CN111954658A - 官能含氟聚合物 - Google Patents
官能含氟聚合物 Download PDFInfo
- Publication number
- CN111954658A CN111954658A CN201980024555.0A CN201980024555A CN111954658A CN 111954658 A CN111954658 A CN 111954658A CN 201980024555 A CN201980024555 A CN 201980024555A CN 111954658 A CN111954658 A CN 111954658A
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- CN
- China
- Prior art keywords
- copolymer
- fluorinated
- alkyl
- ammonium
- coo
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 229920002313 fluoropolymer Polymers 0.000 title abstract description 22
- 239000004811 fluoropolymer Substances 0.000 title abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 94
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 14
- 125000002348 vinylic group Chemical group 0.000 claims abstract description 14
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000005670 ethenylalkyl group Chemical group 0.000 claims abstract description 7
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims abstract description 5
- BQMQLJQPTQPEOV-UHFFFAOYSA-N OP(=O)OC=C Chemical class OP(=O)OC=C BQMQLJQPTQPEOV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000003926 acrylamides Chemical class 0.000 claims abstract description 4
- 125000003545 alkoxy group Chemical group 0.000 claims abstract 3
- -1 vinyl carbon Chemical compound 0.000 claims description 54
- 229920001577 copolymer Polymers 0.000 claims description 43
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 39
- 239000003999 initiator Substances 0.000 claims description 30
- 238000006116 polymerization reaction Methods 0.000 claims description 29
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 125000003118 aryl group Chemical group 0.000 claims description 24
- 229910052783 alkali metal Inorganic materials 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 18
- 229910052731 fluorine Inorganic materials 0.000 claims description 16
- 150000001408 amides Chemical class 0.000 claims description 15
- 229910052736 halogen Inorganic materials 0.000 claims description 15
- 150000002367 halogens Chemical class 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 12
- 229910052794 bromium Inorganic materials 0.000 claims description 12
- 229910052801 chlorine Inorganic materials 0.000 claims description 12
- 229910052740 iodine Inorganic materials 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 239000000839 emulsion Substances 0.000 claims description 10
- 238000009472 formulation Methods 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- LOUICXNAWQPGSU-UHFFFAOYSA-N 2,2,3,3-tetrafluorooxirane Chemical compound FC1(F)OC1(F)F LOUICXNAWQPGSU-UHFFFAOYSA-N 0.000 claims description 9
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 9
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical class [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000001732 carboxylic acid derivatives Chemical group 0.000 claims description 8
- PGFXOWRDDHCDTE-UHFFFAOYSA-N hexafluoropropylene oxide Chemical compound FC(F)(F)C1(F)OC1(F)F PGFXOWRDDHCDTE-UHFFFAOYSA-N 0.000 claims description 8
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 7
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 7
- 150000002576 ketones Chemical class 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 5
- 239000012431 aqueous reaction media Substances 0.000 claims description 5
- 229910002102 lithium manganese oxide Inorganic materials 0.000 claims description 5
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 claims description 5
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 5
