CN1274730C - 氟共聚物 - Google Patents
氟共聚物 Download PDFInfo
- Publication number
- CN1274730C CN1274730C CNB031471269A CN03147126A CN1274730C CN 1274730 C CN1274730 C CN 1274730C CN B031471269 A CNB031471269 A CN B031471269A CN 03147126 A CN03147126 A CN 03147126A CN 1274730 C CN1274730 C CN 1274730C
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- 229920001577 copolymer Polymers 0.000 title claims description 123
- 229910052731 fluorine Inorganic materials 0.000 title claims description 13
- 239000011737 fluorine Substances 0.000 title description 6
- 239000000178 monomer Substances 0.000 claims abstract description 25
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 10
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims abstract description 9
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 claims abstract description 4
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 claims abstract description 4
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 claims abstract description 4
- 229940018557 citraconic acid Drugs 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 43
- 238000006116 polymerization reaction Methods 0.000 claims description 24
- 238000010030 laminating Methods 0.000 claims description 20
- 229920003002 synthetic resin Polymers 0.000 claims description 16
- 239000000057 synthetic resin Substances 0.000 claims description 16
- -1 hexafluoroethylene Chemical compound 0.000 claims description 15
- 125000001153 fluoro group Chemical group F* 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- KHXKESCWFMPTFT-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-(1,2,2-trifluoroethenoxy)propane Chemical compound FC(F)=C(F)OC(F)(F)C(F)(F)C(F)(F)F KHXKESCWFMPTFT-UHFFFAOYSA-N 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 4
- 239000004760 aramid Substances 0.000 claims description 3
- 229920003235 aromatic polyamide Polymers 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 claims description 2
- 229920006122 polyamide resin Polymers 0.000 claims 2
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 abstract description 11
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 abstract 1
- 238000000034 method Methods 0.000 description 32
- 239000010410 layer Substances 0.000 description 28
- 239000012528 membrane Substances 0.000 description 19
- 239000002245 particle Substances 0.000 description 18
- 229920002313 fluoropolymer Polymers 0.000 description 15
