating line and is made the guide roller of coating line, various coating rolls etc.Further, can be as the sealing of dry copier; The print roller of printing equipment, scraper, pipe, valve member; Coating, the coating roll of coating equipment, scraper, pipe, valve member; The printing ink pipe of printer, roller, transmission belt; The transmission belt of dry copier, roller; The roller of printing press, transmission belt etc.
In addition, pipe can be used for analysis-physics and chemistry instrument field.
In the food apparatus instrument field, can enumerate lining, valve, gasket, roller, flexible pipe, barrier film, circle (side) shape ring, pipe, sealing material, transmission belt etc., they can be used for the food mfg operation.Specifically, can be as the sealing of plate-type heat exchanger, the magnetic valve sealing of vending machine etc.
In the atomic power device instrument field, can enumerate gasket, circular rings, flexible pipe, sealing material, barrier film, valve, roller, pipe etc.
In iron and steel domains such as steel plate processing units, can enumerate roller etc., it can be used as steel plate working roll etc.
In the general industry field, can enumerate roller, roller scraper, transmission belt of gasket, circular rings, flexible pipe, sealing material, barrier film, valve, roller, pipe, lining, axle, electric wire, flexible joint, transmission belt, rubber plate, weather strip, PPC duplicating machine etc.Specifically, can be used for the sealing of oil pressure, lubricated apparatus; Bearing seal; The window of dry-cleaning instrument; Other sealing; The sealing of the concentrating unit of uranium hexafluoride; The sealing of magnetic resonance acceleator (vacuum) valve; The sealing of automatic packing machine; Airborne sulphurous acid gas, the chlorine analysis barrier film (public hazards tester) of pump; The roller of printing press, transmission belt; Pickling is with squeeze roll etc.
In electric field, specifically, can be used as the insulation oil cap of bullet train (the Shinkansen), the clipper seal (benching seal) of fluid-tight type transformer, the sleeve pipe of oil well cable etc.
In fuel cell field, specifically, can be used as the sealing material between electrode, the shield retaining (separator), the sealing of hydrogen-oxygen-generation water pipe arrangement etc.
In the electronic unit field, specifically, can be used for printed circuit board (PCB) pre-soaked resins such as heat sink material raw material, electromagnetic shielding material raw material, epoxy material modified, bulb etc. prevent to disperse the liner etc. of hard disk drive of material, computer.
Material as the moulding that can be used in the site operation type is not particularly limited, and for example can enumerate the vehicle motor coating agent of metal gasket; The oil pan gasket of engine; Duplicating machine-printer roller; Building Encapsulant; The magnetic storage device liner; Clean room's sealing agent of filtering element; The coating agent of printer base; The fixing agent of electrical equipment-electronic unit; Wet treatment is prevented in the insulation of electronic machine lead terminal; The sealing of baking ovens such as electric furnace; The end line of sheathed heater is handled; The window frame sealing of microwave oven; CRT wedge (wedge) and groove (neck) bonding; Vehicle parts of electric bonding; The joint seal that kitchen, bathroom, toilet etc. are located etc.
Moulding product of the present invention can be used for above-mentioned various uses suitably, and the peripheral part that particularly acts as a fuel is suitable.In addition, moulding product of the present invention are useful especially as sealing material, gasket, roller, pipe or flexible pipe.
Embodiment
The present invention will be described then to enumerate embodiment below, but the present invention is not limited in following embodiment.
＜hardness 〉
Use is by the particle of the thermoplastic polymer composition of embodiment, comparative example manufacturing, utilize heat extruder under 260 ℃, the condition of 5MPa, to carry out compressed moulding, making thickness is the sheet test film of 2mm, uses these test films to measure A hardness with JIS-K6301 as benchmark.
＜flowability 〉
Use is by the particle of the thermoplastic polymer composition of embodiment, comparative example manufacturing, and utilizing the melt flow determinator to be determined at temperature is 297 ℃, loading is the melt flow rate (MFR) under the condition of 5000g (MFR).
＜compression set rate 〉
The particle of the thermoplastic polymer composition that use is made by embodiment, comparative example utilizes heat extruder to carry out compressed moulding under 260 ℃, the condition of 5MPa, and making thickness is the sheet test film of 2mm and 0.7mm.This sheet test film is overlapping, and making diameter is that 29.0mm, thickness are the cylindric of 12.7mm, is that to be determined at temperature be that 150 ℃, compress variation are the compression set rate of placing under 25% the condition after 22 hours to benchmark with JIS-K6301.
