CN1244600C - 热塑性含氢氟聚合物的制备方法 - Google Patents
热塑性含氢氟聚合物的制备方法 Download PDFInfo
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- CN1244600C CN1244600C CNB951148095A CN95114809A CN1244600C CN 1244600 C CN1244600 C CN 1244600C CN B951148095 A CNB951148095 A CN B951148095A CN 95114809 A CN95114809 A CN 95114809A CN 1244600 C CN1244600 C CN 1244600C
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- pentamethylene
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- halogen atom
- alkyl replaces
- alkene
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- 229920002313 fluoropolymer Polymers 0.000 title claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 239000004811 fluoropolymer Substances 0.000 title claims abstract description 13
- 239000001257 hydrogen Substances 0.000 title claims abstract description 13
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 13
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 claims abstract description 20
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 239000000725 suspension Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 21
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims description 18
- 239000012986 chain transfer agent Substances 0.000 claims description 15
- 125000005843 halogen group Chemical group 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229910052731 fluorine Inorganic materials 0.000 claims description 12
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 11
- 239000011737 fluorine Substances 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 11
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 10
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 10
- -1 perfluoro Chemical group 0.000 claims description 10
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- 230000008569 process Effects 0.000 claims description 9
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- 150000001336 alkenes Chemical class 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 238000007334 copolymerization reaction Methods 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 150000002191 fatty alcohols Chemical class 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
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- 125000004169 (C1-C6) alkyl group Chemical group 0.000 abstract 1