- 239000004811 fluoropolymer Substances 0.000 description 15
- 230000001070 adhesive effect Effects 0.000 description 14
- 150000001408 amides Chemical class 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 229920001038 ethylene copolymer Polymers 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000004927 fusion Effects 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000005336 cracking Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 239000012986 chain transfer agent Substances 0.000 description 5
- 238000000748 compression moulding Methods 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- XRKOOHTZZDPJNE-UHFFFAOYSA-N 1,1,1-trifluorohexane Chemical class CCCCCC(F)(F)F XRKOOHTZZDPJNE-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000005488 sandblasting Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 229920006355 Tefzel Polymers 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
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- 239000006185 dispersion Substances 0.000 description 3
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- QHSJIZLJUFMIFP-UHFFFAOYSA-N ethene;1,1,2,2-tetrafluoroethene Chemical compound C=C.FC(F)=C(F)F QHSJIZLJUFMIFP-UHFFFAOYSA-N 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000005502 peroxidation Methods 0.000 description 3
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 3
- 239000007870 radical polymerization initiator Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- HGXJDMCMYLEZMJ-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOOC(=O)C(C)(C)C HGXJDMCMYLEZMJ-UHFFFAOYSA-N 0.000 description 2
- UHMWWIKRVZTBBR-UHFFFAOYSA-N 1-chloro-1,1,2,2,3-pentafluoropropane Chemical compound FCC(F)(F)C(F)(F)Cl UHMWWIKRVZTBBR-UHFFFAOYSA-N 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 229910001297 Zn alloy Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 230000002180 anti-stress Effects 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 125000005587 carbonate group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- 239000012933 diacyl peroxide Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 230000037452 priming Effects 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000001175 rotational moulding Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- SKYXLDSRLNRAPS-UHFFFAOYSA-N 1,2,4-trifluoro-5-methoxybenzene Chemical compound COC1=CC(F)=C(F)C=C1F SKYXLDSRLNRAPS-UHFFFAOYSA-N 0.000 description 1