＜tensile break strength and tension fracture elongation rate 〉
Use is by the particle of the thermoplastic polymer composition of embodiment, comparative example manufacturing, utilize heat extruder under 260 ℃, the condition of 5MPa, to carry out compressed moulding this particle, making thickness is the sheet test film of 2mm, and it is die-cut into thickness is that 2mm, width are the dumbbell shaped test film of 5mm.Use resulting dumbbell shaped test film, adopting Autograph ((strain) Shimadzu Seisakusho Ltd. system) is that benchmark is determined at tensile break strength and the tension fracture elongation rate in the time of 23 ℃ under the condition of 50mm/min with JIS-K6301.
＜fuel perviousness 〉
The particle of the thermoplastic polymer composition that use is made by embodiment, comparative example utilizes heat extruder to carry out compressed moulding under 260 ℃, the condition of 5MPa this particle, and making thickness is the sheet test film of 2mm.Cutting out diameter by this sheet test film is discoid of 10cm, is that benchmark utilizes agar diffusion method (Cup method) to measure the CE10 (transit dose of toluene/octane-iso/ethanol=45vol%/45vol%/10vol%) in 40 ℃ with JIS-Z0208.
＜contain vinyl fluoride polymkeric substance (a) 〉
Tetrafluoroethylene-ethylene copolymer (TFE: ET=50mol%: 50mol%, fusing point are 220 ℃, are 297 ℃, the MFR=30g/10min of load when the 5000g in temperature)
＜viton (b-1 α) 〉
2 yuan of system rubber that form by vinylidene fluoride (VdF) and R 1216 (HFP) (VdF: HFP=78mol%: 22mol%, the mooney viscosity in the time of 121 ℃=41 are 297 ℃, the load MFR=28g/10min during for 5000g in temperature)
＜fluorine-containing thermoplastic elastomer (b-2) 〉
Contain (tetrafluoroethylene-ethylene copolymer segment)-triblock copolymer of (vinylidene fluoride-tetrafluoraoethylene-hexafluoropropylene copolymer segment)-(tetrafluoroethylene-ethylene copolymer segment) (is 297 ℃, the load MFR=26g/10min during for 5000g in temperature)
Tetrafluoroethylene in the tetrafluoroethylene-ethylene copolymer segment and the ratio=50mol% of ethene: 50mol%
Ratio=the 50mol% of the vinylidene fluoride in vinylidene fluoride-tetrafluoraoethylene-hexafluoropropylene copolymer segment, tetrafluoroethylene, R 1216: 30mol%: 20mol%
＜viton (b-1 β) 〉
3 yuan of system rubber (VdF: TFE: HFP=50mol%: 20mol%: 30mol% that form by vinylidene fluoride (VdF), tetrafluoroethylene (TFE) and R 1216 (HFP), mooney viscosity in the time of 121 ℃=88 are 297 ℃, the MFR=87g/10min of load when the 5000g in temperature)
＜linking agent (C-1) 〉
Polyvalent alcohol system linking agent: 2,2-two (4-hydroxy phenyl) perfluoropropane (Daikin Industries system " bisphenol AF ")
＜linking agent (C-2) 〉
The organic peroxide systems linking agent: 2,5-dimethyl-2,5-two (tert-butyl hydroperoxide)-3-hexin (Japanese grease system " Perhexyn 25B-40 ")
Embodiment 1～3
With the above-mentioned viton of 100 weight parts (b-1 α) and 2.17 weight part linking agents (C-1) and 0.43 weight part crosslinking accelerator (benzyl triphenyl phosphonium chloride phosphine, industry system " TPP-ZC " is learned in Xinghua, north) carry out mixingly with two rollers, make the composition (compound) of viton (b-1 α).
Then with the ratio shown in the table 1 with the above-mentioned vinyl fluoride polymkeric substance (a) that contains, the composition (compound) of viton (b-1 α) is pre-mixed, then with respect to the viton in the 100 weight part above-mentioned compositions (b-1 α), further add 3 weight parts and be subjected to sour agent (consonance chemical industry oxygenerating magnesium " MA150 "), 6 weight part promotor (near river chemical industry hydrogen manufacturing calcium oxide " CARDIC 2000 ") are also mixed, be supplied to biaxial extruder, at hopper temperature is that 250 ℃ and screw rod speed of rotation are to carry out melting mixing under the condition of 300rpm, makes the particle of thermoplastic polymer composition respectively.Use the particle of resulting thermoplastic polymer composition, adopt aforesaid method that hardness, flowability, compression set rate, tensile strength, tensile elongation and fuel perviousness are measured, measurement result is as shown in table 1.
Embodiment 4 and 5
With the ratio shown in the table 1 with above-mentioned contain vinyl fluoride polymkeric substance (a), fluorine-containing thermoplastic elastomer (b-2) and linking agent (C-2) and be pre-mixed after, be supplied to biaxial extruder, at hopper temperature is that 250 ℃ and screw rod speed of rotation are to carry out melting mixing under the condition of 300rpm, makes the particle of thermoplastic polymer composition respectively.Use the particle of resulting thermoplastic polymer composition, adopt aforesaid method that hardness, flowability, compression set rate, tensile strength, tensile elongation and fuel perviousness are measured, measurement result is as shown in table 1.