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 14
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- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 3
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- 150000001721 carbon Chemical group 0.000 description 3
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- HFNSTEOEZJBXIF-UHFFFAOYSA-N 2,2,4,5-tetrafluoro-1,3-dioxole Chemical class FC1=C(F)OC(F)(F)O1 HFNSTEOEZJBXIF-UHFFFAOYSA-N 0.000 description 2
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- 235000019394 potassium persulphate Nutrition 0.000 description 2
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- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical class FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 1
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 239000004159 Potassium persulphate Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
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- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- 230000001066 destructive effect Effects 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
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
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- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- YDDULLXUFDTAKJ-UHFFFAOYSA-M octanoate tetrafluoroazanium Chemical compound F[N+](F)(F)F.CCCCCCCC([O-])=O YDDULLXUFDTAKJ-UHFFFAOYSA-M 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000004978 peroxycarbonates Chemical class 0.000 description 1
- 125000005634 peroxydicarbonate group Chemical group 0.000 description 1
- 229920000233 poly(alkylene oxides) 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
- 238000012545 processing Methods 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
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- 230000035484 reaction time Effects 0.000 description 1
- 229910021481 rutherfordium Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 238000013022 venting Methods 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
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F14/18—Monomers containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/24—Trifluorochloroethene
- C08F214/245—Trifluorochloroethene with non-fluorinated comonomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/26—Tetrafluoroethene
- C08F214/265—Tetrafluoroethene with non-fluorinated comonomers
Abstract
本发明公开了被一个或多个C1-C6烷基进行烷基取代的环戊烷类可用作在-30℃-+30℃的低温下进行悬浮(共)聚合或水乳液(共)聚合的链转移剂，用于制备热塑性含氢氟聚合物，例如乙烯/-氯三氟乙烯和乙烯/四氟乙烯共聚物，或1，1-二氟乙烯的均聚物和共聚物。它们是高效链转移剂，由于是液体，因而易于处理和配料，无毒，得到高度热稳定的烷基端基。
Description
本发明涉及热塑性含氢的氟聚合物(thermoplastic bydrogen-containing fluoropolymer)的制备方法，其中将相应单体在低温下在有机悬浮液或水乳液中通过自由基进行(共)聚合。
本领域已知多种具有热塑性的含氢氟化聚合物。第一种是由全(卤代)含氟烯烃与不含卤素的烯烃的共聚物构成的，例如四氟乙烯(TFE)或一氯三氟乙烯(CTFE)与乙烯的共聚物，其可选地含有0.1-10％(摩尔)的第三种氟化共聚单体(例如见美国专利3624250和4513129)。这样的共聚物的制备通常在悬浮液中进行，尤其是对于CTFE/乙烯共聚物的情况，最好在低温(低于30℃)下进行。之所以需要低的聚合温度是因为这样有利于共聚单体的改变，避免生成使机械性能劣化并造成产物热不稳定的乙烯结块，伴有一个显然的问题就是分解，尤其是高温加工阶段更是如此。
另一种热塑性含氢氟聚合物由聚偏氟乙烯(PVDF)和用少量(0.1-10％(摩尔))其它氟化共聚单体改性的PVDF组成。这样的聚合物通常由高压(通常为25巴左右)和相对高温(通常为30-150℃)下水乳液聚合制得。
近来，申请人已发现新的氟化烯烃单体可选地与非氟化烯烃的水乳液(共)聚合方法，该方法使得低压下及非常低的反应温度甚至达-20℃下操作成为可能。这样的方法，本申请人在欧洲专利申请第94116994.8中有述，现引用其内容作为参考，该方法要求使用自由基光引发剂和紫外—可见射线。通过在这样低的温度下操作，可得到具有高度结构规整性的氟化(共)聚合物，其特征在于高额定温度和改进的机械性能和可加工性能。
一般来讲，也已知为控制最终产物分子量，需要在(共)聚合过程中向反应介质中加入起链转移剂作用的化合物。这种要用在工业规模生产工艺过程中的化合物应具有以下特征：
(a)即使在相对低的浓度下仍然有效；
(b)提供充分稳定的端基，这样不会危害(共)聚合物的稳定性且不会造成不希望的变色；
(c)易于配料；
(d)无毒，且无论如何不会危及环境。
若在如上述方法的-30°-+30°的低温下操作，则很难找到满足上述要求的产品。
目前，通常作为低温链转移剂用于热塑性含氢氟聚合物的产品是氯仿。例如，在美国专利3624250和3847881中在作为链转移剂的氯仿存在下，在0℃在CFC-113中制备CTFE/乙烯共聚物。然而，氯仿的缺点是氯化产物具有显著的致癌活性，因而其工业规模的使用和处理造成显著问题。
在美国专利4513129中，特别建议使用正戊烷、异戊烷、正己烷制备乙烯/CTFE和乙烯/TFE共聚物。根据申请人进行的实验，这些产物作为链转移剂在低温下效率差，因而为达到可观的转移作用，相对于进料单体的总量来讲必须大量使用它们。从而造成对反应介质的过分稀释，导致动力学衰减。该缺点在用不连续工艺过程(间歇式或半间歇式)操作时，例如生产乙烯/CTFE共聚物时，更是不希望的。实际上，在这种情况下，链转移剂的大量存在在反应过程中导致反应混合物单体组成的变化，从而改变了生产的聚合物。换句话说，在反应进行的过程中，有机相CTFE变得越来越少，以至于完全没有可能将反应进行至超过某一转化率。实际上已经知道，为避免乙烯单体在最终产品中富集，从而造成聚合物性能损失的情况，必须使反应介质中CTFE和乙烯之间的摩尔比尽可能保持不变。
若在水乳液中操作，在上述欧洲专利申请第94116994.8中所述的方法中，使用大量链转移剂是不可行的，因为过量有机相会造成乳液不稳定性增加。
申请人现已惊讶地发现，一类特别的烃—烷基取代的环戊烷类在-30℃-+30℃的低温下进行悬浮或水乳液(共)聚合反应制备热塑性含氢氟聚合物时是高效的链转移剂。
因而，本发明的目的是提供热塑性含氢氟聚合物的制备方法，其中将相应的单体在-30℃-+30℃之间的温度下在用一个或多个C1-C6烷基取代的环戊烷作为链转移剂存在下，进行(共)聚合。环戊烷优选被1、2或3个C1-C4烷基取代，可选自例如甲基环戊烷、丙基环戊烷、异丁基环戊烷、2-甲基-1-乙基环戊烷、顺，顺，反-1，2，3-三甲基环戊烷、顺-1，2-二甲基环戊烷或其混合物。特别优选甲基环戊烷。它们完全符合上述的对于工业规模用链转移剂所提出的要求，是液体产品，因而易于操作和配料，而且无毒，得到高度热稳定的烷基端基。
欲加入到反应介质中的烷基取代的环戊烷的量可在相当宽的范围内变化，这取决于所用单体的类型，反应温度和所需的分子量。通常该量相对于送入反应器的单体总量来说在0.01-30％(重量)，优选0.05-10％(重量)范围内。