- YACLCMMBHTUQON-UHFFFAOYSA-N 1-chloro-1-fluoroethane Chemical class CC(F)Cl YACLCMMBHTUQON-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- SYNPRNNJJLRHTI-UHFFFAOYSA-N 2-(hydroxymethyl)butane-1,4-diol Chemical compound OCCC(CO)CO SYNPRNNJJLRHTI-UHFFFAOYSA-N 0.000 description 1
- FDMFUZHCIRHGRG-UHFFFAOYSA-N 3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C=C FDMFUZHCIRHGRG-UHFFFAOYSA-N 0.000 description 1
- XWUCFAJNVTZRLE-UHFFFAOYSA-N 7-thiabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound C1=C(S2)C=CC2=C1 XWUCFAJNVTZRLE-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 1
- 239000004160 Ammonium persulphate Substances 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
- WXQDFOGZIYLEGP-UHFFFAOYSA-N C(C(C)C)#N.C(C(C)C)#N.[N] Chemical compound C(C(C)C)#N.C(C(C)C)#N.[N] WXQDFOGZIYLEGP-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 229920006358 Fluon Polymers 0.000 description 1
- 101000576320 Homo sapiens Max-binding protein MNT Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 229920006121 Polyxylylene adipamide Polymers 0.000 description 1
- 239000004159 Potassium persulphate Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- JMPVESVJOFYWTB-UHFFFAOYSA-N dipropan-2-yl carbonate Chemical class CC(C)OC(=O)OC(C)C JMPVESVJOFYWTB-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- NHGVZTMBVDFPHJ-UHFFFAOYSA-N formyl fluoride Chemical compound FC=O NHGVZTMBVDFPHJ-UHFFFAOYSA-N 0.000 description 1
- 239000002828 fuel tank Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000005355 lead glass Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229920006012 semi-aromatic polyamide Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 238000000807 solvent casting Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B1/00—Layered products having a non-planar shape
- B32B1/08—Tubular products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
-
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Abstract
本发明披露一种氟共聚物,它包含(a)四氟乙烯和/或三氟氯乙烯的聚合单元,(b)氟化单体(不包括四氟乙烯和三氟氯乙烯)聚合单元和(c)至少一种选自下列的聚合单元:衣康酸、衣康酸酐、柠康酸和柠康酸酐,其中,以((a)+(b)+(c))为基准,(a)的量为50-99.8摩尔%,(b)的量为0.1-80摩尔%,(c)的量为0.01-5摩尔%,其体积流量为0.1-1000mm3/sec。
Description
发明领域
本发明涉及氟共聚物,其耐化学性、耐热性、耐候性、耐应力断裂性优良,而且它与合成树脂、金属、金属氧化物、玻璃或陶瓷等物质的粘结性能也良好。
发明背景
氟共聚物如聚四氟乙烯、四氟乙烯/全氟(烷基乙烯基醚)共聚物、乙烯/四氟乙烯共聚物等广泛应用于各个领域如半导体工业和汽车工业。