- 239000003381 stabilizer Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- YXHXDEBLSQQHQE-UHFFFAOYSA-N N.N.OP(O)=O Chemical class N.N.OP(O)=O YXHXDEBLSQQHQE-UHFFFAOYSA-N 0.000 claims description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 4
- 230000000977 initiatory effect Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 3
- VIEVWNYBKMKQIH-UHFFFAOYSA-N [Co]=O.[Mn].[Li] Chemical compound [Co]=O.[Mn].[Li] VIEVWNYBKMKQIH-UHFFFAOYSA-N 0.000 claims description 3
- NDPGDHBNXZOBJS-UHFFFAOYSA-N aluminum lithium cobalt(2+) nickel(2+) oxygen(2-) Chemical compound [Li+].[O--].[O--].[O--].[O--].[Al+3].[Co++].[Ni++] NDPGDHBNXZOBJS-UHFFFAOYSA-N 0.000 claims description 3
- 239000006172 buffering agent Substances 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 229910001416 lithium ion Inorganic materials 0.000 claims description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 3
- VGYDTVNNDKLMHX-UHFFFAOYSA-N lithium;manganese;nickel;oxocobalt Chemical compound [Li].[Mn].[Ni].[Co]=O VGYDTVNNDKLMHX-UHFFFAOYSA-N 0.000 claims description 3
- 239000002923 metal particle Substances 0.000 claims description 3
- 229910001317 nickel manganese cobalt oxide (NMC) Inorganic materials 0.000 claims description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 3
- XVOUMQNXTGKGMA-OWOJBTEDSA-N (E)-glutaconic acid Chemical compound OC(=O)C\C=C\C(O)=O XVOUMQNXTGKGMA-OWOJBTEDSA-N 0.000 claims description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- ZYXUQEDFWHDILZ-UHFFFAOYSA-N [Ni].[Mn].[Li] Chemical compound [Ni].[Mn].[Li] ZYXUQEDFWHDILZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 2
- 125000005210 alkyl ammonium group Chemical group 0.000 claims description 2
- 125000005336 allyloxy group Chemical group 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- 125000005587 carbonate group Chemical group 0.000 claims description 2
- 125000005131 dialkylammonium group Chemical group 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical group 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- 150000001451 organic peroxides Chemical class 0.000 claims description 2
- 150000005621 tetraalkylammonium salts Chemical class 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 125000005208 trialkylammonium group Chemical group 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 239000012736 aqueous medium Substances 0.000 claims 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-L ethenyl-dioxido-oxo-$l^{5}-phosphane Chemical compound [O-]P([O-])(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-L 0.000 claims 1
- 239000000243 solution Substances 0.000 description 22
- 239000004816 latex Substances 0.000 description 19
- 229920000126 latex Polymers 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- 239000004094 surface-active agent Substances 0.000 description 16
- FCBZNZYQLJTCKR-UHFFFAOYSA-N 1-prop-2-enoxyethanol Chemical compound CC(O)OCC=C FCBZNZYQLJTCKR-UHFFFAOYSA-N 0.000 description 15
- 150000003254 radicals Chemical class 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 10
- 239000002033 PVDF binder Substances 0.000 description 9
- 229920002125 Sokalan® Polymers 0.000 description 9
- 239000004584 polyacrylic acid Substances 0.000 description 9
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000013022 venting Methods 0.000 description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 7
- 239000012986 chain transfer agent Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 6
