CN101273069A - 制备含氟聚合物的方法 - Google Patents
制备含氟聚合物的方法 Download PDFInfo
- Publication number
- CN101273069A CN101273069A CNA2006800358015A CN200680035801A CN101273069A CN 101273069 A CN101273069 A CN 101273069A CN A2006800358015 A CNA2006800358015 A CN A2006800358015A CN 200680035801 A CN200680035801 A CN 200680035801A CN 101273069 A CN101273069 A CN 101273069A
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- CN
- China
- Prior art keywords
- fluoropolymer
- fluorinated
- vdf
- exchange resin
- polymerization
- 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 claims abstract description 59
- 239000004811 fluoropolymer Substances 0.000 title claims abstract description 59
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- 239000006185 dispersion Substances 0.000 claims abstract description 52
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 28
- 239000004094 surface-active agent Substances 0.000 claims abstract description 22
- 239000002351 wastewater Substances 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 12
- 150000001336 alkenes Chemical class 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 33
- 239000011347 resin Substances 0.000 claims description 23
- 229920005989 resin Polymers 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract description 22
- 230000000379 polymerizing effect Effects 0.000 abstract description 2
- 239000003957 anion exchange resin Substances 0.000 abstract 3
- 239000000178 monomer Substances 0.000 description 34
- 150000001875 compounds Chemical class 0.000 description 27
- 150000003384 small molecules Chemical class 0.000 description 27
- 238000005342 ion exchange Methods 0.000 description 25
- 238000006243 chemical reaction Methods 0.000 description 19
- 239000007788 liquid Substances 0.000 description 19
- -1 ethylene-tetrafluoroethylene Chemical group 0.000 description 18
- 239000003999 initiator Substances 0.000 description 17
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 16
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 13
- 150000003839 salts Chemical class 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- 239000012986 chain transfer agent Substances 0.000 description 11
- 239000013543 active substance Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 9
- 229910052731 fluorine Inorganic materials 0.000 description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- 230000002829 reductive effect Effects 0.000 description 8
- 125000003010 ionic group Chemical group 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 239000003456 ion exchange resin Substances 0.000 description 6
- 229920003303 ion-exchange polymer Polymers 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 229910052794 bromium Inorganic materials 0.000 description 5
- 238000000119 electrospray ionisation mass spectrum Methods 0.000 description 5
- 238000010556 emulsion polymerization method Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 229910052740 iodine Inorganic materials 0.000 description 5
- 150000002500 ions Chemical group 0.000 description 5
- 239000004816 latex Substances 0.000 description 5
- 229920000126 latex Polymers 0.000 description 5