含氟聚合物的耐热性、耐化学性、耐候性和气体屏蔽性能优良,但是与其他材料的粘结性不够。举例来说,为了使含氟聚合物与合成树脂、金属、金属氧化物、玻璃、陶瓷等粘结在一起,通常采用某种方法使含氟聚合物的表面经过电晕放电处理或钠蚀刻处理,然后涂布粘结剂层使其与材料粘结。这种粘结方法的过程非常麻烦,生产率也低。因此期望研究一种简单的方法,使含氟聚合物与其他材料粘结在一起。
作为在金属基材的表面形成含氟聚合物的涂层膜的方法,举例来说,有先通过如喷沙使金属基材的表面粗糙化,然后涂底漆,含氟聚合物的颗粒沉积在上面,然后在至少是含氟聚合物的熔融温度进行熔融。这种情况下期望研制一种含氟聚合物,其与金属等材料的粘结性能良好,且不需要底漆,因此降低成本且提高生产率。
最近几年,一种含氟聚合物与聚酰胺的层压材料被研究用作汽车的油箱或燃料管的材料。这种层压材料中,需要含氟聚合物层与聚酰胺层彼此牢固粘结。其粘结方法有,例如用试剂处理法、电晕放电处理法或等离子体放电处理法,对含氟聚合物的管材进行表面处理,将各种粘结功能团引到表面,然后粘结剂涂覆在这样的管子上,需要时挤出聚酰胺且层压在含氟聚合物管的外表面。然而,这种粘结方法过程麻烦,层压的生产率低。因此,需要开发一种含氟聚合物,它不需要对含氟聚合物层进行表面处理,从而可以用简单的方法比如共挤压方法形成含氟聚合物与聚酰胺的层压材料。
JP-A-11-193312披露了一种含有马来酸酐聚合单元的氟共聚物。这种共聚物与其它材料的粘结性提高。然而,马来酸酐与氟化单体的共聚性不够高,需要用特殊的聚合方法合成这种氟共聚物。因此用这种方法很难合成相应的氟共聚物来满足各种各样的应用。
英国专利1,087,999的例子中披露了一种氟共聚物,它包含四氟乙烯聚合单元/异丁烯聚合单元/苯甲酸乙烯酯聚合单元/衣康酸聚合单元。该共聚物与金属的粘结性能良好,但其软化温度较低,只有100℃,耐热性也不足。
美国专利3,445,434披露了一种乙烯/四氟乙烯共聚物,包含四氟乙烯聚合单元/乙烯聚合单元/衣康酸聚合单元。然而,这种乙烯/四氟乙烯共聚物的耐热性、机械强度如耐应力开裂性不足。
发明内容
鉴于这些情况,本发明的目的是提供一种氟共聚物,其耐热性、耐化学性和耐候性良好,且与其它材料的粘结性能也良好。
本发明提供一种氟共聚物,它含有(a)四氟乙烯和/或三氟氯乙烯聚合单元,(b)氟化单体(不包括四氟乙烯和三氟氯乙烯)聚合单元和(c)至少一种选自衣康酸、衣康酸酐、柠康酸和柠康酸酐的聚合单元,其中,以((a)+(b)+(c))为基准,(a)为50-99.8摩尔%,(b)为0.1-49.99摩尔%,(c)为0.01-5摩尔%,其体积流量为0.1-1000mm3/sec。
本发明还提供了一种制品,它包括一基材和基材表面上形成的如上所述的氟共聚物层。
较好实施方式
下面,参考较好的实施方案详细描述本发明。
本发明的氟共聚物包含(a)四氟乙烯(下文中称为TFE)和/或三氟氯乙烯(下文中称为CTFE)聚合单元,(b)氟化单体(不包括TFE和CTFE)聚合单元和(c)至少一种选自衣康酸(下文中称为IAC),衣康酸酐(下文中称为IAH),柠康酸(下文中称为CAC)和柠康酸酐(下文中称为CAH)的聚合单元。
本发明的氟共聚物中,以((a)+(b)+(c))为基准,(a)为50-99.8摩尔%,(b)为0.1-49.99摩尔%,(c)为0.01-5摩尔%,在此,((a)+(b)+(c))指(a),(b),(c)的总量。
较好的,(a)为50-99摩尔%,(b)为0.5-49.9摩尔%,(c)为0.1-3摩尔%。更好的,(a)为50-98摩尔%,(b)为1-49.9摩尔%,(c)为0.1-2摩尔%。如果(a),(b),(c)的摩尔含量在这些范围内,氟共聚物的耐热性、耐化学性优良。更进一步说,如果(b)的摩尔含量在此范围内,氟共聚物的加工性能优良,机械性能比如耐应力开裂性优良。如果(c)的摩尔含量在范围内,氟共聚物与其它材料的粘结性能优良。
作为(b)氟化单体,例如可以是氟乙烯、偏二氟乙烯、三氟丙烯、六氟丙烯、CF2=CFOR1(其中R1是指可含有氧原子的C1-10全氟烷基),CF2=CFOR2SO2X1(其中,R2是可含有氧原子的C1-10全氟烷基,X1是卤原子或羟基),CF2=CFOR3CO2X2(其中,R3是可含有氧原子的C1-10全氟烷基,X2是氢原子或最多3个碳原子的烷基),CF2=CF(CF2)pOCF=CF2(其中P为1或2),CH2=CX3(CF2)QX4(其中X3是氢原子或氟原子,Q为2-10的整数,X4是氢原子或氟原子)和全氟(2-亚甲基-4-甲基-1,3-二氧戊烷)。
较好的是偏二氧乙烯、六氟丙烯、CF2=CFOR1或CH2=CX3(CF2)QX4,更好是CF2=CFOR1或CH2=CX3(CF2)QX4。
举例来说,CF2=CFOR1可以是CF2=CFOCF2CF3,CF2=CFOCF2CF2CF3,CF2=CFOCF2CF2CF2CF3或CF2=CFO(CF2)8F。较好是CF2=CFOCF2CF2CF3。
CH2=CX3(CF2)Q 4 4可以是如CH2=CH(CF2)2F,CH2=CH(CF2)3F,CH2=CH(CF2)4F,CH2=CH(CF2)3H或CH2=CH(CF2)4H。较好是CH2=CH(CF2)4F或CH2=CH(CF2)2F。
(c)是至少一种选自IAC、IAH、CAC和CAH的聚合单元。更好的(c)是基于IAH或CAH的聚合单元。下面,IAC、IAH、CAC和CAH一般称为酸性单体。
如果用酸性单体制备氟共聚物,含有基于酸性单的体聚合单元的氟共聚物可以很容易地制备,而不需要采用JP-A-11-193312披露的使用马来酸酐时所要求的专门的聚合反应方法。如果用IAH或CAH制备氟共聚物,含有酸酐聚合单元的氟共聚物更容易制备。
本发明氟共聚物中以所有聚合单元为基准,((a)+(b)+(c))至少50摩尔%为宜,至少55摩尔%更好,最好至少60摩尔%。