- 239000000872 buffer Substances 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000002519 antifouling agent Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- XUKWFDWKURBTFK-UHFFFAOYSA-N 3-ethenoxypropanoic acid Chemical compound OC(=O)CCOC=C XUKWFDWKURBTFK-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 238000010348 incorporation Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 description 3
- QMIWYOZFFSLIAK-UHFFFAOYSA-N 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene Chemical group FC(F)(F)C(=C)C(F)(F)F QMIWYOZFFSLIAK-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- KHAVLLBUVKBTBG-UHFFFAOYSA-N caproleic acid Natural products OC(=O)CCCCCCCC=C KHAVLLBUVKBTBG-UHFFFAOYSA-N 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- 235000017281 sodium acetate Nutrition 0.000 description 3
- 229960002703 undecylenic acid Drugs 0.000 description 3
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 2
- WUMVZXWBOFOYAW-UHFFFAOYSA-N 1,2,3,3,4,4,4-heptafluoro-1-(1,2,3,3,4,4,4-heptafluorobut-1-enoxy)but-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)=C(F)OC(F)=C(F)C(F)(F)C(F)(F)F WUMVZXWBOFOYAW-UHFFFAOYSA-N 0.000 description 2
- 238000004293 19F NMR spectroscopy Methods 0.000 description 2
- GVEUEBXMTMZVSD-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,6-nonafluorohex-1-ene Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C=C GVEUEBXMTMZVSD-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000008351 acetate buffer Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000006257 cathode slurry Substances 0.000 description 2
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical group CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 125000001475 halogen functional group Chemical group 0.000 description 2
- 239000012510 hollow fiber Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 125000005634 peroxydicarbonate group Chemical group 0.000 description 2
- 239000008363 phosphate buffer Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 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 description 1
- NDMMKOCNFSTXRU-UHFFFAOYSA-N 1,1,2,3,3-pentafluoroprop-1-ene Chemical compound FC(F)C(F)=C(F)F NDMMKOCNFSTXRU-UHFFFAOYSA-N 0.000 description 1
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
- ABADUMLIAZCWJD-UHFFFAOYSA-N 1,3-dioxole Chemical class C1OC=CO1 ABADUMLIAZCWJD-UHFFFAOYSA-N 0.000 description 1
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- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 description 1
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- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
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- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 description 1
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- 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
- 239000001294 propane Substances 0.000 description 1
- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical compound CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 description 1
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- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- WZEOZJQLTRFNCU-UHFFFAOYSA-N trifluoro(trifluoromethoxy)methane Chemical compound FC(F)(F)OC(F)(F)F WZEOZJQLTRFNCU-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及新型线型半结晶官能含氟聚合物,其通过氟化乙烯类单体与选自下组的亲水性单体共聚获得:乙烯基烷基酸、乙烯基膦酸酯、官能丙烯酰胺、碳酸酯、乙烯基醚、烷氧基化合物和双亲水基团单体。
Description
发明领域
本发明涉及新型线型半结晶官能含氟聚合物,其通过氟化乙烯类单体与一种或多种亲水性共聚单体共聚获得。共聚单体可以任选地带有卤素官能团。共聚物中最多10.0重量%的共聚单体单元作为两个含氟单体单元之间的单个单体单元存在。本发明还涉及一种用于形成含氟单体/共聚单体共聚物的方法。与单独的含氟聚合物相比,官能含氟聚合物提供了提高的性能,例如,提高的粘附和亲水特性。本发明的含氟聚合物可以用于受益于官能含氟聚合物的应用中,包括:在电极形成组合物和隔膜组合物中用作粘结,或者用于形成亲水性薄膜和中空纤维。
相关背景技术