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000000443 aerosol Substances 0.000 description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 4
- 235000019395 ammonium persulphate Nutrition 0.000 description 4
- 238000005349 anion exchange Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 238000010557 suspension polymerization reaction Methods 0.000 description 4
- RRZIJNVZMJUGTK-UHFFFAOYSA-N 1,1,2-trifluoro-2-(1,2,2-trifluoroethenoxy)ethene Chemical compound FC(F)=C(F)OC(F)=C(F)F RRZIJNVZMJUGTK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000001118 alkylidene group Chemical group 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 3
- 238000002296 dynamic light scattering Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229920001973 fluoroelastomer Polymers 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 150000001261 hydroxy acids Chemical group 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 150000004965 peroxy acids Chemical class 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- FYJQJMIEZVMYSD-UHFFFAOYSA-N perfluoro-2-butyltetrahydrofuran Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C1(F)OC(F)(F)C(F)(F)C1(F)F FYJQJMIEZVMYSD-UHFFFAOYSA-N 0.000 description 2
- RVZRBWKZFJCCIB-UHFFFAOYSA-N perfluorotributylamine Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)N(C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F RVZRBWKZFJCCIB-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- XXQBEVHPUKOQEO-UHFFFAOYSA-N potassium superoxide Chemical compound [K+].[K+].[O-][O-] XXQBEVHPUKOQEO-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 125000005270 trialkylamine group Chemical group 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- USPWUOFNOTUBAD-UHFFFAOYSA-N 1,2,3,4,5-pentafluoro-6-(trifluoromethyl)benzene Chemical compound FC1=C(F)C(F)=C(C(F)(F)F)C(F)=C1F USPWUOFNOTUBAD-UHFFFAOYSA-N 0.000 description 1
- DAVCAHWKKDIRLY-UHFFFAOYSA-N 1-ethenoxy-1,1,2,2,3,3,3-heptafluoropropane Chemical compound FC(F)(F)C(F)(F)C(F)(F)OC=C DAVCAHWKKDIRLY-UHFFFAOYSA-N 0.000 description 1
- ZLFSOCVJMGQPTE-UHFFFAOYSA-N 1-ethenoxy-1,1,2,2-tetrafluoro-2-(trifluoromethoxy)ethane Chemical compound FC(F)(F)OC(F)(F)C(F)(F)OC=C ZLFSOCVJMGQPTE-UHFFFAOYSA-N 0.000 description 1
- YKWORVRLPTZONH-UHFFFAOYSA-N 1-ethenoxy-1,1,2,3,3,3-hexafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)propane Chemical compound FC(F)(F)C(F)(F)C(F)(F)OC(F)(C(F)(F)F)C(F)(F)OC=C YKWORVRLPTZONH-UHFFFAOYSA-N 0.000 description 1
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 1
- JMGNVALALWCTLC-UHFFFAOYSA-N 1-fluoro-2-(2-fluoroethenoxy)ethene Chemical compound FC=COC=CF JMGNVALALWCTLC-UHFFFAOYSA-N 0.000 description 1
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- QZGNGBWAMYFUST-UHFFFAOYSA-N 2-bromo-1,1-difluoroethene Chemical group FC(F)=CBr QZGNGBWAMYFUST-UHFFFAOYSA-N 0.000 description 1
- XYFRHHAYSXIKGH-UHFFFAOYSA-N 3-(5-methoxy-2-methoxycarbonyl-1h-indol-3-yl)prop-2-enoic acid Chemical compound C1=C(OC)C=C2C(C=CC(O)=O)=C(C(=O)OC)NC2=C1 XYFRHHAYSXIKGH-UHFFFAOYSA-N 0.000 description 1