较好的,本发明的氟共聚物除了(a)、(b)、(c)之外还含有(d)基于非氟化单体的聚合单元。(d)的非氟化单体例如可以是最多三个碳原子的烯烃如乙烯或丙烯,乙烯基酯如乙酸乙烯酯,乙烯基醚如乙基乙烯基醚或环己基乙烯基醚。较好用乙烯、丙烯或乙酸乙烯酯。
如果含有(d),((a)+(b)+(c))与(d)的摩尔比为100/5至100/90为宜,100/5至100/80更适合,最好是100/10至100/65最适合。
本发明的氟共聚物最好的具体例子有TFE/CF2=CFOCF2CF2CF3/IAH共聚物,TFE/CF2=CFOCF2CF2CF3/CAH共聚物,TFE/六氟丙烯/IAH共聚物,TFE/六氟丙烯/CAH共聚物,TFE/偏二氟乙烯/IAH共聚物,TFE/偏二氟乙烯/CAH共聚物,TFE/CH2=CH(CF2)4F/IAH/乙烯共聚物,TFE/CH2=CH(CF2)4F/CAH/乙烯共聚物,TFE/CH2=CH(CF2)2F/IAH/乙烯共聚物,TFE/CH2=CH(CF2)2F/CAH/乙烯共聚物,CTFE/CH2=CH(CF2)4F/IAH/乙烯共聚物,CTFE/CH2=CH(CF2)4F/CAH/乙烯共聚物,CTFE/CH2=CH(CF2)2F/IAH/乙烯共聚物,CTFE/CH2=CH(CF2)F/CAH/乙烯共聚物。
本发明的氟共聚物与氟共聚物以外的合成树脂制成层压材料时,宜用共挤出法。对共挤出法,氟共聚物的加工温度宜接近于合成树脂的加工温度。为此目的,(a)、(b)、(c)和需时的(d)的含量要在以上所提到的范围内调节,使氟共聚物的熔点最佳。
较好的,本发明的氟共聚物具有如下的官能团作为的端基:酯基、碳酸酯基、羟基、羧基、甲酰氟(carbonylfluoride)或酸酐,从而提高其与材料的粘结性能。较好的通过适当选择自由基聚合引发剂、链转移剂等引入这样的端基,用于制备氟共聚物。
本发明的氟共聚物的体积流量(下文中称为Q)在0.1-1000mm3/sec。Q值是氟共聚物熔体流动性的一个指数,也可作为分子量的粗标准。也就是说,Q值越大,分子量越低;Q值越小,分子量越高。本发明中,Q值为氟共聚物通过直径2.1mm,长度8mm的小孔,在比树脂的熔融点高50℃的温度下,在7千克负载下挤出的挤出速率,Q值由Shimadzu公司制造的流量测定器测定。如果Q值太小,挤出倾向困难,如果Q值太大,氟共聚物的机械强度会下降。本发明的氟共聚物的Q值宜为5-500mm3/sec,10-200mm3/sec更好。
本发明的氟共聚物的软化温度宜为120-310℃,150-300℃更好。在此,软化温度为在英国专利1,087,999第7页,49-54行所披露的粘结温度,它是接触过热黄铜(铜/锌合金)块时在氟共聚物上沉积熔融物痕迹的最低温度。
制备本发明氟共聚物的方法没有具体限制,可采用使用自由基引发聚合反应的方法。有本体聚合;使用氟代烃、氯代烃、氟氯代烃、醇或烃等有机溶剂的溶液聚合;使用含水介质和乳化剂悬浮聚合,最好是溶液聚合。
自由基聚合反应引发剂较好的是10小时半衰期温度为0-100℃,较好为20-90℃的自由基聚合引发剂,具体例子有,偶氮化合物如氮二异丁腈,非氟化的二酰基过氧化物如过氧化异丁酰、过氧化辛酰、过氧化苯甲酰或过氧化月桂酰等,过二碳酸如过二碳酸二异丙酯,过氧化酯如新戊酸叔丁基过氧酯(tert-butylperoxy pivalate)、异丁酸叔丁基过氧化酯或乙酸叔丁基过氧化酯,氟代二酰基过氧化物如由化学式(Z(CF2)PCOO)2(Z为氢原子、氟原子或氯原子,p为1-10之间的整数)代表的化合物,或无机过氧化物如过硫酸钾、过硫酸钠或过硫酸铵。
本发明中较好的还使用链转移剂来控制氟共聚物的Q值。链转移剂例如可以是甲醇、乙醇等醇类,如氯氟代烃如1,3-二氯-1,1,2,2,3-五氟丙烷或1,1-二氯-1-氟乙烷,或烃类如戊烷、己烷、环己烷。更进一步,宜使用有官能团如酯基、碳酸酯基、羟基、羧基、碳酰氟基等功能团的链转移剂,有活性端基的氟共聚物以外的合成树脂,比如聚酰胺,可以引入到氟共聚物中。这样的链转移剂可以是乙酸、乙酸酐、乙酸甲酯、乙二醇或丙三醇等。
对本发明的聚合反应条件没有特殊限制。聚合温度宜为0-100℃,更好20-90℃。聚合压力宜为0.1-10Mpa,更好0.5-3Mpa。聚合反应时间宜为1-30小时。
聚合反应中酸性单体的浓度宜在0.01-5%范围内,0.1-3%更好,0.1-1%最好。如果酸性单体浓度过高,聚合速率降低。如果在上述范围内,生产过程中聚合速率不会减小,氟共聚物的粘结性能良好。为了保持聚合反应过程中酸性单体浓度在这个范围内,酸性单体宜采用连续加入的方式。
本发明的制品包括基材和基材表面上形成的氟共聚物层。
基材可以是例如以上所述的氟共聚物以外的合成树脂,金属如铁、不锈钢或铝玻璃或陶瓷。基材表面涂布方法例如可采用静电粉尘处理法、旋转模塑法、热喷雾法、流动浸渍法、分散法或溶剂浇铸法。
静电粉尘处理法中,较好的在氟共聚物粉末上施加负高电压,使粉末带电并吸附在基材的表面,附着的氟共聚物在高于熔融温度但低于分解温度的温度下加热、熔融5分钟至1小时,形成厚度一致的涂层膜。
旋转模塑法中,较好的,氟共聚物粉末倒入罐形或圆筒形基材中,在高于氟共聚物熔融温度但低于氟共聚物分解温度的温度下加热5分钟至1小时、同时旋转基材,使氟共聚物熔融,在基材的内表面形成厚度均匀的涂层膜。
热喷雾法中,较好的用粉末热喷雾器把半熔融状态的氟共聚物喷在预热的基材上,形成涂层膜。
流动浸渍法中,优化的一种方法是把氟共聚物粉末放入底部有空气可渗过多孔板的容器中,从孔板中吹入空气使粉末流态化,把基材加热到高于氟共聚物熔融温度但低于氟共聚物分解温度的温度,将其浸渍在流动粉末中1分钟至1小时,形成均匀的涂层膜。
