JP2011510160A - フルオロポリマーの製造方法 - Google Patents
フルオロポリマーの製造方法 Download PDFInfo
- Publication number
- JP2011510160A JP2011510160A JP2010544389A JP2010544389A JP2011510160A JP 2011510160 A JP2011510160 A JP 2011510160A JP 2010544389 A JP2010544389 A JP 2010544389A JP 2010544389 A JP2010544389 A JP 2010544389A JP 2011510160 A JP2011510160 A JP 2011510160A
- Authority
- JP
- Japan
- Prior art keywords
- dispersant
- group
- fluoropolymer
- polymerization
- tetrafluoroethylene
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 229920002313 fluoropolymer Polymers 0.000 title claims description 37
- 239000004811 fluoropolymer Substances 0.000 title claims description 37
- 239000002270 dispersing agent Substances 0.000 claims abstract description 62
- 238000000034 method Methods 0.000 claims abstract description 52
- 239000010702 perfluoropolyether Substances 0.000 claims abstract description 34
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 12
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 11
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 125000004428 fluoroalkoxy group Chemical group 0.000 claims abstract description 7
- -1 hexafluoropropylene, chlorotrifluoroethylene, trifluoroethylene, hexafluoroisobutylene Chemical group 0.000 claims description 45
- 239000006185 dispersion Substances 0.000 claims description 34
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 34
- 229910019142 PO4 Inorganic materials 0.000 claims description 22
- 239000010452 phosphate Substances 0.000 claims description 21
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 21
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 21
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 11
- KHXKESCWFMPTFT-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-(1,2,2-trifluoroethenoxy)propane Chemical compound FC(F)=C(F)OC(F)(F)C(F)(F)C(F)(F)F KHXKESCWFMPTFT-UHFFFAOYSA-N 0.000 claims description 10
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 8
- 239000012736 aqueous medium Substances 0.000 claims description 5
- 150000007942 carboxylates Chemical class 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 3
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 claims description 3
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 claims description 3
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- JMGNVALALWCTLC-UHFFFAOYSA-N 1-fluoro-2-(2-fluoroethenoxy)ethene Chemical compound FC=COC=CF JMGNVALALWCTLC-UHFFFAOYSA-N 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- RFJVDJWCXSPUBY-UHFFFAOYSA-N 2-(difluoromethylidene)-4,4,5-trifluoro-5-(trifluoromethyl)-1,3-dioxolane Chemical compound FC(F)=C1OC(F)(F)C(F)(C(F)(F)F)O1 RFJVDJWCXSPUBY-UHFFFAOYSA-N 0.000 claims 1
- 150000001735 carboxylic acids Chemical group 0.000 claims 1
- 238000010556 emulsion polymerization method Methods 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 34
- 150000003839 salts Chemical class 0.000 abstract description 11
- 239000002253 acid Substances 0.000 abstract description 9