- GVCWGFZDSIWLMO-UHFFFAOYSA-N 4-bromo-3,3,4,4-tetrafluorobut-1-ene Chemical compound FC(F)(Br)C(F)(F)C=C GVCWGFZDSIWLMO-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 208000006558 Dental Calculus Diseases 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 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
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- ASPXBYAQZVXSNS-UHFFFAOYSA-N azane;sulfurous acid;hydrate Chemical compound N.N.O.OS(O)=O ASPXBYAQZVXSNS-UHFFFAOYSA-N 0.000 description 1
- ZJRXSAYFZMGQFP-UHFFFAOYSA-N barium peroxide Chemical compound [Ba+2].[O-][O-] ZJRXSAYFZMGQFP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 238000006115 defluorination reaction Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000012470 diluted sample Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- BEPAFCGSDWSTEL-UHFFFAOYSA-N dimethyl malonate Chemical compound COC(=O)CC(=O)OC BEPAFCGSDWSTEL-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- RMGVZKRVHHSUIM-UHFFFAOYSA-L dithionate(2-) Chemical compound [O-]S(=O)(=O)S([O-])(=O)=O RMGVZKRVHHSUIM-UHFFFAOYSA-L 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
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Abstract
本发明提供了一种制备含氟聚合物的方法,所述方法包括:(i)通过在水乳液聚合反应中使一种或多种氟化烯烃以及可任选的一种或多种氟化或非氟化的共聚单体聚合来提供含氟聚合物颗粒的水分散体,其中在不存在氟化表面活性剂的情况下引发所述聚合反应,并且其中在聚合反应期间不加入氟化表面活性剂;(ii)从所述水分散体中回收所述含氟聚合物,由此获得所述含氟聚合物和废水;以及(iii)使所述废水与阴离子交换树脂接触;或者作为步骤(ii)和(iii)的另外一种选择方式,使所述水分散体与阴离子交换树脂接触,随后从所述水分散体中分离出所述阴离子交换树脂。
Description
相关专利申请的交叉引用
本专利申请要求提交于2005年9月27日的英国专利申请No.GB0519613.4的优先权,所述文献的全文以引用方式并入本文中。
本发明涉及氟化烯烃的水乳液聚合反应以制造含氟聚合物。
含氟聚合物(即具有氟化主链的聚合物)已长期为人们所知,并且由于其具有若干可取的特性(如耐热性、耐化学品性、耐侯性、紫外稳定性等)而已被用于多种应用中。例如,多种含氟聚合物描述于John Scheirs编辑的“Modern Fluoropolymers”(Wiley Science,1997)中。通常已知的或商业采用的含氟聚合物包括聚四氟乙烯(PTFE)、四氟乙烯(TFE)与六氟丙烯(HFP)的共聚物(FEP聚合物)、全氟烷氧基共聚物(PFA)、乙烯-四氟乙烯(ETFE)共聚物、四氟乙烯、六氟丙烯与偏二氟乙烯的三元共聚物(THV)、以及聚偏二氟乙烯聚合物(PVDF)。商业采用的含氟聚合物还包括含氟弹性体和热塑性含氟聚合物。
已知有若干方法可用来制备含氟聚合物。上述方法包括:悬浮聚合法,如(例如)美国专利No.3,855,191、美国专利No.4,439,385和EP649863中所公开的那样;水乳液聚合法,如美国专利No.3,635,926和美国专利No.4,262,101中所公开的那样;溶液聚合法,如美国专利No.3,642,742、美国专利No.4,588,796和美国专利No.5,663,255中所公开的那样;使用超临界CO2的聚合法,如JP 46011031和EP 964009中所公开的那样;以及气相聚合法,如美国专利No.4,861,845中所公开的那样。
目前,最常用的聚合反应方法包括悬浮聚合法,尤其是水乳液聚合法。所述水乳液聚合法通常涉及在氟化表面活性剂的存在下进行的聚合反应,所述氟化表面活性剂一般用于稳定所生成的聚合物颗粒。所述悬浮聚合法通常不涉及使用表面活性剂、但会产生比水乳液聚合法的情况下明显更大的聚合物颗粒。因此,在悬浮聚合的情况下产生的聚合物颗粒会快速地沉淀出来,而对于乳液聚合反应中获得的分散体而言,通常可获得在较长一段时间内都良好的稳定性。
在氟化表面活性剂的存在下进行的水乳液聚合法是制造含氟聚合物的理想方法,这是因为它可以以高收率以及对环境更友好的方式(例如,与在有机溶剂中实施的聚合方法相比)获得稳定的含氟聚合物颗粒分散体。一般使用全氟链烷酸或其盐作为表面活性剂来实施该乳液聚合法。通常使用这些表面活性剂是因为它们可提供多种可取的特性,诸如高速聚合、氟化烯烃与共聚单体的良好共聚性能、可使所得的分散体获得小的粒度、良好的聚合产率(即可制得大量的固体)、以及良好的分散稳定性等。然而,人们已提出有关这些表面活性剂对环境影响的问题,此外这些表面活性剂通常是昂贵的。因此,在本领域中已致力于在不使用氟化表面活性剂的情况下实施乳液聚合法。
美国专利No.5,453,477、WO 96/24622和WO 97/17381中描述了其中不使用表面活性剂的水乳液聚合法,通常用于制备三氟氯乙烯(CTFE)的均聚物和共聚物。例如,WO 97/17381公开了不存在表面活性剂的水乳液聚合法,其中使用由还原剂和氧化剂构成的自由基引发剂体系来引发聚合反应,由此在所述聚合过程中,以一次或多次投料的方式加入该引发剂体系。所称的无皂乳液聚合法进一步公开于WO 02/88206和WO 02/88203中。在后一个PCT专利申请中,教导人们使用二甲醚或甲基叔丁基醚来使得可从含氟聚合物中分离出的低分子量成分的生成减少到最低程度。WO02/88207教导了使用特定的链转移剂来使得水溶性氟化化合物的生成减少到最低程度的无皂乳液聚合法。无皂乳液聚合法进一步公开于RU 2158274中,以制备六氟丙烯与偏二氟乙烯的弹性体共聚物。
虽然本领域中公开的无皂乳液聚合法可解决与使用全氟链烷酸及其盐作为表面活性剂相关的环境问题,但已经发现,由无皂乳液聚合法所得的含氟聚合物分散体仍包含大量的低分子量氟化化合物,这对于环境仍然不利。此外,在使用含氟聚合物的某些应用中,存在上述低分子量化合物可能是不利的。