分散法中,较好的将氟共聚物细粉末悬浮或分散在水或溶剂中,形成的悬浮液或分散液喷在基材上,蒸发除去水或溶剂形成一层均匀的沉积粉末层,随后加热到高于氟共聚物熔融温度但低于氟共聚物分解温度的温度熔融1分钟至1小时,形成均匀的涂层膜。
氟共聚物可以溶解在溶剂中情况,氟共聚物可以通过浇铸、浸渍等方法涂覆在基材的表面。
较好的还对基材表面进行预处理。预处理方法有,例如喷砂处理法、磷酸盐处理法、盐酸处理法或硫酸处理法。通过这样的处理,基材与氟共聚物的粘结性能将提高。
本发明中,制品较好是层压材料,其中本发明的氟共聚物层与氟共聚物以外的合成树脂层直接层压制得的。
可用熔融法制备本发明的氟共聚物与氟共聚物以外的合成树脂的层压材料。熔融法中,从生产率的角度共挤压法较好。共挤压法可制备两层或更多层薄膜或筒形层压材料。从两个或更多挤出机出口的排出的熔融体以熔状态接触,通过模头,形成层压材料。
挤出温度可根据氟共聚物与氟共聚物以外的合成树脂的熔融温度和分解温度调节。螺杆温度宜为100-400℃,模头温度150-400℃。螺杆旋转速度没有特殊限制,较好为10-200rpm。氟共聚物在挤出机中的保留时间为1-20分钟。
与本发明氟共聚物共挤出的合成树脂可以是聚酰胺6、聚酰胺66、聚酰胺46、聚酰胺11、聚酰胺12或聚酰胺MXD6(半芳香族聚酰胺)等聚酰胺,聚酯如聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚萘二甲酸乙二醇酯或聚萘二甲酸丁二醇酯等,聚乙烯,聚(乙烯/VAC),聚丙烯,聚苯乙烯,聚偏二氯乙烯,聚VAC,聚乙烯醇,聚(乙烯/乙烯醇),聚丙烯腈,聚甲醛,对聚苯硫,聚苯醚,聚碳酸酯,聚酰胺-酰亚胺,聚醚酰亚胺,聚砜或聚丙烯酸酯。
优选聚酰胺或聚酯为氟共聚物以外的合成树脂,最好是聚酰胺12或聚萘二甲酸丁二醇酯。
本发明的层压材料更好为氟共聚物层与聚酰胺层直接层压制得的。
包括基材和基材表面上形成的本发明的氟共聚物层的制品的耐热性、耐化学性、耐腐蚀性、抗油性、耐候性、对磨性、润滑性等性质优异,因此可应用于如反应器、食品产品用的容器或管道、医用、半导体、化工设备等领域,也可用于试剂运输的槽车,防碎玻璃板,防碎玻璃瓶,耐磨陶瓷部件等方面。
本发明的氟共聚物以及氟共聚物以外的合成树脂的层压材料的耐热性、耐化学性、耐腐蚀性、抗油性、耐气候性等性质优异,因此可用于汽车部件、工业材料、电和电子部件、机器零件、办公设备部件、家/用电器、容器、片材、薄膜、纤维、单丝和不同形状的模型制品和应用。
更具体地,可用作汽车燃料用的管子或软管、燃料填料胶管、制冷液管、制动管、空调管、燃料输送管、采油管道、涂料喷管、工业管道、食品产品胶管,农用片材或薄膜,内衬,建筑物内部材料(如墙纸),层压钢板,汽车水箱罐等罐子,化学品的瓶子、罐子、包、容器或汽车燃料、粘合剂的罐子。
本发明将更详细描述实施例(实施例1至实施例3和实施例6)和比较例(例4和例5)。然而,本发明决不局限于这些特例。MIT耐折叠试验,IAH或CAH的含量由以下方法测定。
MIT耐折叠试验
根据ASTM D2176测定。将宽度为12.5mm,长度为130mm,厚度为0.23mm的试样安装在由Toyo Seiki Seisakusho制造的MIT测定仪上,在负荷为1.25kg,左右折叠角度135°条件下折叠试样,折叠次数为175次/分,因此可测定直至样品断裂的折叠次数。该试验是测定氟共聚物的耐挠曲疲劳性、测定值可作为抗龟裂性指数。折叠次数越高,抗龟裂性越好。
IAH或CAH的含量
氟共聚物(A)压塑制成厚度为200μm的薄膜。红外吸收光谱中,氟共聚物(A)的IAH或CAH聚合单元的C=O伸展振荡吸收峰在1,870cm-1。测量该吸收峰的吸光率,可由公式M=a L求得基于IAH或CAH聚合单元的含量M(摩尔%),其中,L是在1,870cm-1处的吸光率,a是系数。用IAH为标准化合物测定,a取a=0.87。
软化温度
依照的英国专利1,087,999第7页,49-54行所披露的内容进行测定。软化温度是氟共聚物接触加热的黄铜(铜/锌合金)块在氟共聚物表面能产生熔融沉积痕迹的最低温度。软化温度也被称为粘附温度。
实施例1
内容积为94升的聚合反应容器,配有搅拌器,除去空气,加入71.3千克的1-氢十三氟己烷,20.4千克1,3-二氯-1,1,2,2,3-五氟丙烷(下文中称为AK225cb,Asahi Glass Company Limited制造),562克CH2=CH(CF2)2F和4.45克IAH,反应器内温度升高到66℃。由摩尔比89/11的TFE/E的气体使压力增加到1.5Mpa/G。加入1升含0.7%新戊酸叔丁基过氧酯(tert-butyl peroxypivalate)的1-氢十三氟己烷溶液引发聚合反应。不断加入摩尔比59.5/40.5的TFE/E混合气体使压力在反应过程中保持恒定。以加入的TFE和E总摩尔数为基准,连续加入3.3摩尔%的CH2=CH(CF2)2F和0.8摩尔%IAH。引发聚合反应后9.9小时内加入7.28千克单体混合气体,聚合反应器内温度降到室温,压力降至常压。
得到的氟共聚物1以浆料形式加到200升成粒器,其中已加入77千克水,搅拌下造粒,将温度升到105℃蒸馏除去溶剂,生成氟共聚物颗粒。得到的颗粒在150℃下烘干15小时,得到6.9千克氟共聚物1的颗粒1。
熔体核磁共振分析、氟含量分析和红外吸收光谱分析得到,氟共聚物1的组成是TFE聚合单元/CH2=CH(CF2)2F聚合单元/IAH聚合单元/E聚合单元的摩尔比为93.5/5.7/0.8/62.9。熔点为230℃,软化温度220℃,Q值48mm3/sec,MIT折叠次数为38900次。