含氟聚合物传统上用于需要特殊性质的应用,例如低表面能、高耐化学侵蚀性、耐老化性和电化学稳定性。然而,这些有利的性质也使含氟聚合物难以处理并限制了其应用。例如,含氟聚合物上缺少官能团使其变得难以粘附到基材上,难以促进交联,难以提供用于后续化学修饰的位点,难以被水润湿,以及难以提高亲水性。需要具有改性性质(例如,官能团,其可以增强其性质)的氟化聚合物。
然而,由于含氟自由基的侵扰特性,难以将官能单体单元直接添加至正在聚合的聚合物骨架中,尤其是以无规方式直接添加。官能团通过多种方式添加,例如,通过官能单体与含氟单体直接共聚,以及通过后聚合接枝机理,例如,将马来酸酐接枝到聚偏二氟乙烯均聚物或共聚物上,如US 7,241,817所述,以形成可从阿科玛公司(Arkema Inc)购得的ADX树脂。WO2013/110740和US 7,351,498还描述了含氟聚合物通过单体接枝或共聚而官能化。
US 5,415,958公开了偏二氟乙烯与不饱和二元酸单酯极性单体共聚,将羰基基团引入PVDF骨架,以改进其对不同基材的粘附性。
US 8,337,725公开了偏二氟乙烯与至少一种下式的亲水性(甲基)丙烯酸类单体共聚:
其中,R1、R2、R3中的每一个彼此相同或不同,独立地是氢原子或C1至C3烃基,并且ROH是氢或带有至少一个羟基的C1-C5烃部分。
需要进一步改进氟化聚合物的粘附性能。
本领域中尚未提及通过氟化乙烯类单体与可以任选地带有卤素官能团的亲水性共聚单体进行共聚所获得的官能含氟聚合物,与非官能含氟聚合物相比,其能够改进与基材的粘附性,同时保持良好的机械性能和热性能。
发明内容
本发明涉及一种含有乙烯类单体和亲水性单体的氟化共聚物。
本发明还涉及一种在溶剂中含有氟化共聚物的制剂,并且可以进一步包含活性炭和选自下组的金属颗粒:磷酸铁锂(LFP)、锂镍锰钴氧化物(NMC)、锂锰钴氧化物、锂镍钴铝氧化物、锂锰氧化物和锂镍锰尖晶石。
本发明还构思了一种用于在水性反应介质中制备氟化共聚物的方法,所述方法包括如下步骤:
a)形成水性乳液,所述水性乳液包含:至少一种引发剂、稳定剂、至少一种含氟单体和亲水性单体,
b)在加热和压力下,在搅拌下引发所述至少一种含氟单体与所述亲水性单体的共聚。
本发明还涉及由氟化共聚物形成的制品,其获益于官能共聚物的特别性质。这些制品可在以下应用中找到用途:用于电池或电容器的电极或隔膜;亲水性多孔薄膜或中空纤维薄膜;在至少一个表面上涂覆有所述官能含氟聚合物的制品,浸渍织造和非织造纤维,以及多层结构,其中,所述官能含氟聚合物在含氟聚合物层和与所述含氟聚合物层不相容的聚合物层之间形成连接层(tie layer)。
发明详述
含氟聚合物(特别是聚偏二氟乙烯(PVDF)及其共聚物)在用于锂离子电池的电极制品中用作粘结剂。随着对更好电池性能的需求增加,降低电极中粘结剂含量的需求随之增加了。为了降低粘结剂含量,重要的是提高粘结剂材料的性能。初始性能通过粘合测试来确定,由此对所配制的电极进行剥离测试。该测试的结果的改善意味着改善了粘结性能,并有可能降低总体粘结剂加载量,增加活性物质加载量,并提高电池容量。已显示出氟化乙烯类单体与酸官能共聚单体的共聚物导致该类型粘附性能的改善。这些方法也具有反应生产率低、难以向迅速增长的市场供应足够数量的材料的缺点。此处,我们提出了一种新型共聚物和方法,生产率得以显著改进(即,减少了用于聚合的时间)。
本发明通过提供一种含有氟化乙烯类单体和亲水性共聚单体的氟化共聚物解决了上述问题。
氟化乙烯类单体选自下组:偏二氟乙烯(VDF)、四氟乙烯(TFE)、三氟乙烯(TrFE)、三氟氯乙烯(CTFE)、六氟丙烯(HFP)、氟乙烯(VF)、六氟异丁烯(HFIB)、全氟丁基乙烯(PFBE)、五氟丙烯、3,3,3-三氟-1-丙烯、2-三氟甲基-3,3,3-三氟丙烯、2,3,3,3-四氟丙烯、氟化乙烯基醚(其包括全氟甲基醚(PMVE)、全氟乙基乙烯基醚(PEVE)、全氟丙基乙烯基醚(PPVE)、全氟丁基乙烯基醚(PBVE)、更长链的全氟化乙烯基醚)、氟化间二氧杂环戊烯、部分氟化或全氟化的C4和更高级的α-烯烃、部分氟化或全氟化的C3和更高级环状烯烃,以及它们的组合。
亲水性共聚单体选自:乙烯基烷基酸、乙烯基膦酸酯、官能丙烯酰胺、碳酸酯、乙烯基醚、烯丙氧基化合物,以及乙烯基或烯丙基双亲水基团单体,以及它们的组合。
根据本发明的官能共聚物的特征还在于以下实施方式。
根据一个实施方式,氟化共聚物包含0.01至10.0重量%的一种或多种亲水性单体和90.0至99.99重量%的氟化乙烯类单体。
根据一个实施方式,氟化共聚物包含偏二氟乙烯和一种或多种亲水性单体。
根据一个实施方式,氟化共聚物包含偏二氟乙烯和一种或多种亲水性单体,其中,所述亲水性单体含有在至少一个乙烯基碳上的至少一种卤素原子。
根据一个实施方式,所述亲水性单体含有在至少一个乙烯基碳上的至少一个氟原子。
本发明还涉及一种在溶剂中包含氟化共聚物的制剂。溶剂优选选自:N-甲基吡咯烷酮(NMP)、二甲基亚砜(DMSO)、N,N-二甲基甲酰胺(DMF)、亚磷酸三乙酯(TEP)、丙酮、四氢呋喃、甲基乙基酮(MEK)、甲基异丁基酮(MiBK)、乙酸乙酯(EA)、乙酸丁酯(BA)、碳酸二甲酯(DMC)、碳酸二乙酯(DEC)或碳酸乙基甲基酯(MEC)。
根据一个实施方式,该制剂还包含悬浮在所述溶剂中的锂盐颗粒和活性碳。锂盐颗粒选自下组:磷酸铁锂(LFP)、锂镍锰钴氧化物(NMC)、锂锰钴氧化物(LCO)、、锂锰氧化物(LMO)、锂镍钴铝氧化物(NCA)和锂镍锰氧化物(LNMO)。该制剂特别适合于形成电池电极膜,尤其是用于锂离子电池的正电极。本发明包括一种电池,所述电池包含如本文所述的氟化共聚物。
本发明还构思了一种用于在水性反应介质中制备氟化共聚物的方法,所述方法包括如下步骤:
a)形成水性乳液,所述水性乳液包含:至少一种引发剂、稳定剂、至少一种氟化乙烯类单体和如上所述的亲水性单体,
b)在加热和压力下,在搅拌下引发所述至少一种氟化乙烯类单体与所述亲水性单体的共聚。
根据本发明的聚合反应可以通过向反应器中加入水(优选去离子水)、至少一种氟化乙烯类单体、至少一种如上文限定的亲水性单体以及任选的表面活性剂、链转移剂和/或防污剂中的一种或多种来进行。可以在引入单体之前,吹扫掉反应器中的空气。将水添加到反应器中,然后使反应器达到所需的起始温度,但是可以在使反应器达到该起始温度之前或之后添加其它材料。加入至少一种自由基引发剂以开始并维持聚合反应。可以任选地添加另外的单体以补充消耗掉的单体,并且可以在聚合期间任选地添加其它材料以维持反应并控制最终产物性质。
“共聚物”用于表示具有两种或更多种不同单体单元的聚合物。“聚合物”用于表示均聚物和共聚物。聚合物可以是直链的、支化的、星形的、梳状的、嵌段的或任何其他结构。聚合物可以是均质的、非均质的,并且可以具有共聚单体单元的梯度分布。引用的所有参考文献均通过引用纳入本文。如本文所用,除非另有说明,否则,百分比应指重量百分比。除非另有说明,否则,分子量是使用聚甲基丙烯酸甲酯标准物,通过GPC测定的重均分子量。在聚合物存在一定程度的交联时,由于不溶性聚合物级分而不能采用GPC,使用可溶性级分/凝胶级分或由凝胶中提取后的可溶性级分分子量。结晶度和熔融温度如ASTM D3418所述通过DSC以10℃/分钟的加热速率进行测量。熔体粘度根据ASTM D3835在230℃进行测量,表示为千泊@100秒-l。
亲水性单体
与一种或多种含氟单体组合使用的亲水性共聚单体包括但不限于一种或多种以下物质,并且将特定类别的多于一种的单体与以下不同类别的两种或更多种单体的混合物掺混在一起以形成三元共聚物:
A)乙烯基烷基酸,
具有下式结构作为共聚单体(M1):
其中,R1、R2和R3是氢或卤素(F、Cl、Br、I)。
其中,R4是C1至C16直链、支化、芳族或环烷基基团,C1至C16氟化直链、支化、芳族或环烷基基团,六氟环氧丙烷低聚物,或四氟环氧乙烷低聚物。
其中,R5是羧酸(C(O)OH)、碱金属羧酸盐(COO-M+)、羧酸铵盐(COO-NH4 +)、羧酸烷基铵盐(COO-N(Alk)4 +)、醇(OH)、酰胺(C(O)NH2)、二烷基酰胺(C(O)NAlk2)、磺酸(S(O)(O)OH)、碱金属磺酸盐(S(O)(O)O-M+)、磺酸铵盐(S(O)(O)O-NH4 +)、磺酸烷基铵盐(S(O)(O)O-N(Alk)4 +)。
B)乙烯基烷基酸,
其具有下式M2:
其中:R1、R2和R3是氢或卤素(F、Cl、Br、I);