由于在氟化表面活性剂的存在下(尤其是在作为表面活性剂的全氟链烷酸及其盐的存在下)制得的含氟聚合物分散体所具有的有利特性,所以已经教导了在聚合反应后从废水流中回收氟化表面活性剂,并且将它们从所得分散体中除去,如WO 99/62830、WO 99/62858和WO 00/35971中所公开的那样。然后可将以上回收的氟化表面活性剂再次用于后续的聚合反应中。因此,回收解决了氟化表面活性剂的成本问题并且在一定程度上解决了环境问题。所述回收方法的缺点在于,它需要加入非离子表面活性剂以避免阴离子交换树脂阻塞。这些非离子表面活性剂的使用增加了回收方法的成本。此外,在某些应用中,非离子表面活性剂的存在是不利的或不可接受的。
目前期望找到一种可供选用的含氟聚合物制备方法,所述方法无需加入氟化表面活性剂,尤其是作为表面活性剂的全氟链烷酸或其盐。此外,期望找到一种可获得对环境更加友好的产物的方法。此外,还期望找到一种简单、便捷且成本有效的方法。优选地是,由上述方法获得的含氟聚合物在它们的常规应用中具有等同或得到改善的特性。
根据本发明,提供一种制备含氟聚合物的方法,所述方法包括:
(i)通过在水乳液聚合反应中使一种或多种氟化烯烃以及可任选的一种或多种氟化或非氟化的共聚单体聚合来提供含氟聚合物颗粒的水分散体,其中在不存在氟化表面活性剂的情况下引发聚合反应,并且其中在聚合反应期间不加入氟化表面活性剂;
(ii)从水分散体中回收含氟聚合物,由此获得所述含氟聚合物和废水;
(iii)并且使所述废水与阴离子交换树脂接触;或
作为步骤(ii)和(iii)的另外一种选择方式,使所述水分散体与阴离子交换树脂接触,随后从所述水分散体中分离出所述阴离子交换树脂。
已经发现,可在不预先加入非离子表面活性剂的情况下,使在不加入氟化表面活性剂的条件下制得的含氟聚合物分散体经受阴离子交换树脂处理。因此,即使不存在非离子表面活性剂,阴离子交换树脂也不会发生阻塞。同样,由从分散体中凝聚含氟聚合物而产生的废水(该废水仍可包含少量的含氟聚合物颗粒)也可在不加入非离子表面活性剂的情况下经受阴离子交换树脂处理。此外,已经发现,阴离子交换树脂可高度有效地去除具有一个或多个离子端基的低分子量氟化化合物。因此,可获得更为环境友好、且可提供得到改善的特性的含氟聚合物。例如,当每单位质量的含氟聚合物产品中离子基团的量较大时,含氟聚合物的处理会受到不利影响和/或含氟聚合物可能不具有特定应用所期望的纯度。这在使用含氟聚合物来制备用于半导体应用或燃料管理系统中的含氟弹性体时尤其如此。
水乳液聚合
除了不含氟化表面活性剂以外,通常以公知的方式来实施水乳聚合法。反应釜通常为在聚合反应期间能够承受内部压力的可加压釜。通常,所述反应器包括使反应器内容物充分混合的机械搅拌器和热交换系统。
可将任何量的含氟单体加入到反应容器中。可分批地或以连续或半连续的方式加入单体。半连续是指在聚合过程中将多批单体加入到容器中。单体加入到容器中的独立速率取决于特定单体随时间延长而消耗的速率。优选地是,单体加入速率与单体消耗速率(即单体转化为聚合物的速率)相同。
向反应釜中加入水,其量不是关键性的。通常使用链转移剂,然而这并不是必需的。当使用链转移剂时,通常在引发聚合反应之前将链转移剂加入到反应容器中。还可以在聚合反应期间以连续或半连续的方式实施链转移剂的进一步加入。例如,通过首先在初始量的链转移剂存在下使单体聚合,然后在聚合过程中的后面时刻与附加单体一起加入另外的链转移剂,由此来便捷地制备具有双峰分子量分布的含氟聚合物。
根据本发明,可使用的链转移剂包括:醚,诸如二甲醚和甲基叔丁基醚;烷烃,诸如甲烷、乙烷、丙烷、丁烷和戊烷;含溴或含碘的链转移剂;酯,诸如丙二酸二乙酯、丙二酸二甲酯和乙酸乙酯;醇,诸如甲醇和乙醇;酮,诸如丙酮;以及环醚,诸如四氢呋喃。
通常,在初始加入单体之后通过将引发剂或引发剂体系加入到水相中来引发聚合反应。例如,过氧化物可用作自由基引发剂。过氧化物引发剂的具体实例包括:过氧化氢、过氧化钠或过氧化钡、和二戊二酸过氧化物,以及水溶性过酸及其水溶性盐,例如铵盐、钠盐或钾盐。过酸的实例包括过乙酸。还可使用过酸的酯,其实例包括过氧乙酸叔丁酯和过氧化新戊酸叔丁酯。可用的另一类引发剂是水溶性偶氮化合物。适合用作引发剂的氧化还原体系包括(例如)过二硫酸盐与酸式亚硫酸盐的组合或过二硫酸盐与二亚硫酸盐的组合、硫代硫酸盐与过二硫酸盐的组合、或过二硫酸盐与肼的组合。其它可用的引发剂是过硫酸、高锰酸或锰酸的铵盐、碱金属盐或碱土金属盐,或锰酸。引发剂的用量通常在聚合混合物的总重量的0.03重量%至2重量%之间,优选在0.05重量%至1重量%之间。可在聚合反应起始时加入全部量的引发剂,或者在聚合反应期间以连续的方式将引发剂加入到聚合反应中,直至转化率为70%至80%为止。还可以在起始时加入部分引发剂,并且在聚合反应期间以单份或独立地追加多份的形式加入剩余的引发剂。还可优选地加入促进剂,例如铁、铜和银的水溶性盐。
在聚合反应引发阶段,通常将密封的反应釜及其内容物预热至反应温度。优选的聚合反应温度为30℃至80℃,并且压力通常介于4至30巴之间,具体地讲介于8至20巴之间。所述水乳液聚合反应体系还可包含助剂,诸如缓冲剂和络合物形成剂。
聚合反应结束时可获得的聚合物固体量按重量计通常介于10%和45%之间,优选介于20%和40%之间,并且所得含氟聚合物的平均粒度(体积平均直径)通常为至少200nm,一般为300nm或更大,并且典型的范围介于300至700nm之间。
根据本发明,可在不加入氟化表面活性剂的情况下实施水乳液聚合反应。也就是说,可在不含氟化表面活性剂的情况下引发或触发聚合反应,并且在聚合反应期间不加入氟化表面活性剂。根据一个实施例,按照美国专利No.5,453,477和WO 97/17381中所公开的方法实施水乳液聚合反应。根据WO 97/17381中所公开的无皂水乳液聚合法,可使用由还原剂和氧化剂构成的自由基引发剂体系来引发聚合反应,并且在聚合反应期间以一次或多次加料的方式加入引发剂体系。适用的氧化剂包括:过硫酸盐,诸如硫酸钾和硫酸铵;过氧化物,诸如过氧化氢、过氧化钾、过氧化铵、叔丁基过氧化氢、过氧化异丙苯和叔戊基过氧化氢;三乙酸锰、高锰酸钾、抗坏血酸;以及它们的混合物。适宜的还原剂包括亚硫酸钠,诸如亚硫酸氢钠、亚硫酸钠、焦亚硫酸钠、重亚硫酸钠、亚硫酸铵一水合物和硫代硫酸钠、羟胺、肼、亚铁离子、有机酸(诸如草酸和柠檬酸)、以及它们的混合物。
初始进料中所加入的氧化剂的量通常介于10和10000ppm之间。初始进料中的还原剂的量也通常介于10和10000ppm之间。在聚合反应期间,将至少另外一批氧化剂和还原剂追加到聚合体系中。可分批进行追加,或者连续进行追加。
根据另一个实施例,无皂水性聚合反应涉及氧化剂和还原剂的初始进料,以及在聚合反应期间还原剂或氧化剂的一批或多批追加进料,但不是两者都追加。本发明的该实施例所具有的优点在于,可以以简单且便捷的方式实施水性聚合反应,同时仍能以高速率和较好的收率获得稳定的聚合物分散体。
本发明的水乳液聚合法包括使至少一种氟化烯烃聚合。氟化烯烃的实例包括四氟乙烯、三氟氯乙烯、六氟丙烯和偏二氟乙烯。根据本发明的具体实施例,所述水乳液聚合法涉及使一种或多种氟化烯烃与可任选的一种或多种氟化或非氟化的共聚单体共聚。共聚单体的实例包括全氟烷基乙烯基单体、乙烯、丙烯、氟化烯丙基醚(具体地讲是全氟化烯丙基醚)、以及氟化乙烯基醚(具体地讲是全氟乙烯醚)。还可包括其它氟化或非氟化的单体。
根据本发明,可用于水乳液聚合反应中的氟化共聚单体的实例包括符合以下化学式的那些:
CF2=CF-O-Rf(I)