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 229920001973 fluoroelastomer Polymers 0.000 abstract description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 4
- 150000001768 cations Chemical class 0.000 abstract description 4
- 125000003709 fluoroalkyl group Chemical group 0.000 abstract description 3
- 150000002148 esters Chemical class 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 description 22
- 235000021317 phosphate Nutrition 0.000 description 21
- 239000000243 solution Substances 0.000 description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 18
- 229920001577 copolymer Polymers 0.000 description 18
- 229920000642 polymer Polymers 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- CSCPPACGZOOCGX-WFGJKAKNSA-N acetone d6 Chemical compound [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 13
- 239000002245 particle Substances 0.000 description 13
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 11
- WVPKAWVFTPWPDB-UHFFFAOYSA-M dichlorophosphinate Chemical compound [O-]P(Cl)(Cl)=O WVPKAWVFTPWPDB-UHFFFAOYSA-M 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 239000000155 melt Substances 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- 229920001519 homopolymer Polymers 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 125000000542 sulfonic acid group Chemical group 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000701 coagulant Substances 0.000 description 5
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 5
- 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 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- BLTXWCKMNMYXEA-UHFFFAOYSA-N 1,1,2-trifluoro-2-(trifluoromethoxy)ethene Chemical compound FC(F)=C(F)OC(F)(F)F BLTXWCKMNMYXEA-UHFFFAOYSA-N 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 3
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000012674 dispersion polymerization Methods 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- PGFXOWRDDHCDTE-UHFFFAOYSA-N hexafluoropropylene oxide Chemical class FC(F)(F)C1(F)OC1(F)F PGFXOWRDDHCDTE-UHFFFAOYSA-N 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- BYKNGMLDSIEFFG-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptan-1-ol Chemical compound OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)F BYKNGMLDSIEFFG-UHFFFAOYSA-N 0.000 description 2
- YSYRISKCBOPJRG-UHFFFAOYSA-N 4,5-difluoro-2,2-bis(trifluoromethyl)-1,3-dioxole Chemical compound FC1=C(F)OC(C(F)(F)F)(C(F)(F)F)O1 YSYRISKCBOPJRG-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910010082 LiAlH Inorganic materials 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000004530 micro-emulsion Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- PRAOHDPDNVDCIZ-UHFFFAOYSA-N phosphono 2,3,3,3-tetrafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)propanoate Chemical compound OP(O)(=O)OC(=O)C(F)(C(F)(F)F)OC(F)(F)C(F)(F)C(F)(F)F PRAOHDPDNVDCIZ-UHFFFAOYSA-N 0.000 description 2
- 229920002620 polyvinyl fluoride Polymers 0.000 description 2
- 239000000843 powder 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