其中:R4和R5分别是氢、C1至C16直链烷基、支化烷基、芳基或环烷基基团,C1至C16氟化直链烷基、支化烷基、芳基或环烷基基团,六氟环氧丙烷低聚物或四氟环氧乙烷低聚物,碱金属离子(Li+、Na+、K+、Rb+、Cs+),铵离子(NH4 +),或烷基铵(NAlk4 +)。
C)官能丙烯酰胺,
具有下式结构作为共聚单体(M3):
其中:R1、R2和R3是氢或卤素(F、Cl、Br、I)。
其中:R4和R6分别是C1至C16直链、支化、芳族或环烷基基团,C1至C16氟化直链、支化、芳族或环烷基基团,六氟环氧丙烷低聚物或四氟环氧乙烷低聚物。
其中:R5和R7分别是羧酸(C(O)OH)、碱金属羧酸盐(COO-M+)、羧酸铵盐(COO-NH4 +)、羧酸烷基铵盐(COO-N(Alk)4 +)、醇(OH)、酰胺(C(O)NH2)、二烷基酰胺(C(O)NAlk2)、磺酸(S(O)(O)OH)、碱金属磺酸盐(S(O)(O)O-M+)、磺酸铵盐(S(O)(O)O-NH4 +)、磺酸烷基铵盐(S(O)(O)O-N(Alk)4 +)、酮(C(O))或乙酰丙酮(C(O)-CH2-C(O))、或膦酸酯(P(O)(OH)2)、碱金属或铵的膦酸盐。
D)碳酸酯,
其包括共聚单体M4:
其中:R1、R2和R3是氢或卤素(F、Cl、Br、I)。
其中:R4是化学键,C1至C16直链烷基、支化烷基、芳基或环烷基基团,C1至C16氟化直链烷基、支化烷基、芳基或环烷基基团。
其中:R5是C1至C16环烷基基团、C1至C16氟化环烷基基团,其含有碳酸酯基团作为环结构的一部分。
E)乙烯基醚,具有下式结构作为共聚单体(M5):
其中:R1、R2和R3是氢或卤素(F、Cl、Br、I)。
其中:R4是C1至C16直链、支化、芳族或环烷基基团,C1至C16氟化直链、支化、芳族或环烷基基团,六氟环氧丙烷低聚物,或四氟环氧乙烷低聚物。
其中:R5是羧酸(C(O)OH)、碱金属羧酸盐(COO-M+)、羧酸铵盐(COO-NH4 +)、羧酸烷基铵盐(COO-N(Alk)4 +)、醇(OH)、酰胺(C(O)NH2)、二烷基酰胺(C(O)NAlk2)、磺酸(S(O)(O)OH)、碱金属磺酸盐(S(O)(O)O-M+)、磺酸铵盐(S(O)(O)O-NH4 +)、磺酸烷基铵盐(S(O)(O)O-N(Alk)4 +)、酮(C(O))、乙酰丙酮(C(O)-CH2-C(O))。
F)烯丙氧基化合物,具有下式结构作为共聚单体(M6):
其中:R1、R2和R3是氢或卤素(F、Cl、Br、I)。
其中:R4是CH2或CF2;
其中:R5是C1至C16直链、支化、芳族或环烷基基团,C1至C16氟化直链、支化、芳族或环烷基基团,六氟环氧丙烷低聚物或四氟环氧乙烷低聚物。
其中:R6是羧酸(C(O)OH)、碱金属羧酸盐(COO-M+)、羧酸铵盐(COO-NH4 +)、羧酸烷基铵盐(COO-N(Alk)4 +)、醇(OH)、酰胺(C(O)NH2)、二烷基酰胺(C(O)NAlk2)、磺酸(S(O)(O)OH)、碱金属磺酸盐(S(O)(O)O-M+)、磺酸铵盐(S(O)(O)O-NH4 +)、磺酸烷基铵盐(S(O)(O)O-N(Alk)4 +)、酮(C(O))或乙酰丙酮(C(O)-CH2-C(O)),或膦酸酯(P(O)(OH)2),碱金属或铵的膦酸盐。
G)多亲水基团共聚单体
本发明也考虑具有两个或更多个亲水基团的单体。其包括但不限于:衣康酸、马来酸、戊烯二酸、富马酸及它们的酸酐,碱金属盐、铵盐及单烷基铵盐、二烷基铵盐、三烷基铵盐和四烷基铵盐。
基于单体总量,亲水性共聚单体在反应器中的用量可以为例如约0.001至约15重量%。优选地,基于单体总量,其用量可以为约0.01至约5重量%。在各种实施方式中,基于单体总量,亲水性单体的总量为至少0.01重量%、至少0.05重量%、至少0.1重量%、至少1.0重量%或至少2.0重量%。在其它实施方式中,基于单体总量,亲水性单体的总量不超过13.0重量%、10.0重量%、9.0重量%、7.0重量%、6.0重量%、5.0重量%。亲水性共聚单体可以在溶液中使用,例如,在水性溶液中使用,以便于操作。
聚合物可以包含0.01重量%至15.0重量%的所述亲水性单体以及85.0重量%至99.99重量%的氟化乙烯类单体。
表面活性剂
聚合中使用的表面活性剂可以是本领域已知可用于PVDF乳液聚合的任意表面活性剂,包括全氟化、部分氟化和非氟化的表面活性剂。在优选实施方式中,本公开的PVDF乳液可以不含含氟表面活性剂,并且在聚合的任意部分中均不使用含氟表面活性剂。PVDF聚合中可用的非氟化表面活性剂性质可以是离子和非离子的,包括但不限于:3-烯丙氧基-2-羟基-1-丙烷磺酸盐,聚乙烯基膦酸、聚丙烯酸、聚乙烯基磺酸以及它们的盐,聚乙二醇和/或聚丙二醇以及它们的嵌段共聚物,膦酸烷基酯和硅氧烷基表面活性剂。
表面活性剂还可以与亲水性共聚单体组合使用,从而为聚合物乳液提供进一步的稳定性。优选的表面活性剂是非氟化烃表面活性剂、硅氧烷表面活性剂或它们的组合。例如,亲水性(甲基)丙烯酸类共聚单体可以与十二烷基苯磺酸钠(SDDBS)、辛基磺酸钠、月桂基硫酸钠、月桂基硫酸铵和月桂醇聚氧乙烯醚硫酸钠组合使用。在本发明的某些实施方式中,在水性乳液中不存在含氟表面活性剂和/或在氟化乙烯类单体与亲水性(甲基)丙烯酸类共聚单体的共聚期间不引入含氟表面活性剂。在一个实施方式中,稳定剂是聚电解质。在另一实施方式中,聚合物乳液的稳定剂是官能化纤维素。
引发剂
术语“引发剂”以及“自由基引发剂”和“游离基引发剂”这样的表达是指一种化学物质,其能够自发地或通过暴露于热或光来提供自由基来源。合适的引发剂的示例包括过氧化物、过氧二碳酸盐/酯以及偶氮化合物。“引发剂”还包括可用于提供自由基来源的氧化还原体系。术语“自由基”以及“游离基”这样的表达是是指包含至少一个未配对电子的化学物质。
以足以引发并以所需反应速率维持聚合反应的量,将自由基引发剂加入反应混合物中。添加的顺序可以根据所需的方法和胶乳乳液特性而变化。
自由基引发剂可以包括:过硫酸盐,如过硫酸钠、过硫酸钾或过硫酸铵。例如,添加至反应混合物的过硫酸盐的量(基于添加至反应混合物的单体的总重量)可以为约0.002重量%至约1.0重量%。
自由基引发剂可以包括有机过氧化物,例如,烷基过氧化物、二烷基过氧化物、二酰基过氧化物、过氧二碳酸酯和过氧酯,或它们的混合物。优选的二烷基过氧化物是二叔丁基过氧化物(DTBP),其可以以占单体总量约0.01至约5重量%的量添加至反应混合物中,并且优选以占单体总量约0.05至约2.5重量%的量添加。优选的过氧二碳酸酯引发剂是过氧二碳酸二正丙酯和过氧二碳酸二异丙酯,其可以以占单体总量约0.5至约2.5重量%的量添加到反应混合物中。过氧酯引发剂包括过氧新戊酸叔戊酯、过氧新戊酸叔丁酯和琥珀酸过氧化物。
自由基引发剂可包括偶氮引发剂,例如2,2'-偶氮二(2-甲基丙脒)二盐酸盐。
自由基引发剂可以包括氧化还原体系。“氧化还原体系”是指包括氧化剂、还原剂和任选地作为电子转移介质的促进剂的体系。氧化剂包括:例如,过硫酸盐;过氧化物,例如过氧化氢;氢过氧化物,例如叔丁基氢过氧化物和异丙苯氢过氧化物;以及氧化性金属盐,例如硫酸铁。还原剂包括:例如,甲醛合次硫酸钠、亚硫酸钠、亚硫酸钾、抗坏血酸、亚硫酸氢盐、偏亚硫酸氢盐和还原性金属盐。促进剂是氧化还原体系的成分,其在不同的氧化态下能够与氧化剂和还原剂反应,从而加速了整个反应。促进剂包括例如过渡金属盐,例如硫酸亚铁。在氧化还原体系中,氧化剂和还原剂的用量可占单体总量的约0.01至约0.5重量%。任选的促进剂的用量可以占单体总量的约0.005-约0.025重量%。氧化还原体系见述于G.S.Misra和U.D.N.Bajpai,Prog.Polym.Sci.,1982,8(1-2),第61-131页。
链转移剂
将链转移剂添加到聚合反应中以调节产物的分子量。它们可以在反应开始时以单个部分或在整个反应过程中以递增或连续方式添加到聚合反应中。链转移剂的添加量和添加方式取决于所采用的特定链转移剂的活性,并取决于聚合物产物的所需分子量。基于添加到反应混合物中的单体总重量,添加到聚合反应中的链转移剂的量优选为约0.05至约5重量%,更优选为约0.1至约2重量%。
含氧化合物(如醇、碳酸酯/盐、酮、酯和醚)可以用作链转移剂。可用作链转移剂的含氧化合物的示例包括异丙醇,见述于美国专利4,360,652。可以在含卤素单体的聚合中用作链转移剂的其它种类的化合物包括:例如,卤代烃和氢卤烃,例如氯代烃。烷烃(例如,乙烷和丙烷)可以用作链转移剂。