其中Rf代表可包含一个或多个氧原子的全氟化脂族基团。优选地是,全氟乙烯醚符合以下通式:
CF2=CFO(RfO)n(R’fO)mR“f (II)
其中Rf和R’f是具有2至6个碳原子的不同的直链或支链的全氟亚烷基,m和n独立地为0至10,并且R“f为具有1至6个碳原子的全氟烷基。符合以上化学式的全氟乙烯醚的实例包括全氟代-2-丙氧基丙基乙烯基醚(PPVE-2)、全氟代-3-甲氧基正丙基乙烯基醚、全氟代-2-甲氧基乙基乙烯基醚、全氟代甲基乙烯基醚(PMVE)、全氟代正丙基乙烯基醚(PPVE-1)和
CF3-(CF2)2-O-CF(CF3)-CF2-O-CF(CF3)-CF2-O-CF=CF2。
此外,所述聚合反应还涉及具有官能团(例如,能够参与过氧化物固化反应的基团)的共聚单体。上述官能团包括卤素(诸如Br或I)以及腈基。可列于此处的上述共聚单体的具体实例包括:
(a)具有以下化学式的溴代或碘代(全)氟烷基-(全)氟乙烯基醚:
Z-Rf-O-CX=CX2
其中每个X可相同或不同,并且代表H或F,Z为Br或I,Rf为C1-C12(全)氟亚烷基,其可任选地包含氯和/或醚氧原子;例如:BrCF2-O-CF=CF2、BrCF2CF2-O-CF=CF2、BrCF2CF2CF2-O-CF=CF2、CF3CFBrCF2-O-CF=CF2等;和
(b)包含溴或碘的氟化烯烃,诸如具有以下化学式的那些:
Z’-(Rf’)r-CX=CX2,
其中每个X独立地代表H或F,Z’为Br或I,Rf’为C1-C12全氟亚烷基,其可任选地包含氯原子,并且r为0或1;例如:三氟溴乙烯、4-溴代-全氟丁烯-1等;或溴代氟代烯烃,诸如1-溴代-2,2-二氟乙烯和4-溴代-3,3,4,4-四氟丁烯-1。
可用的含腈单体的实例包括符合以下一种化学式的那些:
CF2=CF-CF2-O-Rf-CN
CF2=CFO(CF2)LCN
CF2=CFO[CF2CF(CF3)O]g(CF2)vOCF(CF3)CN
CF2=CF[OCF2CF(CF3)]kO(CF2)uCN
其中L代表2至12的整数;g代表0至4的整数;k代表1或2;v代表0至6的整数;u代表1至6的整数,Rf为全氟亚烷基或二价全氟醚基团。含腈液态氟化单体的具体实例包括全氟代(8-氰基-5-甲基-3,6-二氧杂-1-辛烯)、CF2=CFO(CF2)5CN、和CF2=CFO(CF2)3OCF(CF3)CN。
根据一个特定实施例,可将氟化液体加入到聚合体系中。术语“液体”是指化合物在聚合过程中所用的温度和压力条件下应为液体。通常,所述氟化液体具有的沸点在大气压下为至少50℃,优选为至少80℃。具体地讲,氟化液体包括高度氟化的烃以及液态氟化单体。与本发明相关的术语“高度氟化”用于表示其中大部分且优选所有的氢原子已被氟原子取代的化合物,以及其中大部分氢原子已被氟原子取代并且其余的大部分或所有氢原子已被溴、氯或碘取代的化合物。通常,与本发明相关的高度氟化的化合物仅具有少数(例如1个或2个)被除氟之外的卤素取代的氢原子,并且/或者仅具有一或两个残余氢原子。当并非所有氢原子皆被氟或另一种卤素取代时(即所述化合物未被全氟化时),氢原子通常应位于化合物中的使得基本不会在其上发生链转移的某一位置处,即使得所述化合物起到聚合反应中的惰性物的作用,并且所述化合物不参与自由基聚合反应。其中所有氢均已被氟和/或其它卤原子取代的化合物在本文中被称为“全氟化”。
可用作氟化液体的液态氟化烃化合物通常包含3至25个碳原子,优选5至20个碳原子,并且可包含选自氧、硫或氮中的最多2个杂原子。高度氟化的烃化合物优选为全氟化烃化合物。适宜的全氟化烃包括:全氟化的直链、支链和/或环状的脂肪族饱和化合物,诸如全氟化的直链、支链或环状的烷烃;全氟化芳族化合物,诸如全氟化苯,或全氟化十四氢代菲。它还可以是全氟化烷基胺,诸如全氟化三烷基胺。它还可以是全氟化环状脂肪族化合物,诸如萘烷;并且优选环中包含氧或硫的杂环脂肪族化合物,诸如全氟代-2-丁基四氢呋喃。
全氟化烃的具体实例包括全氟化-2-丁基四氢呋喃、全氟化萘烷、全氟化甲基萘烷、全氟化甲基环己烷、全氟化(1,3-二甲基环己烷)、全氟化二甲基十氢化萘、全氟化芴、全氟化(十四氢代菲)、全氟化二十四碳烷、全氟化煤油、八氟萘烷、聚(三氟氯乙烯)的低聚物、全氟代(三烷基胺)(诸如全氟代(三丙胺)、全氟代(三丁胺)或全氟代(三戊胺))、和八氟甲苯、六氟苯、以及商业用的氟化溶剂,诸如均由3M Company生产的Fluorinert FC-75、FC-72、FC-84、FC-77、FC-40、FC-43、FC-70、FC5312、或FZ 348。适宜的高度氟化的惰性液态烃化合物是
C3F7-O-CF(CF3)-CF2-O-CHF-CF3。
所述氟化液体还可单独地包含液态氟化单体、或者以与上述液态氟化化合物组合的方式包含液态氟化单体。液态氟化单体的实例包括在聚合条件下为液体的那些,并且那些单体选自(全)氟化乙烯基醚、(全)氟化烯丙基醚和(全)氟化烷基乙烯基单体。
在一个具体的实施例中,将所述氟化液体以其气态形式(即以所谓的热气的形式)加入到聚合反应釜中。作为另外一种选择,可以通过将氟化液体供入适宜的喷嘴以形成气雾剂,从而以气雾剂的形式将其加入到聚合反应釜中。在一个具体的实施例中,所述喷嘴可被蒸汽加热。通常,以待制得的含氟聚合物的重量为基准,所述氟化液体的用量按重量计为0.001%至3%,优选0.005%至1.5%。
根据一个特定实施例,所制得的含氟聚合物为无定形含氟聚合物。上述聚合物在固化后形成含氟弹性体,其可在半导体工业或燃料管理系统中得到应用,其中它们可用于(例如)垫圈、燃料管和燃料箱中。
所述含氟聚合物(无论是无定形的还是半结晶的)可具有部分氟化或完全氟化的主链。当所述含氟聚合物具有部分氟化的主链时,其主链中包含的氟的量按重量计通常为至少20%,例如按重量计为至少30%,并且按重量计通常为至少50%。
低分子量氟化化合物的去除或回收
已经发现,如上所述制得的含氟聚合物分散体包含具有阴离子端基的低分子量氟化化合物。上述阴离子端基的实例包括羧酸基团、磺酸基团和硫酸基团,这些酸的盐也包括在内。这些低分子量氟化化合物的分子量和含量通常随聚合反应条件的变化而变化。从环境观点来看,最值得关注的是被氟化的、具有一个或多个离子基团、并且分子量为1000g/mol或更低、特别是为900g/mol或更低的那些化合物。已经发现,分子量为最多约1000g/mol(例如最多约900或800g/mol)的低分子量氟化化合物可有效且容易地用阴离子交换树脂回收。
本领域的技术人员应该理解,低分子量氟化化合物的结构取决于被聚合的单体、聚合反应条件以及具体的引发剂体系和/或所用的链转移剂。一般来讲,在上述聚合反应条件下,所形成的低分子量氟化化合物将是具有一个或两个离子基团的化合物。通常,上述离子基团包括羧酸基团、磺酸基团、硫酸基团、以及上述酸的盐。所述低分子量氟化化合物通常还包含由参与聚合反应的单体衍生的单元。上述单元的多种组合可存在于所述低分子量氟化化合物中。例如,对TFE、HFP和VDF的共聚而言,低分子量氟化化合物的混合物可由以下通式来表示:
G-(tfe)a(hfp)b(vdf)c-Z
其中G和Z代表端基,其可包含如上所述的离子基团,tfe、hfp、vdf各自代表由单体TFE、HFP和VDF衍生的单元,a为0至10,b为0至8,c为0至15(例如0至12)并且a+b+c之和介于1至15之间,例如1至12之间。在一个具体的实施例中,G和Z独立地代表Y-(CX2)n-,其中Y代表氢原子、羧酸基团、磺酸基团或硫酸基团、或上述酸的盐,每个X独立地代表H、F或CF3,并且n为0或1,条件是G和Z中至少有一个代表其中Y不同于氢原子的基团。