若在水乳液中操作，如EP-617058中所述，可通过加入支链脂肪醇进一步提高烷基取代的环戊烷的有效性。该支链脂肪醇具有3-12个碳原子，其特征在于羟基数与甲基数之比低于或等于0.5。可选自例如：异丙醇、叔丁醇、颇哪醇、2，4-二甲基-3-戊醇、2，4，4-三甲基-1，3-戊二醇或其混合物。
所谓热塑性含氢氟聚合物是指可通过含氢含氟烯烃的均聚或后者与全氟代单体共聚得到的聚合物，或全(卤代)含氟烯烃与不含卤原子的烯烃之间的共聚物。特别是，本发明的方法可有利地用于：
(1)C2-C8全(卤代)含氟烯烃(例如TFE或一氯三氟乙烯(CTFE)与不含卤原子的C2-C8烯烃(例如乙烯、丙烯或异丁烯)的共聚物，不含卤原子的烯烃与全(卤代)含氟烯烃之间的摩尔比为40∶60至60∶40，可选地含少量，通常为0.1-10％(摩尔)一种或多种氟化共聚单体，选自例如式CX2＝CFRf的化合物，其中X是H或F，Rf是C2-C10氟代烷基，其可选地含一个或多个醚基(见例如US-4513129，U8-3624250)，或选自全氟代二氧杂环戊烯类(perfluorodioxols)(例如参见专利US-3865845、US-3978030、E9-73087、EP-76581、EP-80187)；
(2)聚偏氟乙烯或用少量通常为0.1-10％(摩尔)的一种或多种氟化共聚单体改性的聚偏氟乙烯，所述氟化共聚单体选自例如氟乙烯、一氯三氟乙烯、六氟丙烯、四氟乙烯、三氟乙烯等(参见例如专利US-4524194和US-4739024)。
该(共)聚合反应可在悬浮液或水乳液中，在合适的自由基引发剂存在下进行。
对于悬浮(共)聚合的情况，反应介质包括有机相，通常向其中加入水以有利于分散反应热。该有机相可不加入溶剂，由单体本身形成，或将单体溶于合适的有机溶剂中形成。至于有机溶剂通常使用氯氟烃，例如CCl2F2(CFC-12)、CCl3F(CFC-11)、CCl2FCClF2(CFC-113)、CClF2CClF2(CFC-114)等。由于这些产物对于同温臭氧层具有毁坏性作用，近来已建议使用替代产品，例如专利US-5182342中所述的仅含碳、氟、氢并可选地含氧的化合物。一种有效的替代品是由EP-612767中所述的支链烃组成的，其具有6-25个碳原子，且甲基数和碳原子数之比大于0.5，例如2，3-二甲基丁烷、2，3-二甲基戊烷、2，2，4-三甲基戊烷、2，2，4，6，6-五甲基庚烷、2，2，4，4，6-五甲基庚烷等及其混合物。
对于水乳液(共)聚合来讲，需存在合适的表面活性剂。最常使用的是下式的氟化表面活性剂：
Rf-X-M+
其中Rf是C5-C16(全)氟代烷基链或(全)氟代聚氧化烯链，X-是-COO-或-SO3 -，M+是选自H+、NH4 +、碱金属离子的离子。其中可提到的是：全氟代辛酸铵、用一个或多个羧基封端的(全)氟代聚氧化烯等。
反应压力通常为5-100巴，优选10-40巴。
本发明的方法可有利地在全氟代聚氧化烯乳液或微乳状液存在下进行，见专利US-4789717和US-4864006所述，也可有利地在具有含氢端基和/或含氢重复单元的含氟聚氧化烯微乳状液存在下进行，见EP-625526中所述。
由于反应温度低，热分解自由基引发剂的选择要限制在一定范围内。一般来讲，其30℃半衰期必须少于10小时，例如可选自式(Rf-CO-O)2的过氧化二酰，其中Rf是C1-C10(全)卤代烷基(参见例如EP-185242和US-4513129)或全氟代聚氧化烯基团(参见例如专利EP-186215和US-5021516)。其中，特别优选过氧化二(三氯乙酰)。另一类引发剂包括过氧化二碳酸二烷基酯，其中烷基具有1-8个碳原子，例如过氧化二碳酸二正丙酯和过氧化二碳酸二异丙酯(见专利EP-526216)。
所述乳液技术可在紫外可见射线下用自由基光引发剂有利地进行，见上述欧洲专利申请第94116994.8号所述。在此情况下，所有在紫外可见射线下产生能促进氟化烯烃单体(共)聚合的自由基的化学物质，不管在水中是可溶的还是不可溶的，均可用作引发剂。例如可选自下列产品：有机或无机过氧化物、酮、过氧化酰、二酮或多酮、过氧化碳酸酯、二烷基硫醚、过氧化酯、过渡金属配合物、卤化或多卤化有机化合物。因而，可在相当宽的范围内选择用作引发剂的产品—而这些引发剂在常规方法中通常是不能使用的—得到特别稳定的端基。例如对于过氧化二叔丁基和丙酮的情况便是如此，得到甲基端基，对于含氢氟聚合物的情况特别稳定。
下面介绍本发明的一些工作实施例，其目的仅是说明性的，并不限制本发明的范围。
实施例1
向装有350rpm下工作的搅拌器的3加仑抛光Pflaudler高压釜中加入5.31软化水以及表1所示量的一氯三氟乙烯(CTFE)和甲基环戊烷。将反应器调温至15℃，用乙烯加压至193psig。然后向高压釜中缓慢加入由保温在-17℃的过氧化三氯乙酰(TCAP)在CFC-113中的溶液组成的自由基引发剂。连续向反应器中送入乙烯以在整个聚合过程中将压力维持恒定。其它反应参数和所得聚合物的熔体流动指数见表1。所得聚合物(以及实施例2-10所得的聚合物)的CTFE/乙烯摩尔比等于约50/50，第二熔融温度(second melting temperalure)为240℃(由示差扫描量热计DSC测得)。
实施例2
按同样条件重复实施例1，只是用更大量的甲基环戊烷作链转移剂。数据见表1。
实施例3-10(比较例)