通过挤出机,颗粒1在260℃下熔融捏合,保留时间2分钟,制得氟共聚物1的颗粒1。
将聚酰胺12(3030JLX,Ube工业有限公司生产)供给圆筒形成外层,将颗粒1供给圆筒内形成内层,将它们传送到圆筒的各自传送区。聚酰胺12与颗粒1在传送区的加热温度分别调节到240℃和260℃。调节共挤出模头温度到260℃,两层共挤出成型得到两层层压管。层压管的外径为8mm,内径为6mm,厚度1mm,聚酰胺外层和氟共聚物内层分别为0.7mm和0.3mm。内层与外层牢固地粘结在一起没有剥落,也不会被剥离。
实施例2
实施例1中制得的氟共聚物1的颗粒1在300℃下压塑得到厚度1mm,宽度2.5cm,长度10cm的片材。该片材放在SUS304板上进行喷砂处理,并保持在260℃下20分钟,以熔融氟共聚物1形成涂层膜。在形成涂层膜过程中,涂层膜没有颜色变化,而且耐热性优异。进行剥离试验,但是涂层膜断裂,因为氟共聚物1与SUS304板牢固粘结在一起。
有氟共聚物1涂层膜的SUS304板于100℃浸渍在浓盐酸中一星期,然后进行剥离试验,涂层膜牢固结合,不能被剥离。
颗粒1在300℃下压塑,制得厚度为0.1mm的薄膜,用超级紫外测试仪进行加速耐候试验500小时,观察外表没有变化,因此薄膜的耐候性优异。
实施例3
使用和实施例1相同的反应容器,除去空气,加入902千克的AK225cb,0.216千克的甲醇,31.6千克的CF2=CFOCF2CF2CF3和0.43千克的IAH。反应器内温度升高到50℃,加入TFE使压力达到0.38MPa。加入50毫升0.25%过氧化二全氟丁酰(di(perfluoroobutyryl)peroxide)AK225cb溶液作出聚合反应引发剂,引发聚合反应。在聚合反应过程中连续加入TFE使压力保持恒定。聚合反应引发剂溶液需要有选择地加入,使TFE加入速度充分稳定。还可任选加入上述聚合反应引发剂溶液以保持TFE加料速度基本不变,该引发剂溶液的总加入量为120毫升。连续加入IAH,加入量为TFE加入量的1摩尔%。聚合反应引发后6小时内加入7.0千克TFE,反应结束,聚合反应器内温度降到室温,除去未反应的TFE。
得到的氟共聚物2以浆料形式加到200升成粒器中,该成粒器中已加入75千克水,搅拌,将温度升到105℃蒸发除去溶剂,生成氟共聚物颗粒。得到的颗粒在150℃下烘干5小时,得到7.5千克氟共聚物2的颗粒2。
熔体核磁共振分析、氟含量分析和红外吸收光谱分析得到,氟共聚物2的组成是TFE聚合单元/CF2=CFOCF2CF2CF3聚合单元/IAH聚合单元摩尔比为97.7/2.0/0.3。熔点为292℃,软化温度280℃,Q值15mm3/sec,MIT折叠次数为46000次。
氟共聚物2的颗粒2在340℃下压塑得到厚度1mm,宽度2.5cm,长度10cm的片材。该片放在SUS304板上进行喷砂处理,在340℃下保持20分钟,以熔融氟共聚物2形成涂层膜。在形成过程中,涂层膜没有颜色变化,而且耐热性优异。涂层膜进行剥离试验,因为氟共聚物2与SUS304板牢固粘结在一起,因此涂层膜断裂。
有氟共聚物2涂层膜的SUS304板于100℃浸渍在浓盐酸中1星期,然后进行剥离试验,但氟共聚物2涂层膜和SUS304板牢固结合,不能被剥离。氟共聚物2在340℃下压塑,制得厚度为0.1mm的薄膜,用超级紫外测试仪进行加速耐候试验500小时,观察外表没有变化,因此薄膜的耐候性优异。
实施例4
按照与实施例2相同的方法,在SUS304板上涂覆乙烯/四氟乙烯共聚物(FluonETFE LM2300N,Asahi Glass Company Limited生产)薄膜。剥离试验结果表明,Fluon ETFE LM2300N的涂层膜与SUS304板的剥离强度为10N/cm,剥离强度不足。
实施例5
使用和实施例1相同的反应容器,除去空气,加入53.1千克的1-氢十三氟己烷和42.5千克AK225cb。反应器内温度升高到66℃。加入TFE/E单体摩尔比为89/11的单体混合物使压力增加到1.5MPa/G。加入0.2升0.7%新戊酸叔丁基过氧酯的1-氢十三氟己烷溶液引发聚合反应。在聚合反应中连续加入摩尔比59.5/40.5的TFE/E混合单体使压力保持恒定。在反应过程中连续加入以TFE和E总摩尔数为基准的0.8摩尔%的IAH。聚合反应引发后6.5小时内加入7.28千克单体混合气体,之后反应器内温度降至室温,压力降至常压。
得到的氟共聚物3以浆料形成加到200升成粒器中,该成粒器中已加入77千克水,搅拌使造粒,将温度升到105℃蒸发除去溶剂。得到的颗粒在150℃下烘干15小时,得到7.5千克氟共聚物3的颗粒3。
熔体核磁共振分析、氟含量分析和红外吸收光谱分析得到,氟共聚物3的组成:TFE聚合单元/IAH聚合单元/E聚合单元的摩尔比为99.2/0.8/67.0。熔点为260℃,软化温度250℃,Q值48mm3/sec,MIT折叠次数为4900次,抗应力开裂性不足。
实施例6
将聚萘二甲酸丁二醇酯(PELPRENE EN-5000,Toyobo Co.,Ltd.生产)施涂在圆筒上形成外层,将实施例1颗粒1施涂在圆筒内形成内层,将它们传送到各自的圆筒传送区。聚萘二甲酸丁二醇酯与颗粒1在传送区的加热温度分别调节到250℃和260℃。调节共挤出模头温度至260℃,得到两层层压管。层压管的外径为8mm,内径为6mm,厚度1mm,聚酰胺外层和氟共聚物内层厚度分别为0.7mm和0.3mm。内层与外层牢固地粘结在一起没有剥落,且不能剥离。
根据以上所述,本发明的氟共聚物与诸如氟共聚物以外的合成树脂、金属、金属氧化物、玻璃或陶瓷等基材粘结性能良好,而且耐热性、耐化学性、耐候性和抗应力开裂性等性能优异。