根据一个回收低分子量氟化化合物的实施例,可以将所述分散体凝聚,并且可以将所述含氟聚合物从其中分离出来。例如,通过加入盐(诸如氯化镁或氯化铝),通过加入酸(诸如HCl或草酸),通过加入有机溶剂(诸如C1-C4链烷醇,如甲醇)或EP 1395634中公开的酮,通过冷冻凝聚或通过如(例如)EP 1268573中所述的高剪切凝聚的方法,可从所述分散体中凝聚出所述含氟聚合物。
凝聚后,沉淀出的聚合物可通过过滤分离出来。通常,可用水和/或水/溶剂混合物来反复洗涤和漂洗分离出的含氟聚合物,以从所述聚合物中除去不需要的物质。
在含氟聚合物的凝聚以及可任选的洗涤操作之后,残余的废水包含低分子量氟化化合物,以及在含氟聚合物凝聚和分离后残余的微量或少量的含氟聚合物颗粒。现已发现,与现有技术中的教导不同,所述废水可在不加入或不含非离子表面活性剂的情况下与阴离子交换树脂接触。不希望受到任何理论的束缚,据信不需要所述非离子表面活性剂是因为:与在氟化表面活性剂(诸如全氟链烷酸及其盐)存在的情况下实施的聚合反应相比,通常无皂乳液聚合反应可获得更大的粒度。另一个起作用的因素是,所述颗粒的表面通常在离子交换后仍具有较大量的离子基团。
优选地是,在弱酸性、中性或碱性条件下实施阴离子交换法。离子交换树脂可以为OH-形式,然而也可使用氟离子、氯离子或硫酸根离子这样的阴离子。离子交换树脂的具体碱度不是非常关键的。强碱性树脂由于具有较高的效率而为优选的。可以通过将废水输送通过包含离子交换树脂的柱子来实施述方法,或作为另外一种选择,可将废水与离子交换树脂搅拌,并且其后通过过滤分离出阴离子交换树脂。随后,可通过洗脱吸附后的树脂,而从阴离子交换树脂中回收低分子量的氟化化合物。适用于洗脱阴离子交换树脂的混合物是氯化铵、甲醇和水的混合物。作为另外一种选择,还可在有机溶剂(例如甲醇)的存在下,使用强酸(例如H2SO4)从离子交换树脂中回收低分子量的氟化化合物;此方法的有益效果在于,所得混合物可用于将包含(例如)COO-的物质转变成相应的酯,或将O-SO3 --物质转变成包含OH-的衍生物。如此回收的氟化化合物自身可被用作(通常在纯化以及可任选的衍生化之后)氟化单体的水乳液聚合反应中的乳化剂组合物。此外,所回收的氟化化合物还可用作(例如)氟化单体合成中的反应物。
由于在与阴离子交换树脂接触之前,无需将非离子表面活性剂加入到废水中,因此本发明方法所提供的优点在于无需进行进一步的、用于从其中去除非离子表面活性剂的废水处理。因此,所述方法在经济和生态方面均具有吸引力。
在根据本发明的一个可供选择的实施例中,使所述含氟聚合物分散体与阴离子交换树脂接触。含氟聚合物分散体的处理条件基本上与上述处理废水的那些条件相同,并且可使用类似的阴离子交换树脂。与上述的废水处理相类似,可以通过引导分散体通过含有阴离子交换树脂的柱子的方法,或通过将阴离子交换树脂与分散体搅拌、随后进行后续过滤步骤的方法,来处理所述分散体。同样,在用阴离子交换树脂处理分散体的情况下,已发现无需存在非离子表面活性剂,从而避免分散体凝聚和阴离子交换树脂被阻塞。
此外,此实施例所提供的优点在于,所获得的分散体基本上不含分子量为1000g/mol或更低、且具有一个或多个离子基团的氟化化合物。基本上不含是指具有所述分子量的这些氟化化合物的总量为零,或者以固体量为基准,其含量不大于500ppm,通常含量小于100ppm。由此获得的分散体可容易地用于涂敷基底,诸如织物、金属表面、玻璃和塑料表面。
在另一个实施例中,可以将所得的分散体(已从其中除去具有离子基团、且分子量为1000g/mol的氟化化合物或在该分散体中已基本除去上述氟化化合物)凝聚,由此可以从所述分散体中回收含氟聚合物。与没有预先除去氟化化合物就将分散体进行凝聚的实施例相比,此实施例提供的优点在于可获得污染度更低的废水。具体地讲,分散体凝聚之后所获得的废水(其基本上不含低分子量的氟化化合物)无需进行去除低分子量氟化化合物和/或任何非离子表面活性剂的进一步处理。
以下实例进一步阐明了本发明,但无意于将本发明限制在其中。
实例
测试方法:
根据ISO/DIS 13321,使用Malvern Zetazizer 1000 HSA通过动态光散射进行胶乳粒度测定。在测量之前,用0.001mol/L KCl溶液稀释由聚合反应生成的聚合物胶乳,所有情况下的测量温度均为20℃。
使用Metrohm 712电导计,记录室温(23℃)下的水相电导率。
通过电喷雾离子化质谱(ESI-MS)实施水溶性低分子量氟化化合物的分子量表征。以5000rpm的速度将40mL聚合物分散体样品离心1小时。将透明的水相进行倾析,并且在无任何其它处理的情况下进行分析。根据它们的分子量分离不同的氟化化合物。使用配备Hamilton Gastight#101注射器(1000μl)的Harvard Apparatus11 Plus型泵进行样品注射。采用以下的条件:注射后在30℃下的流速为20μl/min,并且运行时间为10分钟。通过配备ESI-MS接口(在阴离子模式下运行)的Micromass Quattro 2进行对低分子量氟化化合物的质量检测。使用MassLynx 3.4版软件进行原始数据采集和分析。
在测定经过离子交换的样品和未经过交换的样品之前,用C8F17SO3 -Li+作为内标,将样品稀释至浓度为0.99μg/mL。将相应的波谱按未交换样品中的内标强度(5.12E+5 TIC)规一化,以补偿两次运行之间的敏感度波动。在假定MS响应在最多为600m/z的质量范围内为线性的条件下,来评定强度高于内标约2%(浓度>20ng/mL)的峰。当实验值与计算值的最大偏差低于+/-0.2m/z时,认为鉴别出了特定的低分子量氟化化合物。
实例1
向配备叶轮搅拌器的总容量为49L的聚合釜中加入29L去离子水。将该无氧釜加热至70℃,并且将搅拌系统设定在240rpm。向釜中加入6g二甲醚达到0.5巴的绝对压力,加入1040g六氟丙烯(HFP)达到8.0巴的绝对压力,并且加入450g偏二氟乙烯(VDF),达到15.5巴的绝对反应压力。通过160g 25%的APS(过二硫酸铵)水溶液引发聚合反应。当反应开始时,通过以0.653的HFP(kg)/VDF(kg)进料比将HFP和VDF加入到气相中,来保持绝对反应压力为15.5巴。还保持反应温度为70℃。5h后完成8.17kg TFE的进料,关闭单体阀门,并且在10min内使单体反应到绝对压力降至10.6巴。将反应器放空,并用N2吹扫三个循环。
如此获得的42.6kg聚合物分散体具有33.0%的固体含量。根据动态光散射分析,胶乳粒径为460nm。为除去离子性低分子量氟化化合物,使用氢氧化钠将分散体调节至pH=7,并且用去离子水稀释至固体含量为20%。电导率为1400μS/cm。
使用市售可得的强碱性离子交换树脂IRA402Cl(容量1.3mol/l)来除去低分子量氟化化合物。用350mL阴离子交换树脂填充玻璃柱,并且用10个床体积(BV)的去离子水(1BV等于350mL)冲洗。然后使得自实例1的分散体自底至顶通过离子交换柱。流速为0.5至1BV/h。当10BV的分散体通过离子交换柱后,取样,并且用ESI-MS测定残余的低分子量氟化化合物的含量。没有观察到柱子堵塞,并且去除低分子量氟化化合物后的分散体固体含量和胶乳平均粒度没有改变。离子交换后,分散体的pH为pH=3。电导率为1920μS/cm。