按同样条件重复实施例1，用甲基环己烷(实施例3-4)、异丁烷(实施例5-6)、氯仿(实施例7-8)、环戊烷(实施例9)和正戊烷(实施例10)作链转移剂。通过与实施例1-2比较可注意到，甲基环戊烷显然比其它具有类似结构的烃更有效，因而，在最终产品所需的MFI相同时，其用量与氯仿的相比相当少。
实施例11
在500ml装有900rpm下工作的搅拌器的高压釜中抽真空后加入110ml异辛烷和3.0ml甲基环戊烷。将反应器调至10℃，然后用四氟乙烯/TFE)加压至15.5巴，再用乙烯加压至23.1巴的工作压力。然后不连续地向高压釜中送入浓度为0.03g/ml，保温在-15℃的过氧化三氯乙酰(TCAP)的异辛烷溶液。开始加入约0.015g TCAP，接着在聚合过程中每小时加三次。通过连续以49/51的摩尔比送入乙烯/TFE混合物而在整个反应过程中将压力保持恒定。330分钟后，得到38.7g干燥聚合物。测得产物的第二熔融温度为294.5℃(DSC)，MFI(ASTMD3159-83)为0.3g/10分钟。
实施例12
在0.61不锈钢AISI316高压釜的一侧壁上装上在600rpm下工作的搅拌器，嵌入石英窗，相应放置Hanau(R)TQ-150紫外灯。该灯是高压汞灯，发射240-600nm的射线，对于240-330nm范围内的射线，功率为13.2W。
将高压釜抽真空，顺次加入：
——325ml软化水；
——2.0g式CF3O-(CF2-CF(CF3O)m-(CF2O)n-CF2COO-K↑的表面活性剂，其m/n＝26.2；平均分子量595，溶于50ml水中；
——1.0ml甲基环戊烷。
然后将高压釜调至10℃，用TFE将压力调至11.3巴(绝对压力)，然后用乙烯调至15巴(绝对压力)。然后打开紫外灯，并开始加入0.2g过硫酸钾(KPS)溶于200ml水得到的溶液。连续加入引发剂，流速为25ml/小时，总量40ml。通过49/51的摩尔比连续送入乙烯/TFE混合物在整个反应期间将压力维持在15巴(绝对压力)。450分钟后，关掉灯，将高压釜放气，并在室温卸料。这样得到胶乳，将其在150℃烘箱中凝结并干燥。对所得聚合物(6.0g)进行熔体流动指数(MFI)测定(ASTM D3159-83)，得到具有很大流动性的聚合物(MFI＞300g/10分钟)。
表1
| EX. | CTA | CTFE(Kg) | CTA/CTFE(g/Kg) | TCAP溶液浓度(g/ml) | TCAP总量(g) | 反应时间(小时) | 制得的聚合物(g) | MFI(ASTM 3275-89)(g/10分钟) |
| 1 | 甲基环戊烷 | 1.37 | 11.6 | 0.07 | 18.2 | 5 | 350 | 2.6 |
| 2 | 甲基环戊烷 | 1.34 | 18.9 | 0.07 | 18.5 | 3.25 | 870 | 20.7 |
| 3* | 甲基环己烷 | 1.71 | 25.0 | 0.081 | 8.0 | 5 | 914 | 1.8 |
| 4* | 甲基环己烷 | 1.36 | 48.7 | 0.07 | 11.6 | 8 | 628 | 9.3 |
| 5* | 异丁烷 | 1.41 | 30.6 | 0.07 | 10.43 | 2.25 | 930 | 3.7 |
| 6* | 异丁烷 | 1.38 | 39.9 | 0.07 | 10.88 | 3.75 | 622 | 13.2 |
| 7* | 氯仿 | 1.38 | 9.1 | 0.07 | 14.0 | 3.25 | 874 | 4.4 |
| 8* | 氯仿 | 1.31 | 12.8 | 0.055 | 6.9 | 15.5 | 805 | 27.7 |
| 9* | 环戊烷 | 1.39 | 21.6 | 0.07 | 8.82 | 2.5 | 1222 | 2.9 |
| 10* | 正戊烷 | 2.35 | 33.8 | 0.094 | 11.0 | 5.5 | 1365 | s.f. |
*比较例
CTA：链转移剂
CTFE：一氯三氟乙烯
TCAP：过氧化三氯乙酰
s.f.：流动性极差
Claims (10)
1.热塑性含氢氟聚合物的制备方法，其中在-30℃至+30℃的温度下、在用一个或多个C1-C6烷基取代的环戊烷作为链转移剂存在下，使含氢氟烯烃进行均聚合、或者使含氢氟烯烃与全氟代单体进行共聚合或者使全(卤代)含氟烯烃与不含卤原子的烯烃进行共聚合，其中所述烷基取代的环戊烷的加入量按进料单体的总量计算为0.01-30％(重量)。
2.权利要求1的方法，其中所述环戊烷被1、2或3个C1-C4烷基取代。
3.权利要求2的方法，其中所述烷基取代的环戊烷是甲基环戊烷。
4.权利要求1的方法，其中该方法是在具有3-12个碳原子的支链脂肪醇存在下在水乳液中操作，所述支链脂肪醇的特征在于羟基数与甲基数之比低于或等于0.5。
5.权利要求1的方法，其中均聚合或共聚合在紫外-可见射线下用自由基光引发剂在水乳液中操作。
6.权利要求1的方法，其中均聚合或共聚合在有机溶剂中的悬浮液中操作。
7.权利要求1的方法，其中用C2-C8全(卤代)含氟烯烃与不含卤原子的C2-C8烯烃制备共聚物，不含卤原子的C2-C8烯烃与C2-C8全(卤代)含氟烯烃的摩尔比在40∶60至60∶40之间。
8.权利要求7的方法，其中所述全(卤代)含氟烯烃选自四氟乙烯和一氯三氟乙烯，而不含卤原子的烯烃是乙烯。
9.权利要求7的方法，其中所述共聚物含有0.1-10％(摩尔)的一种或多种氟化共聚单体。