缓冲剂
聚合反应混合物可任选地包含缓冲剂以在整个聚合反应中维持受控的pH。pH优选控制在约4至约8,以最大程度抑制产物中产生不期望的颜色。
缓冲剂可以包括有机酸或无机酸或其碱金属盐,或者该有机或无机酸的碱或盐,其至少一个pKa值和/或pKb值范围为约4至约10,优选约4.5至约9.5。在本发明实践中的优选缓冲剂包括:例如,磷酸盐缓冲剂和乙酸盐缓冲剂。“磷酸盐缓冲剂”是磷酸的一种盐或其多种盐的混合物。“乙酸盐缓冲剂”是乙酸的盐。
在采用过硫酸钾作为自由基引发剂的情况下优选采用缓冲剂。与过硫酸盐自由基引发剂一起使用的优选缓冲剂是乙酸钠。基于加入反应中的过硫酸盐引发剂的重量,乙酸钠缓冲剂的优选量为约50重量%至约150重量%。在一个优选实施方式中,引发剂进料在水溶液中大致包括等重量的过硫酸钾和乙酸钠。
防污剂
向反应中添加石蜡或烃油用作防污剂,以最大程度减少或防止聚合物粘附到反应器部件上。任何长链饱和烃蜡或油都可以完成该功能。添加到反应器中的油或蜡的量是用于使反应器部件上形成聚合物粘附最小化的量。该量通常与反应器的内表面积成比例,并且可以在每平方厘米反应器内表面积约1mg至约40mg之间变化。石蜡或烃油的量优选为约5mg/cm2反应器内表面积。
共聚条件
用于聚合的温度可以根据所选引发剂体系进行变化,例如20℃至130℃。聚合温度优选35℃至130℃,最优选70℃至125℃。
用于聚合的压力可以根据反应设备的容量、所选引发剂体系和单体的选择在280kPa至20000kPa之间变化。聚合压力优选2,000-11,000kPa,并且最优选2,750-6,900kPa。
聚合在搅拌或其他搅动下进行。搅拌/搅动可以是恒定的,或者可以变化以对聚合过程中的工艺条件进行优化。在一个实施方式中,使用多种搅拌速度和多种温度来控制反应。
根据本发明方法的一个实施方式,在装有搅拌器和热控制装置的加压聚合反应器中装入水(优选去离子水)、一种或多种卤代单体(1)和至少一种氟化乙烯类单体。混合物可以任选地含有:表面活性剂、缓冲剂、防污剂或用于调节聚合物产物分子量的链转移剂中的一种或多种。
在将一种或多种单体引入之前,优选从反应器中去除空气,以获得不含氧的环境用于聚合反应。
聚合成分的组合顺序可以变化,但是通常优选在引发氟化乙烯类单体聚合之前,至少部分亲水性单体存在于水性反应介质中。在反应期间,可以将另外量的亲水性单体加入反应器中。
在一个实施方式中,将水、引发剂、亲水性单体和任选的表面活性剂、防污剂、链转移剂和/或缓冲剂加入反应器中,并将反应器加热至所需的反应温度。然后,优选以提供基本恒定压力的速率,使一种或多种氟化乙烯类单体进料至反应器中。
或者,可以将氟化乙烯类单体、亲水性单体和引发剂与一种或多种任选成分一起加入反应器中。如本领域中已知的,可以想到含氟聚合物共聚方法的其它变化。
当所需重量的单体已经进料至反应器中时,终止单体进料。任选地添加额外的自由基引发剂,并允许反应进行合适时间以反应完。反应器压力随着反应器内单体消耗而下降。
共聚反应完成后,使反应器回到环境温度,并将残留的未反应单体排空以达到大气压。然后从反应器中回收包含共聚物的水性反应介质,其为胶乳。胶乳由反应组分的稳定混合物组成,即,水、亲水性单体、引发剂(和/或引发剂的分解产物)和共聚物固体。
通常,胶乳包含约10重量%至约50重量%的共聚物固体。胶乳中的聚合物可以是尺寸范围为约30nm至约800nm的小颗粒形式。
产物处理
共聚反应的产物是胶乳,其可以该形式使用,通常在来自聚合过程的固体副产物过滤后使用,或者可以进行凝结以分离出固体,该固体随后可以洗涤并干燥。为了以胶乳形式使用,可以通过添加表面活性剂来使胶乳稳定,该表面活性剂可以与聚合期间存在的表面活性剂相同或不同(如果存在的话)。该随后添加的表面活性剂可以例如是离子表面活性剂或非离子表面活性剂。在本发明的一个实施方式中,未将含氟表面活性剂添加到胶乳中。对于固体产品,胶乳可以机械凝结或通过添加盐或酸来凝结,然后通过众所周知的方法例如过滤来分离。一旦分离,可以通过洗涤或其它技术来纯化固体产物,并且可以对其进行干燥以作为粉末使用,粉末可以进一步加工成颗粒、丸粒等。
在一个实施方式中,以水中胶乳或溶剂溶液的形式,将根据本发明的官能共聚物施加至基材,所述溶剂选自上文所列溶剂。任选地,可以在官能共聚物层之前,将底漆层施加到基材上。
在一个实施方式中,所述基材是多孔的,例如,多孔薄膜。
实施例
通过19F NMR测定共聚单体的掺入
通过19F NMR测定共聚单体的掺入程度。在带有5mm TXO探针的Bruker AV III500(11.7T)上于80℃获取19F和1H NMR光谱。各样品在80℃的DMSO-d6中溶解至少24小时以进行分析。相对于材料的所有19F信号的总积分,对出现在93.5ppm处的峰进行积分,其对应于掺入的共聚单体单元在α位置的–CF2-基团[--CH2-CF2-CH2-CH(R)-CH2-CF2-(其中,R表示具有亲水性官能团的键或间隔基)]。获得由这些积分所确定的值之比作为共聚单体的掺入量。使用这种方法,确定最小可检测掺入量为100ppm。ppm的单体量的测量以重量/重量计。
实施例1:通过在剧烈搅拌下将2.0g十一碳烯酸(UDA)添加到192.0g去离子水和6.0g的1摩尔氢氧化钠(NaOH)的溶液中来制备十一碳烯酸钠溶液(NaUDA)。
向2升高压釜中添加1,000g去离子水、1.6g低分子量聚丙烯酸(BASF CP-10S)和50g的NaUDA溶液。通过输入60psi的氮气并排气,使高压釜脱氧,再重复此过程两次。开始搅拌,将高压釜加热至83℃并用偏二氟乙烯加压至650psi。各2.0重量%的过硫酸钾(KPS)和乙酸钠以5毫升/分钟开始进料。压力开始下降后,以1.0毫升/分钟开始另外的NaUDA进料,KPS进料减至1.0毫升/分钟,并通过另外的VDF进料保持压力。以这种方式继续进料,提高NaUDA进料速率以调节瞬时VDF进料需求,从而保持500-1,000g/小时。以这种方式将NaUDA进料提高至5.0毫升/分钟。继续所有进料,直到将总共700g的VDF进料至反应器中。停止单体进料,并使压力自发降低10分钟,此时将反应器排空至达到大气压并冷却至室温。从反应器中排出胶乳,并在对流烘箱中干燥过夜。
实施例2:遵循实施例1中概述的步骤,不同的是通过使用6.0g UDA、18.0g NaOH和176.0g去离子水将NaUDA溶液浓度提高至3.0重量%,并且将KPS溶液浓度提高至4.0重量%。
实施例3:通过在剧烈搅拌下将6.65g乙烯基膦酸(VPA)添加到123.1g的0.5N氢氧化钠溶液和29.8g去离子水的溶液中来制备乙烯基膦酸钠溶液(NaVPA)。
向2升高压釜中添加900g去离子水、2.3g低分子量聚丙烯酸(BASF CP-10S)和25g的NaVPA溶液。通过输入60psi的氮气并排气,使高压釜脱氧,再重复此过程两次。开始搅拌,将高压釜加热至83℃并用偏二氟乙烯加压至650psi。各4.0重量%的过硫酸钾(KPS)以5.0毫升/分钟开始进料。压力开始下降后,以1.0毫升/分钟开始另外的NaVPA进料,KPS进料减至1.0毫升/分钟,并通过另外的VDF进料保持压力。以这种方式继续进料,提高NaVPA进料速率以调节瞬时VDF进料需求,从而保持500-1,000g/小时。以这种方式将NaVPA进料提高至5.0毫升/分钟。继续所有进料,直到将总共700g的VDF进料至反应器中。停止单体进料,并使压力自发降低10分钟,此时将反应器排空至达到大气压并冷却至室温。从反应器中排出胶乳,并在对流烘箱中干燥过夜。
实施例4:遵循实施例3中概述的步骤,不同的是KPS溶液浓度降低至2.5重量%。熔点(C,DSC第二次加热)测定为161.8。结晶焓为48.0J/g。
实施例5:实施例(丙烯酰胺):向2升高压釜中添加900g去离子水、2.3g低分子量聚丙烯酸(BASF CP-10S)和25g的1.0重量%丙烯酰胺水性溶液。通过输入60psi的氮气并排气,使高压釜脱氧,再重复此过程两次。开始搅拌,将高压釜加热至83℃并用偏二氟乙烯加压至650psi。各4.0重量%的过硫酸钾(KPS)以5.0毫升/分钟开始进料。压力开始下降后,以1.0毫升/分钟开始另外的丙烯酰胺进料,KPS进料减至1.0毫升/分钟,并通过另外的VDF进料保持压力。以这种方式继续进料,提高丙烯酰胺进料速率以调节瞬时VDF进料需求,从而保持500-1,000g/小时。以这种方式将丙烯酰胺进料提高至5.0毫升/分钟。继续所有进料,直到将总共700g的VDF进料至反应器中。停止单体进料,并使压力自发降低10分钟,此时将反应器排空至达到大气压并冷却至室温。从反应器中排出胶乳,并在对流烘箱中干燥过夜。