而且,本发明的氟共聚物与金属、玻璃或陶瓷的粘结性能良好,因此,不用底漆就可得到包括基材和基材表面上形成的氟共聚物层的制品。这样的制品耐热性、耐化学性、耐腐蚀性、抗油性、耐气候性、耐磨性、润滑性等性质优异。
本发明的氟共聚物与氟共聚物以外的合成树脂的共挤出加工性优良,因此氟共聚物层与氟共聚物以外的合成树脂层能直接层压成型得到层压材料,而且两层之间的粘结性良好。
在2002年6月27日提出申请的申请号为2002-188061、2002年8月20日提出申请的申请号为2002-238811、2003年1月21日提出申请的申请号为2003-11923的日本专利的全部内容包括说明书、权利要求、摘要全文引做参考。
Claims (11)
1.一种氟共聚物,它包含:(a)四氟乙烯聚合单元,(b)氟化单体聚合单元,该氟化单体是至少一种选自以下的单体:CF2=CFOR1,其中R1是可含有氧原子的C1-10全氟烷基;CF2=CF(CF2)POCF=CF2,其中P为1或2;全氟(2-亚甲基-4-甲基-1,3-二氧戊烷;和CH2=CX3(CF2)QX4,其中X3是氢原子或氟原子,Q为2-10的整数,X4是氢原子或氟原子;和(c)至少一种选自下列的聚合单元:衣康酸、衣康酸酐,柠康酸和柠康酸酐,其中,以((a)+(b)+(c))为基准,(a)的量为50-99.8摩尔%,(b)的量为0.1-49.99摩尔%,(c)的量为0.01-5摩尔%,其体积流量为0.1-1000mm3/sec。
2.如权利要求1所述的氟共聚物,其特征在于所述氟共聚物还包含(d)非氟化单体的聚合单元,((a)+(b)+(c))/(d)的摩尔比为100/5至100/90。
3.一种制品,包括基材和基材表面上形成的如权利要求1或权利要求2所述的氟共聚物层。
4.如权利要求3所述的制品,其特征在于所述制品是如权利要求1或2所述的氟共聚物与氟共聚物以外的合成树脂直接层压成型制得的层压材料,条件是不包括具有氟聚合物层和直接层压在该层上的聚酰胺树脂层的多层层压管。
5.层压材料,包括如权利要求1或2所述的氟共聚物层与直接层压在其上的聚酰胺层,条件是不包括具有氟聚合物层和直接层压在该层上的聚酰胺树脂层的多层层压管。
6.如权利要求1或2所述的氟共聚物,其特征在于所述氟化单体是至少一种选自下列的单体:偏二氟乙烯、六氟乙烯、CF2=CFOR1,其中R1是可含有氧原子的C1-10全氟烷基、CH2=CX3(CF2)QX4,其中X3是氢原子或氟原子,Q为2-10的整数,X4指氢原子或氟原子。
7.如权利要求6所述的氟共聚物,其特征在于,CF2=CFOR1为CF2=CFOCF2CF2CF3。
8.如权利要求6所述的氟共聚物,其特征在于,CH2=CX3(CF2)QX4为CH2=CH(CF2)2F或CH2=CH(CF2)4F。
9.如权利要求2所述的氟共聚物,其特征在于非氟化单体是乙烯。
10.如权利要求1所述的氟共聚物,其特征在于(a)量为50-98摩尔%,(b)量为1-49.9摩尔%,(c)量为0.1-2摩尔%。
11.如权利要求2所述的氟共聚物,其特征在于,((a)+(b)+(c))/(d)的摩尔比为100/10至100/65。
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CNB031471269A Expired - Fee Related CN1274730C (zh) | 2002-06-27 | 2003-06-27 | 氟共聚物 |
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EP (2) | EP1531164B1 (zh) |
CN (2) | CN100522558C (zh) |
BR (2) | BR0301985B1 (zh) |
DE (2) | DE60301445T2 (zh) |
ES (2) | ES2248680T3 (zh) |
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EP1531164A1 (en) | 2005-05-18 |
US20040001956A1 (en) | 2004-01-01 |
CN1644353A (zh) | 2005-07-27 |
DE60301445T2 (de) | 2006-06-14 |
CN1477133A (zh) | 2004-02-25 |
CN100522558C (zh) | 2009-08-05 |
EP1375539B1 (en) | 2005-08-31 |
DE60308694D1 (de) | 2006-11-09 |
BR0301985A (pt) | 2004-08-31 |
DE60301445D1 (de) | 2005-10-06 |
BR0301985B1 (pt) | 2013-09-24 |
DE60308694T2 (de) | 2007-08-23 |
US20050118368A1 (en) | 2005-06-02 |
US7078470B2 (en) | 2006-07-18 |
EP1531164B1 (en) | 2006-09-27 |
ES2248680T3 (es) | 2006-03-16 |
ES2271771T3 (es) | 2007-04-16 |
EP1375539A1 (en) | 2004-01-02 |
US7205367B2 (en) | 2007-04-17 |
BR0313005B1 (pt) | 2014-03-11 |
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