- 239000012265 solid product Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- LLUADCONOGDDDD-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-(1,1,1,2-tetrafluoropropan-2-yloxy)propane Chemical compound FC(F)(F)C(F)(C)OC(F)(F)C(F)(F)C(F)(F)F LLUADCONOGDDDD-UHFFFAOYSA-N 0.000 description 1
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- BCLQALQSEBVVAD-UHFFFAOYSA-N 2,3,3,3-tetrafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)propanoyl fluoride Chemical compound FC(=O)C(F)(C(F)(F)F)OC(F)(F)C(F)(F)C(F)(F)F BCLQALQSEBVVAD-UHFFFAOYSA-N 0.000 description 1
- 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 1
- BQAFVKASCKYHFR-UHFFFAOYSA-N 4-(1-ethenoxypropan-2-yloxy)butanoic acid Chemical compound C=COCC(C)OCCCC(O)=O BQAFVKASCKYHFR-UHFFFAOYSA-N 0.000 description 1
- MKTOIPPVFPJEQO-UHFFFAOYSA-N 4-(3-carboxypropanoylperoxy)-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OOC(=O)CCC(O)=O MKTOIPPVFPJEQO-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920001780 ECTFE Polymers 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 235000017284 Pometia pinnata Nutrition 0.000 description 1
- 240000007653 Pometia tomentosa Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005192 alkyl ethylene group Chemical group 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 230000003698 anagen phase Effects 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- YYZXBILMVHNALP-UHFFFAOYSA-N azane;bis(1,1,2,2,3,3,4,4,5,5,8,8,8-tridecafluorooctyl) hydrogen phosphate Chemical class N.FC(F)(F)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)OP(=O)(O)OC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F YYZXBILMVHNALP-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- AQYSYJUIMQTRMV-UHFFFAOYSA-N hypofluorous acid Chemical compound FO AQYSYJUIMQTRMV-UHFFFAOYSA-N 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000004712 monophosphates Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- 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
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
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Abstract
Description
(−CFCF3−CF2−O−)n (XI)
(−CF2−CF2−CF2−O−)n (XII)
(−CF2CF2−O−)n−(CF2−O−)m (XIII)
(−CF2CFCF3−O−)n−(CF2−O−)m (XIV)
を有する。
コモノマー含有率(PPVE)は、米国特許第4,743,658号明細書、列5、行9〜23に開示されている方法に従ってFTIRによって測定した。
第1段階において、ホスホロジクロリデートをフルオロアルキルアルコールから製造した。冷却器および温度プローブを備えた反応フラスコへ、1H,1H,7H−パーフルオロヘプタン−1−オール(150グラム、0.45モル)および塩化カルシウム(10.2グラム、0.092モル)を加えた。内容物を窒素下に撹拌しながら、オキシ塩化リン(207.3グラム、1.35モル)をフラスコに加えた。内容物の温度は周囲温度から約15℃に低下した。反応混合物を次に110℃に6時間加熱した。
1H−NMR(400MHz,アセトン−d6):δ6.83(tt,J=51Hz,5.2Hz,1H),5.20(m,2H);
19F−NMR(376.89MHz,アセトン−d6):−119.4(m,2F),−121.7(m,2F),−122.4(m,2F),−122.9(m,2F),−129.1(m,2F),−138.0(dm,J=51Hz,2F)。
1H−NMR(400MHz,アセトン−d6):δ9.68(S,−OH’s),6.82(tt,J=51Hz,10.5Hz,1H),4.61(m,2H);
19F−NMR(376.89MHz,アセトン−d6):−120.5(m,2F),−122.1(m,2F),−123.1(m,2F),−123.3(m,2F),−129.5(m,2F),−138.4(dm,J=51Hz,2F)。
第1段階において、ホスホロジクロリデートをフルオロアルキルアルコールから製造した。冷却器および温度プローブを備えた反応フラスコに、1H,1H−パーフルオロヘキサン−1−オール(50グラム、0.166モル)および塩化カルシウム(2.9グラム、0.026モル)を加えた。フラスコ内容物を窒素下に撹拌しながら、オキシ塩化リン(207グラム、1.35モル)をこのアルコールにゆっくり加えた。反応混合物を次に110℃に5時間加熱した。