以内标为基准,计算出离子交换前的低分子量氟化化合物的总量为约600μg/mL,离子交换后该总量小于60μg/mL。因此,所鉴别的低分子量氟化化合物的去除率为约90%。
在离子交换处理前/后的水相中,鉴别出有以下的低分子量氟化化合物:
结构归属(m/z实验值/计算值) | 离子交换前的信号强度[TIC] | 离子交换后的信号强度[TIC] | 强度减弱率[%] |
[H-(VDF)2-SO4]-(224.86/224.98) | 1.7·106 | 2.5·104 | 98.5 |
[H-(VDF)3-SO4]-(288.92/288.99) | 2.2·106 | 3.5·104 | 98.4 |
[H-(VDF)4-SO4]-(352.92/353.00) | 3.0·106 | 1.3·104 | 99.6 |
[H-(VDF)5-SO4]-(417.04/417.01) | 1.5·106 | 4.4·103 | 99.7 |
[H-(VDF)6-SO4]-(481.04/481.02) | 6.2·105 | 4.9·103 | 99.2 |
[H-(VDF)7-SO4]-(544.92/545.03) | 1.2·105 | 1.6·103 | 98.7 |
[H-(VDF)8-SO4]-(608.93/609.04) | 3.0·104 | 1.4·103 | 95.3 |
[H-(VDF)1-CH2COO]-(122.96/123.03) | 5.1·106 | 1.8·104 | 99.6 |
[H-C(CF3)F-COO]-(144.95/144.99) | 7.2·106 | 3.3·105 | 95.4 |
[H-(HFP)1-C(CF3)F-COO]-(295.03/294.98) | 3.3·105 | 6.1·103 | 98.2 |
[H-(VDF)2-(HFP)1-SO4]-(374.95/374.97) | 2.9·105 | 6.8·103 | 97.6 |
[H-(VDF)3-(HFP)1-SO4]-(439.00/438.99) | 1.7·105 | 1.1·104 | 93.5 |
[H-(VDF)4-(HFP)1-SO4]-(502.93/503.00) | 6.4·104 | 2.7·103 | 95.8 |
[H-(VDF)1-(HFP)2-SO4]-(460.93/460.95) | 5.0·105 | 1.3·104 | 97.4 |
H-(VDF)1-C(CF3)F-COO]-(208.93/209.00) | 7.2·105 | 6.4·104 | 91.1 |
H-(VDF)2-C(CF3)F-COO]-(272.91/273.02) | 5,8·105 | 3.9·104 | 93.3 |
[SO4-(VDF)2-SO4H]-(320.96/320.94) | 2.6·105 | 1.8·104 | 93.1 |
[SO4-(VDF)3-SO4H]-(384.82/384.95) | 1.7·105 | 2.1·104 | 87.6 |
[SO4-(VDF)4-SO4H]-(449.00/448.96) | 2.7·105 | 5.3·103 | 98.0 |
[SO4-(VDF)2-(HFP)1-SO4H]-(421.06/420.93) | 2.4·105 | 4.5·103 | 98.1 |
[SO4-(VDF)3-(HFP)1-SO4H]-(485.05/484.94) | 3.0·104 | 1.1·103 | 96.3 |
[SO4-(VDF)1-C(CF3)F-COOH]-(305.02/304.96) | 6.9·105 | 6.6·104 | 90.4 |
[SO4-(VDF)2-C(CF3)F-COOH]-(368.95/368.97) | 2.8·105 | 1.3·104 | 95.4 |
[SO4-(VDF)3-C(CF3)F-COOH]-(432.94/432.98) | 3.6·105 | 5.1·103 | 98.6 |
[OOCCH2-(VDF)1-CH2-COOH]-(180.94/181.03) | 1.9·106 | 6.0·104 | 96.8 |
[OOCCH2-(VDF)2-CH2-COOH]-(244.98/245.04) | 9.8·106 | 1.0·105 | 99.0 |
TIC=质量信号强度(总离子流)
实例2
向配备叶轮搅拌器的总体积为49L的聚合釜中加入29.0L去离子水。然后,将无氧釜加热至70℃,并且将搅拌系统设定在240rpm。向所述釜中加入54g 25%的氨水溶液、30g PPVE-2、1710g HFP以达到12.1巴的绝对压力,加入200g VDF达到15.0巴的绝对压力,加入220g TFE达到17.0巴的绝对反应压力。通过加入溶于120ml水中的40g过二硫酸铵(APS)引发聚合反应。反应开始时,通过以1.318的VDF(kg)/TFE(kg)进料比和1.135的HFP(kg)/TFE(kg)进料比将TFE、VDF、HFP和PPVE-2加入到气相中,来保持绝对反应压力为17.0巴。还保持反应温度为70℃。在1.5小时的持续时间内,另外加入25g热喷雾气雾剂形式的PPVE-2。在加入1.8kg TFE(对应于62分钟的聚合反应时间后达到50%的单体目标进料)后,将一份75g的二甲醚链转移剂加入到容器中,这导致单体消耗量急剧降低。使单体进料再维持285分钟的聚合反应时段,并且以热喷雾气雾剂的形式加入25g额外量的PPVE-2。在那一时段后,完成3.6kg TFE的单体进料。中断单体进料,并且关闭单体阀门。在30分钟内,使单体气相反应到容器压力降至12.2巴;然后将反应器放空,并用N2吹扫三个循环。
在反应器底部,回收如此获得的固体含量为33.4%的43.3kg聚合物分散体,并且根据动态光散射分析,该分散体由直径为540nm的胶乳颗粒组成。通过ESI-MS进一步分析此分散体。
按照实例1中所述的方法除去低分子量化合物,并进行表征。
计算出分散体水相中低分子量氟化化合物的总量为约1700μg/mL。离子交换后,其量降至100ppm。
可对以下的低分子量氟化化合物进行表征:
1)
结构归属(m/z实验值/计算值) | 离子交换前的信号强度[TIC] | 离子交换后的信号强度[TIC] | 强度减弱率[%] |
[H-(VDF)1-SO4]-(160.83/160.97) | 2·106 | 9·103 | 99 |
至 | |||
[H-(VDF)5-SO4]-(417.00/417.01) | 6·104 | 5·103 | 93 |
TIC=质量信号强度(总离子流)
2)
结构归属(m/z实验值/计算值) | 离子交换前的信号强度[TIC] | 离子交换后的信号强度[TIC] | 强度减弱率[%] |
[H-(TFE)1-CH2-COO]-(158.89/159.01) | 3·106 | 3·104 | 99 |
至 | |||
[H-(TFE)3-CF2-COO]-(394.94/394.98) | 1·105 | 3·103 | 98 |
3)
结构归属(m/z实验值/计算值) | 离子交换前的信号强度[TIC] | 离子交换后的信号强度[TIC] | 强度减弱率[%] |