10.权利要求1-6之任一项所述的方法，其中所述热塑性含氢氟聚合物为用0.1-10％(摩尔)的一种或多种氟化共聚单体改性的聚偏氟乙烯。
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| US3624250A (en) * | 1970-01-20 | 1971-11-30 | Du Pont | Copolymers of ethylene/tetrafluoroethylene and of ethylene/chlorotrifluoroethylene |
| US3865845A (en) * | 1971-02-24 | 1975-02-11 | Paul Raphael Resnick | Fluorinated dioxoles |
| US3847881A (en) * | 1973-04-30 | 1974-11-12 | Allied Chem | Stress-crack resistant ethylene-perhaloethylene copolymers |
| US3978030A (en) * | 1973-08-01 | 1976-08-31 | E. I. Du Pont De Nemours And Company | Polymers of fluorinated dioxoles |
| JPS5838707A (ja) * | 1981-08-20 | 1983-03-07 | イ−・アイ・デユポン・デ・ニモアス・アンド・カンパニ− | パ−フルオロ−２，２−ジメチル−１，３−ジオキソ−ルの無定形共重合体 |
| US4360652A (en) * | 1981-08-31 | 1982-11-23 | Pennwalt Corporation | Method of preparing high quality vinylidene fluoride polymer in aqueous emulsion |
| US4429143A (en) * | 1981-09-28 | 1984-01-31 | E. I. Du Pont De Nemours & Co. | Cyclic monomers derived from trifluoropyruvate esters |
| US4399264A (en) * | 1981-11-19 | 1983-08-16 | E. I. Du Pont De Nemours & Co. | Perfluorodioxole and its polymers |
| FR2542319B1 (fr) * | 1983-03-10 | 1985-07-19 | Solvay | Procede pour la polymerisation dans un milieu aqueux de mise en suspension du fluorure de vinylidene |
| JPS59197411A (ja) * | 1983-04-25 | 1984-11-09 | Daikin Ind Ltd | エチレン−テトラフルオロエチレンまたはクロロトリフルオロエチレン系共重合体 |
| EP0176347B1 (en) * | 1984-09-24 | 1991-12-18 | AUSIMONT S.p.A. | Process for preparing vinylidene fluoride homopolymers and its copolymers |
| JPS6187702A (ja) * | 1984-10-05 | 1986-05-06 | Seitetsu Kagaku Co Ltd | 吸水性樹脂の製造方法 |
| EP0185242A3 (en) * | 1984-12-20 | 1986-11-05 | Ausimont, U.S.A. | Copolymers of chlorotrifluoroethylene, ethylene and perfluoroalkylethylenes |
| JPS61152652A (ja) * | 1984-12-27 | 1986-07-11 | Daikin Ind Ltd | 含フツ素ジアシルパ−オキサイドおよびその用途 |
| IT1189092B (it) * | 1986-04-29 | 1988-01-28 | Ausimont Spa | Processo di polimerizzazione in dispersione acquosa di monomeri fluorurati |
| IT1204903B (it) * | 1986-06-26 | 1989-03-10 | Ausimont Spa | Processo di polimerizzazione in dispersione acquosa di monomeri florati |
| US5021516A (en) * | 1989-06-26 | 1991-06-04 | E. I. Du Pont De Nemours And Company | Poly(perfluoroether)acyl peroxides |