实施例6:实施例(碳酸亚乙烯酯):向2升高压釜中添加900g去离子水、2.3g低分子量聚丙烯酸(BASF CP-10S)和25g的1.0重量%碳酸亚乙烯酯水溶液。通过输入60psi的氮气并排气,使高压釜脱氧,再重复此过程两次。开始搅拌,将高压釜加热至83℃并用偏二氟乙烯加压至650psi。各4.0重量%的过硫酸钾(KPS)以5.0毫升/分钟开始进料。压力开始下降后,以1.0毫升/分钟开始另外的碳酸亚乙烯酯进料,KPS进料减至1.0毫升/分钟,并通过另外的VDF进料保持压力。以这种方式继续进料,提高碳酸亚乙烯酯进料速率以调节瞬时VDF进料需求,从而保持500-1,000g/小时。以这种方式将碳酸亚乙烯酯进料提高至5.0毫升/分钟。继续所有进料,直到将总共700g的VDF进料至反应器中。停止单体进料,并使压力自发降低10分钟,此时将反应器排空至达到大气压并冷却至室温。从反应器中排出胶乳,并在对流烘箱中干燥过夜。
实施例7:实施例(碳酸亚乙烯酯):向2升高压釜中添加900g去离子水、2.3g低分子量聚丙烯酸(BASF CP-10S)和25g的1.0重量%羧乙基乙烯基醚水溶液。通过输入60psi的氮气并排气,使高压釜脱氧,再重复此过程两次。开始搅拌,将高压釜加热至83℃并用偏二氟乙烯加压至650psi。各4.0重量%的过硫酸钾(KPS)以5.0毫升/分钟开始进料。压力开始下降后,以1.0毫升/分钟开始另外的羧乙基乙烯基醚进料,KPS进料减至1.0毫升/分钟,并通过另外的VDF进料保持压力。以这种方式继续进料,提高羧乙基乙烯基醚进料速率以调节瞬时VDF进料需求,从而保持500-1,000g/小时。以这种方式将羧乙基乙烯基醚进料提高至5.0毫升/分钟。继续所有进料,直到将总共700g的VDF进料至反应器中。停止单体进料,并使压力自发降低10分钟,此时将反应器排空至达到大气压并冷却至室温。从反应器中排出胶乳,并在对流烘箱中干燥过夜。
实施例8:通过在剧烈搅拌下将6.0g的烯丙氧基乙醇(AOE)添加至294.0g的去离子水中来制备AOE溶液。
向2升高压釜中添加900g去离子水、2.3g低分子量聚丙烯酸(BASF CP-10S)和10g的AOE溶液。通过输入60psi的氮气并排气,使高压釜脱氧,再重复此过程两次。开始搅拌,将高压釜加热至83℃并用偏二氟乙烯加压至650psi。各4.0重量%的过硫酸钾(KPS)进料以5.0毫升/分钟开始。压力开始下降后,以1.0毫升/分钟开始另外的AOE进料,KPS进料减至1.0毫升/分钟,并通过另外的VDF进料保持压力。以这种方式继续进料,提高AOE进料速率以调节瞬时VDF进料需求,从而保持500-1,000g/小时。以这种方式将AOE进料提高至5.0毫升/分钟。继续所有进料,直到将总共700g的VDF进料至反应器中。停止单体进料,并使压力自发降低10分钟,此时将反应器排空至达到大气压并冷却至室温。从反应器中排出胶乳,并在对流烘箱中干燥过夜。
实施例9:遵循实施例3中概述的步骤,不同的是AOE溶液浓度升高至4.0重量%(12.0g AOE+288.0g去离子水)。
实施例10:通过在剧烈搅拌下将12.0g的烯丙氧基丙二醇(AOPD)添加至288.0g的去离子水中来制备AOPD溶液。
向2升高压釜中添加900g去离子水、2.3g低分子量聚丙烯酸(BASF CP-10S)和10g的AOPD溶液。通过输入60psi的氮气并排气,使高压釜脱氧,再重复此过程两次。开始搅拌,将高压釜加热至83℃并用偏二氟乙烯加压至650psi。各4.0重量%的过硫酸钾(KPS)进料以5.0毫升/分钟开始。压力开始下降后,以1.0毫升/分钟开始另外的AOPD进料,KPS进料减至1.0毫升/分钟,并通过另外的VDF进料保持压力。以这种方式继续进料,提高AOPD进料速率以调节瞬时VDF进料需求,从而保持500-1,000g/小时。以这种方式将AOPD进料提高至5.0毫升/分钟。继续所有进料,直到将总共700g的VDF进料至反应器中。停止单体进料,并使压力自发降低10分钟,此时将反应器排空至达到大气压并冷却至室温。从反应器中排出胶乳,并在对流烘箱中干燥过夜。
实施例11:遵循实施例10中概述的步骤,不同的是KPS溶液浓度降低至2.5重量%。
实施例12:通过在剧烈搅拌下将6.0g的丙烯酸(AA)和6.0g的AOE添加至288.0g的去离子水中来制备AA和AOE的溶液(AA/AOE)。
向2升高压釜中添加900g去离子水、2.3g低分子量聚丙烯酸(BASF CP-10S)和10g的AOPD溶液。通过输入60psi的氮气并排气,使高压釜脱氧,再重复此过程两次。开始搅拌,将高压釜加热至83℃并用偏二氟乙烯加压至650psi。各4.0重量%的过硫酸钾(KPS)进料以5.0毫升/分钟开始。压力开始下降后,以1.0毫升/分钟开始另外的AA/AOE进料,KPS进料减至1.0毫升/分钟,并通过另外的VDF进料保持压力。以这种方式继续进料,提高AA/AOE进料速率以调节瞬时VDF进料需求,从而保持500-1,000g/小时。以这种方式将AA/AOE进料提高至5.0毫升/分钟。继续所有进料,直到将总共700g的VDF进料至反应器中。停止单体进料,并使压力自发降低10分钟,此时将反应器排空至达到大气压并冷却至室温。从反应器中排出胶乳,并在对流烘箱中干燥过夜。
阴极制剂和制备:此处描述了一个用于实验室规模的阴极浆料制备过程。首先将本发明的PVDF共聚物溶解在N-甲基吡咯烷酮(NMP)溶剂中,通常浓度为5-10重量%。将导电碳添加剂(例如来自特密高公司(Timcal)的SuperP-Li)添加到粘结剂溶液中,并使用离心行星式混合器Thinky AR-310以2000rpm混合120秒,重复3次,每次间隔1分钟空气冷却。将导电碳分散在粘结剂溶液中后,将活性材料(如(优美科公司(Umicore)))和少量NMP添加到混合物中,并进行混合以形成厚而均匀的糊料,通常以2000rpm混合60秒。然后将少量的NMP加入到糊料中,并以60秒/2000rpm的条件进行混合,以逐渐降低浆料固体含量(每次添加NMP固含量约为1.5%)和粘度。多次重复该稀释步骤,直到浆料粘度达到用于涂覆的合适水平,通常为3,000-15,000cP@l/s剪切速率。我们实验室的阴极的典型配方是活性材料/碳/PVDF=97/1.5/1.5(重量/重量/重量)(以干基计)。
然后在自动涂膜机(Elcometer 4340)上使用可调节刮刀将阴极浆料浇铸到铝箔(厚度为15mm)上。然后将湿铸件转移到对流烘箱中,并在120℃下干燥30分钟。干燥后,使用辊磨机(IRM,国际辊磨机公司(international roll mill))将电极压延至3.2-3.6g/cm3的最终密度,并且典型值为3.4g/cm3。干阴极的典型面积质量加载量为180-220g/cm2。
采用ASTM D903,通过180°剥离测试获得阴极的剥离强度,但有三处修改。第一处修改是所使用的拉伸速率为50毫米/分钟(剥离速率为25毫米/分钟)。第二处修改是没有在受控的湿度和温度下的两周调节期。阴极在制造后一天测试。第三处修改是阴极通过3M公司的410M双面胶带粘结至对齐板上,并用测试机的手柄来剥离柔性铝箔集电器。
表1
*根据NMR分析灵敏度四舍五入至最接近的100ppm
ppm以重量/重量测量。
Claims (24)
1.一种氟化共聚物,其包含:氟化乙烯类单体和选自下组的一种或多种亲水性单体:乙烯基烷基酸、乙烯基膦酸酯、官能丙烯酰胺、碳酸酯、乙烯基醚、烷氧基化合物和双亲水基团单体。
2.如权利要求1所述的共聚物,其包含:最高达10.0重量%的所述亲水性单体。
3.如权利要求1所述的共聚物,其中,所述氟化乙烯类单体包括偏二氟乙烯。
4.如权利要求1所述的共聚物,其中,所述亲水性单体中的至少一种包括在乙烯碳上的至少一种卤素。
5.如权利要求4所述的共聚物,其中,所述至少一种卤素包括氟。
6.如权利要求1所述的共聚物,其中,所述乙烯基烷基酸共聚单体具有式(M1):
其中,R1、R2和R3是氢或卤素(F、Cl、Br、I);