Embodiment 6～8
With the above-mentioned viton of 100 weight parts (b-1 β) and 2.0 weight part linking agents (C-1) and 0.55 weight part crosslinking accelerator (8-benzyl-1,8-diazabicyclo [5,4,0]-7-undecylene muriate, with the pure medicine of light (strain) system " DBU-B ") carry out mixingly with two rollers, make the composition (compound) of viton (b-1 β).
Then with the ratio shown in the table 1 with the above-mentioned vinyl fluoride polymkeric substance (a) that contains, the composition of viton (b-1 β) is pre-mixed, then with respect to the viton (b-1 β) in the 100 weight part above-mentioned compositions (compound), further add 3 weight parts and be subjected to sour agent (consonance chemical industry oxygenerating magnesium " MA150 "), 6 weight part promotor (near river chemical industry hydrogen manufacturing calcium oxide " CARDIC 2000 ") are also mixed, be supplied to biaxial extruder, at hopper temperature is that 250 ℃ and screw rod speed of rotation are to carry out melting mixing under the condition of 300rpm, makes the particle of thermoplastic polymer composition respectively.Use the particle of resulting thermoplastic polymer composition, adopt aforesaid method that hardness, flowability, compression set rate, tensile strength, tensile elongation and fuel perviousness are measured, measurement result is as shown in table 1.
Carry out morphological observation as can be known by scanning electron microscope (NEC (strain) system), the thermoplastic polymer composition that is obtained by embodiment 1～8 has fluoro-resin (A) and forms the structure that external phase and crosslinked fluororubber (B) form disperse phase.
Comparative example 1
Only use the particle of fluoro-resin (A), adopt aforesaid method that hardness, flowability, compression set rate, tensile strength, tensile elongation and fuel perviousness are measured, measurement result is as shown in table 1.
Comparative example 2
With the above-mentioned viton of 100 weight parts (b-1 α) and 2.17 weight part linking agents (C-1), 0.43 weight part crosslinking accelerator (benzyl triphenyl phosphonium chloride phosphine, north Xinghua industry system " TPP-ZC "), 3 weight parts are subjected to sour agent (consonance chemical industry oxygenerating magnesium " MA150 "), 6 weight part promotor (near river chemical industry hydrogen manufacturing calcium oxide " CARDIC 2000 ") to carry out mixing with two rollers, in 160 ℃ the pressurization crosslinked 10 minutes after, crosslinked 4 hours of 180 ℃ of bakers, make crosslinked viton (b-1 α).Utilize aforesaid method to make test film by the sheet material of resulting crosslinked fluororubber (b-1 α), adopt aforesaid method that hardness, tensile break strength, tension fracture elongation rate and compression set rate are measured and chemical resistant properties is estimated, the result is as shown in table 1.
Table 1
| Embodiment | Comparative example | ||||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 1 | 2 | ||
| Combined amount (weight part) | Contain vinyl fluoride polymkeric substance (a) | 40 | 50 | 60 | 50 | 30 | 40 | 50 | 60 | 100 | |
| Viton (b-1 α) | 60 | 50 | 40 | 100 | |||||||
| Fluorine-containing thermoplastic elastomer (b-2) | 50 | 70 | |||||||||
| Viton (b-1 β) | 60 | 50 | 40 | ||||||||
| Linking agent (C-1) | 1.30 | 1.09 | 0.87 | 1.30 | 1.09 | 0.87 | 2.17 | ||||
| Linking agent (C-2) | 0.1 | 0.14 | |||||||||
| Evaluation result | The dispersion particle diameter of viton (B) (μ m) | 8 | 9 | 9 | 0.5 | 0.6 | 5 | 5 | 6 | - | - |
| Hardness JIS-A | 90 | 94 | 95 | 93 | 85 | 85 | 90 | 94 | - | 60 | |
| MFR(g/10min) | 1.5 | 4.7 | 1 5 | 10 | 15 | 2.3 | 7.3 | 20.3 | 30 | - | |
| Compression set rate (%) | 37 | 48 | 60 | 97 | 95 | 39 | 50 | 67 | - | 12 | |
| Tensile break strength (MPa) | 12 | 16 | 20 | 18 | 20 | 11 | 15 | 18 | 20 | 8 | |
| Tension fracture elongation rate (%) | 240 | 290 | 280 | 410 | 450 | 225 | 267 | 253 | 300 | 270 | |
| Fuel perviousness (gmm/m 2My god) | 8.7 | 4.7 | 3.2 | 18.3 | 26.1 | 4.8 | 3.2 | 1.9 | 0.9 | 67 | |
Utilizability on the industry
Thermoplastic polymer composition of the present invention contains fluororesin and crosslinked fluororubber, and this crosslinked fluororubber is to process and form by making at least a kind fluorubber or fluorine-containing thermoplastic elastomer (TPE) carry out dynamic crosslinking under melting condition, thereby this thermoplastic polymer composition has excellent heat resistance-chemical resistance-oil resistivity-fuel shielding concurrently, have flexibility, and processing and forming is excellent.