| EP0526216B1 (en) * | 1991-08-01 | 1995-12-27 | Kureha Chemical Industry Co., Ltd. | Method of making vinylidene fluoride polymer |
| US5182342A (en) * | 1992-02-28 | 1993-01-26 | E. I. Du Pont De Nemours And Company | Hydrofluorocarbon solvents for fluoromonomer polymerization |
| US5264530A (en) * | 1992-05-01 | 1993-11-23 | E. I. Du Pont De Nemours And Company | Process of polymerization in an aqueous system |
| IT1263955B (it) * | 1993-02-23 | 1996-09-05 | Ausimont Spa | Processo di (co) polimerizzazione radicalica di monomeri olefinici fluorurati |
| IT1271136B (it) * | 1993-03-23 | 1997-05-27 | Ausimont Spa | Processo di (co)polimerizzazione in emulsione acquosa di monomeri olefinici fluorurati |
| IT1265067B1 (it) * | 1993-05-18 | 1996-10-30 | Ausimont Spa | Processo di (co)polimerizzazione in emulsione acquosa di monomeri olefinici fluorurati |
-
1994
- 1994-03-21 IT ITMI940520A patent/IT1271621B/it active IP Right Grant
-
1995
- 1995-03-10 DE DE69501349T patent/DE69501349T2/de not_active Expired - Fee Related
- 1995-03-10 AT AT95103469T patent/ATE161857T1/de not_active IP Right Cessation
- 1995-03-10 EP EP95103469A patent/EP0673952B1/en not_active Expired - Lifetime
- 1995-03-16 US US08/405,799 patent/US5510435A/en not_active Expired - Lifetime
- 1995-03-17 CA CA002144892A patent/CA2144892A1/en not_active Abandoned
- 1995-03-20 KR KR1019950005876A patent/KR100341450B1/ko not_active IP Right Cessation
- 1995-03-20 RU RU95103972A patent/RU2136700C1/ru active
- 1995-03-21 CN CNB951148095A patent/CN1244600C/zh not_active Expired - Fee Related
- 1995-03-22 JP JP06321895A patent/JP3509983B2/ja not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| DE69501349T2 (de) | 1998-04-16 |
| CN1112130A (zh) | 1995-11-22 |
| ITMI940520A0 (it) | 1994-03-21 |
| US5510435A (en) | 1996-04-23 |
| JPH07300503A (ja) | 1995-11-14 |
| KR100341450B1 (ko) | 2002-11-23 |
| CA2144892A1 (en) | 1995-09-22 |
| EP0673952A1 (en) | 1995-09-27 |
| RU2136700C1 (ru) | 1999-09-10 |
| EP0673952B1 (en) | 1998-01-07 |
| JP3509983B2 (ja) | 2004-03-22 |
| KR950032341A (ko) | 1995-12-20 |
| DE69501349D1 (de) | 1998-02-12 |
| IT1271621B (it) | 1997-06-04 |
| ATE161857T1 (de) | 1998-01-15 |
| ITMI940520A1 (it) | 1995-09-21 |
| RU95103972A (ru) | 1997-03-20 |
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