其中,R4是C1至C16直链、支化、芳族或环烷基基团,C1至C16氟化直链、支化、芳族或环烷基基团,六氟环氧丙烷低聚物,或四氟环氧乙烷低聚物;并且
其中,R5是羧酸(C(O)OH)、碱金属羧酸盐(COO-M+)、羧酸铵盐(COO-NH4 +)、羧酸烷基铵盐(COO-N(Alk)4 +)、醇(OH)、酰胺(C(O)NH2)、二烷基酰胺(C(O)NAlk2)、磺酸(S(O)(O)OH)、碱金属磺酸盐(S(O)(O)O-M+)、磺酸铵盐(S(O)(O)O-NH4 +)、磺酸烷基铵盐(S(O)(O)O-N(Alk)4 +)。
8.如权利要求1所述的共聚物,其中,所述官能丙烯酰胺共聚单体具有式(M3):
其中:R1、R2和R3是氢或卤素(F、Cl、Br、I);
其中:其R4和R6分别是C1至C16直链、支化、芳族或环烷基基团、C1至C16氟化直链、支化、芳族或环烷基基团,六氟环氧丙烷低聚物或四氟环氧乙烷低聚物;
其中:R5和R7分别是羧酸(C(O)OH)、碱金属羧酸盐(COO-M+)、羧酸铵盐(COO-NH4 +)、羧酸烷基铵盐(COO-N(Alk)4 +)、醇(OH)、酰胺(C(O)NH2)、二烷基酰胺(C(O)NAlk2)、磺酸(S(O)(O)OH)、碱金属磺酸盐(S(O)(O)O-M+)、磺酸铵盐(S(O)(O)O-NH4 +)、磺酸烷基铵盐(S(O)(O)O-N(Alk)4 +)、酮(C(O))或乙酰丙酮(C(O)-CH2-C(O)),或膦酸酯(P(O)(OH)2),碱金属或铵的膦酸盐。
10.如权利要求1所述的共聚物,其中,所述乙烯基醚共聚单体具有式(M5):
其中:R1、R2和R3是氢或卤素(F、Cl、Br、I);
其中:R4是C1至C16直链、支化、芳族或环烷基基团,C1至C16氟化直链、支化、芳族或环烷基基团,六氟环氧丙烷低聚物或四氟环氧乙烷低聚物;并且
其中:R5是羧酸(C(O)OH)、碱金属羧酸盐(COO-M+)、羧酸铵盐(COO-NH4 +)、羧酸烷基铵盐(COO-N(Alk)4 +)、醇(OH)、酰胺(C(O)NH2)、二烷基酰胺(C(O)NAlk2)、磺酸(S(O)(O)OH)、碱金属磺酸盐(S(O)(O)O-M+)、磺酸铵盐(S(O)(O)O-NH4 +)、磺酸烷基铵盐(S(O)(O)O-N(Alk)4 +)、酮(C(O))、乙酰丙酮(C(O)-CH2-C(O))。
11.如权利要求1所述的共聚物,其中,所述烯丙氧基共聚单体具有式(M6):
其中:R1、R2和R3是氢或卤素(F、Cl、Br、I);
其中:R4是CH2或CF2;
其中:R5是C1至C16直链、支化、芳基或环烷基基团,C1至C16氟化直链、支化、芳基或环烷基基团,六氟环氧丙烷低聚物或四氟环氧乙烷低聚物;
其中:R6是羧酸(C(O)OH)、碱金属羧酸盐(COO-M+)、羧酸铵盐(COO-NH4 +)、羧酸烷基铵盐(COO-N(Alk)4 +)、醇(OH)、酰胺(C(O)NH2)、二烷基酰胺(C(O)NAlk2)、磺酸(S(O)(O)OH)、碱金属磺酸盐(S(O)(O)O-M+)、磺酸铵盐(S(O)(O)O-NH4 +)、磺酸烷基铵盐(S(O)(O)O-N(Alk)4 +)、酮(C(O))或乙酰丙酮(C(O)-CH2-C(O)),或膦酸酯(P(O)(OH)2),碱金属或铵的膦酸盐。
12.如权利要求1所述的共聚物,其中,所述多亲水官能共聚单体选自:衣康酸、马来酸、戊烯二酸、富马酸及它们的酸酐,碱金属盐、铵盐及单烷基铵盐、二烷基铵盐、三烷基铵盐和四烷基铵盐。
13.一种包含在溶剂中的权利要求1-12中任一项所述的氟化共聚物的制剂。
14.如权利要求13所述的制剂,其中,所述溶剂选自下组:N-甲基吡咯烷酮(NMP)、二甲基亚砜(DMSO)、N,N-二甲基甲酰胺(DMF)、亚磷酸三乙酯(TEP)、丙酮、四氢呋喃、甲基乙基酮(MEK)、甲基异丁基酮(MiBK)、乙酸乙酯(EA)、乙酸丁酯(BA)、碳酸二甲酯(DMC)、碳酸二乙酯(DEC)和碳酸乙基甲基酯(EMC)。
15.如权利要求13所述的制剂,所述制剂还包含悬浮在所述溶剂中的金属颗粒和活性碳,所述金属颗粒选自下组:磷酸铁锂(LFP)、锂镍锰钴氧化物(NMC)、锂锰钴氧化物、锂镍钴铝氧化物、锂锰氧化物(LMO)和锂镍锰(LNMO)。
16.一种用于在水性反应介质中制备权利要求1所述的氟化共聚物的方法,所述方法包括如下步骤:
a)形成水性乳液,所述水性乳液包含:至少一种引发剂、稳定剂、至少一种氟化乙烯类单体和选自下组的至少一种亲水性单体:乙烯基烷基酸、乙烯基膦酸酯、官能丙烯酰胺、碳酸酯、乙烯基醚、烷氧基化合物和双亲水基团单体;
b)在加热和超大气压下,在搅拌下引发所述至少一种氟化乙烯类单体与所述亲水性单体的共聚。
17.如权利要求16所述的方法,其中,水性介质另外包含至少一种缓冲剂。
18.如权利要求16至17中任一项所述的方法,其中,聚合在约70℃至约125℃的温度下进行。
19.如权利要求16至18中任一项所述的方法,其中,聚合在约2750kPa至约6900kPa的聚合压力下进行。
20.如权利要求16至19中任一项所述的方法,其中,引发剂是过硫酸盐或有机过氧化物。
21.一种包含权利要求11至13中任一项所述制剂的制品,其中,所述制品是电池电极膜,尤其是用于锂离子电池的正电极。
22.一种电池,其包含权利要求1至12中任一项所述的氟化共聚物。
23.一种经涂覆的基材,其上以水中的乳液形式或以溶剂溶液形式施加有权利要求1至12中任一项所述的共聚物。
24.一种多孔薄膜,其包括以水中的乳液形式或以溶剂溶液形式施加的权利要求1至12中任一项所述的共聚物。
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EP (1) | EP3774713A4 (zh) |
JP (1) | JP2021521297A (zh) |
KR (1) | KR20200143717A (zh) |
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CN114752025A (zh) * | 2022-05-24 | 2022-07-15 | 阳光储能技术有限公司 | 改性聚偏氟乙烯及其制备方法、隔膜及锂离子电池 |
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KR20230017792A (ko) * | 2020-06-02 | 2023-02-06 | 알케마 인코포레이티드 | 개선된 특성들을 갖는 배터리 전극들의 제조 방법 |
CN114292560B (zh) * | 2022-01-12 | 2024-01-05 | 上海船舶工艺研究所(中国船舶集团有限公司第十一研究所) | 一种高耐久性水性氟碳漆及其制备方法 |
CN114832634A (zh) * | 2022-04-25 | 2022-08-02 | 自然资源部天津海水淡化与综合利用研究所 | 一种聚四氟乙烯膜亲水改性剂及其制备方法 |
FR3137846A1 (fr) | 2022-07-12 | 2024-01-19 | Arkema France | Procédé de purification du chlorotrifluoroéthylène |
FR3137913A1 (fr) | 2022-07-12 | 2024-01-19 | Arkema France | Procédé de séparation d’hydrofluorooléfines |
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JP2021521297A (ja) | 2021-08-26 |
FR3079834A1 (fr) | 2019-10-11 |
WO2019199753A1 (en) | 2019-10-17 |
EP3774713A4 (en) | 2022-06-22 |
US20210163647A1 (en) | 2021-06-03 |
KR20200143717A (ko) | 2020-12-24 |
EP3774713A1 (en) | 2021-02-17 |
FR3079834B1 (fr) | 2021-09-10 |
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