Claims (16)
1. thermoplastic polymer composition, it contains 10 weight %～95 weight % fluoro-resin (A) and 90 weight %～5 weight % crosslinked fluororubbers (B), wherein, described fluoro-resin (A) contain fusing point be 120 ℃～330 ℃ contain vinyl fluoride polymkeric substance (a), described crosslinked fluororubber (B) is in the presence of fluoro-resin (A) and linking agent (C), makes at least a kind viton (b-1) or fluorine-containing thermoplastic elastomer (b-2) carry out dynamic crosslinking under melting condition and handles and to form.
2. thermoplastic polymer composition as claimed in claim 1, wherein, the described fusing point that contains vinyl fluoride polymkeric substance (a) is 150 ℃～310 ℃.
3. thermoplastic polymer composition as claimed in claim 1 or 2, wherein, the described vinyl fluoride polymkeric substance (a) that contains is for being selected from by at least a polymkeric substance in following (a-1), (a-2), (a-3) and the group (a-4) formed,
Described (a-1) is the multipolymer of tetrafluoroethylene and ethene;
Described (a-2) is the multipolymer of the perfluoro-ethylene unsaturated compound shown in tetrafluoroethylene and the following general formula (1);
Described (a-3) is for containing the unitary multipolymer of perfluoro-ethylene unsaturated compound shown in 19 moles of %～90 mole % tetrafluoroethylene units, 9 moles of %～80 mole % ethylene unit and the 1 mole of following general formula of %～72 mole % (1);
Described (a-4) is poly(vinylidene fluoride);
Described general formula (1) is:
CF
2＝CF-R
f 1 (1)
In the general formula (1), R
f 1Expression-CF
3Or-OR
f 2, R
f 2The expression carbonatoms is 1～5 perfluoroalkyl.
4. as any described thermoplastic polymer composition of claim 1～3, wherein, described linking agent (C) is for being selected from least a kind of material in the group of being made up of organo-peroxide, polyamine compounds, polyol.
5. as any described thermoplastic polymer composition of claim 1～4, wherein, described composition is the structure that fluoro-resin (A) forms external phase and crosslinked fluororubber (B) formation disperse phase.
6. thermoplastic polymer composition as claimed in claim 5, wherein, the average mark shot of described crosslinked fluororubber (B) directly is 0.01 μ m～30 μ m.
7. as any described thermoplastic resin composition of claim 1～6, wherein, described fluoro-resin (A) is 0.1～1.5 with the ratio of the melt viscosity of viton (b-1) or fluorine-containing thermoplastic elastomer (b-2).
8. as any described thermoplastic resin composition of claim 1～7, wherein, the melt flow rate (MFR) of described composition is 0.5g/10min～30g/10min.
9. as any described thermoplastic resin composition of claim 1～8, wherein, the fuel perviousness of described composition is 0.1gmm/m
2My god～20gmm/m
2My god.
10. moulding product, it contains any described thermoplastic polymer composition of claim 1～9.
11. a sealing material, it contains any described thermoplastic polymer composition of claim 1～9.
12. a fuel periphery part, it contains any described thermoplastic polymer composition of claim 1～9.
13. a single layer fuel flexible pipe, it contains any described thermoplastic polymer composition of claim 1～9.
14. a single layer fuel container, it contains any described thermoplastic polymer composition of claim 1～9.
15. a multilayer fuel hose, it contains the layer that right requires 1～9 any described thermoplastic polymer composition.
16. a multilayer fuel container, it contains the layer that right requires 1～9 any described thermoplastic polymer composition.
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| JP342771/2004 | 2004-11-26 | ||
| JP2004342771 | 2004-11-26 | ||
| JP267183/2005 | 2005-09-14 | ||
| JP2005267183 | 2005-09-14 | ||
| PCT/JP2005/021666 WO2006057331A1 (en) | 2004-11-26 | 2005-11-25 | Thermoplastic polymer composition |
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| CN101065440A true CN101065440A (en) | 2007-10-31 |
| CN101065440B CN101065440B (en) | 2012-01-18 |
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| CN200580040551XA Active CN101065440B (en) | 2004-11-26 | 2005-11-25 | Thermoplastic polymer composition |
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| Publication number | Publication date |
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| CN101065442A (en) | 2007-10-31 |
| CN101065440B (en) | 2012-01-18 |
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