[H-(VDF)1-(TFE)1-CH2-COO]-(222.87/223.02) | 2·106 | 2·104 | 99 |
[H-(TFE)1-(VDF)1-SO4]-(260.85/260.97) | 2·106 | 3·105 | 99 |
[H-(VDF)1-(TFE)2-CH2-COO]-(322.96/323.01) | 7·105 | 1·104 | 98 |
[H-(TFE)1-(VDF)2-SO4]-(325.02/324.98) | 2·106 | 2·104 | 99 |
4)
结构归属(m/z实验值/计算值) | 离子交换前的信号强度[TIC] | 离子交换后的信号强度[TIC] | 强度减弱率[%] |
[H-(HFP)1-(VDF)1-SO4]-(310.96/310.96) | 1·106 | 6·104 | 95 |
[H-(HFP)1-(VDF)2-SO4]-(374.95/374.97) | 7·105 | 3·103 | 99 |
5)
结构归属(m/z实验值/计算值) | 离子交换前的信号强度[TIC] | 离子交换后的信号强度[TIC] | 强度减弱率[%] |
[H-(VDF)1-(TFE)1-(HFP)1-CH2-COO]-(372.95/373.01) | 5·105 | 7·103 | 99 |
[H-(VDF)1-(TFE)1-(HFP)1-CF2-COO]-(408.94/408.99) | 3·105 | 1·104 | 96 |
[H-(VDF)1-(TFE)1-(HFP)1-SO4]-(410.82/410.96) | 1·105 | 1·104 | 99 |
6)
结构归属(m/z实验值/计算值) | 离子交换前的信号强度[TIC] | 离子交换后的信号强度[TIC] | 强度减弱率[%] |
[SO4-(VDF)1-C(CF3)F-COOH]-(305.02/304.96) | 7·105 | 7·104 | 90 |
至 | |||
[SO4-(VDF)3-C(CF3)F-COOH]-(432.94/432.98) | 4·105 | 5·103 | 99 |
[OOCCH2-(VDF)1-CH2-COOH]-(180.94/181.03) | 2·106 | 6·104 | 97 |
[OOCCH2-(VDF)2-CH2-COOH]-(244.98/245.04) | 10·106 | 1·105 | 99 |
7)
结构归属(m/z实验值/计算值) | 离子交换前的信号强度[TIC] | 离子交换后的信号强度[TIC] | 强度减弱率[%] |
1[H-C(CF3)F-COO]-(144.89/144.99) | 2·107 | 6·104 | 99 |
1其它可能的结构:HS2O5 -(计算值144.93),[O-(VDF)2-H]-(计算值145.03)
2其它可能的结构:[H-(TFE)2-CF2-COO]-(计算值294.98)
Claims (6)
1.一种制备含氟聚合物的方法,所述方法包括:
(i)通过在水乳液聚合反应中使一种或多种氟化烯烃以及可任选的一种或多种氟化或非氟化的共聚单体聚合来提供含氟聚合物颗粒的水分散体,其中在不存在氟化表面活性剂的情况下引发所述聚合反应,并且其中在聚合反应期间不加入氟化表面活性剂;
(ii)从所述水分散体中回收所述含氟聚合物,由此获得所述含氟聚合物和废水;
(iii)以及使所述废水与阴离子交换树脂接触;或
(iv)作为步骤(ii)和(iii)的另外一种选择方式,使所述水分散体与阴离子交换树脂接触,并且随后从所述水分散体中分离出所述阴离子交换树脂。
2.根据权利要求1所述的方法,其中所述含氟聚合物为无定形含氟聚合物。
3.根据权利要求1所述的方法,其中所述含氟聚合物颗粒具有300nm或更大的体积平均直径。
4.根据权利要求1所述的方法,其中所述含氟聚合物具有部分氟化的主链。
5.根据权利要求1所述的方法,其中所述水分散体和所述废水基本上不含非离子表面活性剂。
6.根据权利要求1所述的方法,其中所述水分散体中的固体量按重量计介于10%和40%之间。
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-
2006
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- 2006-09-26 CN CNA2006800358015A patent/CN101273069A/zh active Pending
- 2006-09-26 RU RU2008111363/04A patent/RU2008111363A/ru not_active Application Discontinuation
- 2006-09-26 WO PCT/US2006/037590 patent/WO2007038561A1/en active Application Filing
- 2006-09-26 EP EP06825150A patent/EP1928922A4/en not_active Withdrawn
- 2006-09-26 KR KR1020087007142A patent/KR20080046684A/ko not_active Application Discontinuation
Cited By (5)
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CN101648122B (zh) * | 2009-09-03 | 2012-05-02 | 中昊晨光化工研究院 | 一种含氟乳化剂的制备方法 |
CN109799126A (zh) * | 2014-07-25 | 2019-05-24 | 立佳有限公司 | 稀释生物样品成分的分析方法 |
CN110494516A (zh) * | 2017-04-11 | 2019-11-22 | 索尔维特殊聚合物意大利有限公司 | 用于制造氟聚合物的方法 |
CN110494516B (zh) * | 2017-04-11 | 2022-11-04 | 索尔维特殊聚合物意大利有限公司 | 用于制造氟聚合物的方法 |
CN113728015A (zh) * | 2019-04-26 | 2021-11-30 | 大金工业株式会社 | 氟聚合物水性分散液的制造方法和氟聚合物水性分散液 |
Also Published As
Publication number | Publication date |
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EP1928922A1 (en) | 2008-06-11 |
GB0519613D0 (en) | 2005-11-02 |
WO2007038561A1 (en) | 2007-04-05 |
EP1928922A4 (en) | 2009-06-03 |
RU2008111363A (ru) | 2009-11-10 |
US20070072985A1 (en) | 2007-03-29 |
KR20080046684A (ko) | 2008-05-27 |
GB2430437A (en) | 2007-03-28 |
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