1H−NMR(400MHz,アセトン−d6):δ5.25(m,2H);
19F−NMR(376.89MHz,アセトン−d6):−80.7(m,3F),−119.3(m,2F),−122.4(m,4F),−125.7(m,2F)。
1H−NMR(400MHz,アセトン−d6):δ4.60(m,2H);
19F−NMR(376.89MHz,アセトン−d6):−82.2(m,3F),−121.5(m,2F),−123.9(m,2F),−124.0(m,2F),−127.3(m,2F)。
第1段階において、フルオロアルキルアルコールを2−トリフルオロメチル−3−オキサ−2,4,4,5,5,6,6,6−オクタフルオロヘキサノイルフルオリド(HFPOダイマー)から製造した。冷却器および温度プローブを備えた反応フラスコに、LiAlH4(13.5g、0.355モル)および500mlのエーテル溶媒を装入し、内容物を0℃に冷却した。(NaBH4をLiAlH4の代わりに用いてもよい)。HFPO−ダイマー(149.4g、0.45モル)をゆっくり加え、反応フラスコ内容物温度を外部冷却で10℃未満に制御した。添加が完了した後、反応混合物を5〜10℃で2〜3時間撹拌した。反応混合物を400mlの6N HCl/500mL氷水混合物へゆっくり移し、エーテル層を分離した。底部層を200mLのエーテルで(2回)抽出した。エーテル層を一緒にし、硫酸マグネシウム上で乾燥させ、次に蒸留してフルオロアルコール(2−トリフルオロメチル−3−オキサ−2,4,4,5,5,6,6,6−オクタフルオロヘキサン−1−オール)(HFPOダイマーアルコール)を透明な無色の液体として得た。Bp.112℃〜114℃。収量:127グラム(89%)。
1H−NMR(400MHz,アセトン−d6):δ 4.30(m);
19F−NMR(376.89MHz,アセトン−d6):−80.5〜−82.5(m,8F),−129.4(m,2F),−134.6(dm,1F)。
19F−NMR(376.89MHz,アセトン−d6):−80.5〜−82.5(m,8F),−129.4(m,2F),−135.1(dm,1F)。
1H−NMR(400MHz,アセトン−d6):δ 4.80(m);
19F−NMR(376.89MHz,アセトン−d6):−80.6〜−82.5(m,8F),−129.4(m,2F),−134.7(dm,1F)。
本実施例では、用いた分散剤は、以下の手順によって製造した、水溶液中の19重量%の部分中和した(すなわち1個のP−(OH)がP−(ONH4)で置き換えられた)2,2,3,3,4,4,5,5,6,6,7,7−ドデカフルオロ−1−ヘプタンリン酸エステル(DA7)であった。反応フラスコ中の25mLの蒸留H2Oに、pH約9.0まで2、3滴のNH4OHを加えた。上記の溶液を撹拌し、40℃で加熱しながら、数部分(合計6.84g)の2,2,3,3,4,4,5,5,6,6,7,7−ドデカフルオロ−1−ヘプタンリン酸エステル(上記の通り製造された)を加えた。2、3滴のNH4OHを再び加えてこれらの部分間でpHを約6に調整した。生じた水溶液は、幾分穏やかな泡形成と共に透明になった。それは、30mLの総容量および19重量%の部分中和分散剤(DA7)を有した。
分散剤の溶液が、以下の手順によって調製された、18.3重量%の分散剤DA7とカルボキシレート末端基を有する3.7重量%のパーフルオロポリエーテル(PFPE)(DuPontから入手可能なKrytox(登録商標)157 FSL)との組み合わせを含有したことを除いて実施例1の一般手順を繰り返した。反応フラスコ中の25mLの蒸留H2Oに、pH約9.0まで2、3滴のNH4OHを加えた。上記の溶液を撹拌し、40℃で加熱しながら、数部分(合計6.84g)の2,2,3,3,4,4,5,5,6,6,7,7−ドデカフルオロ−1−ヘプタンリン酸エステル(上記の通り製造された)を加えた。2、3滴のNH4OHを再び加えてこれらの部分間でpHを約6に調整した。生じた水溶液は、幾分穏やかな泡形成と共に透明になった。それは、30mLの総容量を有した。この溶液に次に、1.37gのKrytox(登録商標)157 FSLを加え、溶液を撹拌しながら50℃に加熱した。Krytox(登録商標)157 FSLは迅速に溶解して無色透明な溶液を与えた。
用いた分散剤(DA8)が、以下の手順によって製造された、水溶液中の19重量%の部分中和した2,2,3,3,4,4,5,5,6,6,6−ウンデカフルオロ−1−ヘキサリン酸エステル(すなわち1個のP−(OH)がP−(ONH4)で置き換えられた)であったことを除いて実施例1の一般手順を繰り返した。反応フラスコ中の25mLの蒸留H2Oに、pH約9.0まで2、3滴のNH4OHを加えた。上記の溶液を撹拌し、40℃で加熱しながら、数部分(合計6.84g)の2,2,3,3,4,4,5,5,6,6,6−ウンデカフルオロ−1−ヘキサリン酸エステル(上記の通り製造された)を加えた。2、3滴のNH4OHを再び加えてこれらの部分間でpHを約6に調整した。生じた水溶液は、幾分穏やかな泡形成と共に透明になった。それは、30mLの総容量を有した。
分散剤の溶液が、以下の手順によって調製された、18.3重量%の分散剤DA8と、カルボキシレート末端基を有する3.7重量%のパーフルオロポリエーテル(PFPE)(DuPontから入手可能なKrytox(登録商標)157 FSL)との組み合わせを含有したことを除いて実施例1の一般手順を繰り返した。反応フラスコ中の25mLの蒸留H2Oに、pH約9.0まで2、3滴のNH4OHを加えた。上記の溶液を撹拌し、40℃で加熱しながら、数部分(合計6.84g)の2,2,3,3,4,4,5,5,6,6,6−ウンデカフルオロ−1−ヘキサリン酸エステル(上記の通り製造された)を加えた。2、3滴のNH4OHを再び加えてこれらの部分間でpHを約6に調整した。生じた水溶液は、幾分穏やかな泡形成と共に透明になった。それは、30mLの総容量を有した。この溶液に次に、1.37gのKrytox(登録商標)157 FSLを加え、溶液を、Krytox(登録商標)157 FSLがゆっくり溶解して、無色透明な溶液をもたらす間室温で数時間撹拌した。
用いた分散剤(HFPO−DP)が、水溶液中の部分中和した2−トリフルオロメチル−3−オキサ−2,4,4,5,5,6,6,6−オクタフルオロヘキサノイルリン酸エステル(すなわち1個のP−(OH)がP−(ONH4)で置き換えられた)の7.8gの11重量%水溶液であったことを除いて実施例1の一般手順を繰り返した。またモノマーフィードは、60gのTFEが消費された後に止めた。
Claims (9)
- 開始剤および少なくとも1つの分散剤を含む水性媒体中で少なくとも1つのフルオロモノマーを重合させてフルオロポリマーの水性分散体を得る工程を含む、非弾性フルオロポリマーの製造のための乳化重合法であって、前記分散剤が式X−Rf−(CH2)n−O−P(O)(OM)2(式中、nは1または2であり、X=HまたはFであり、M=一価のカチオンであり、RfはC4〜C6のフルオロアルキルまたはフルオロアルコキシ基である)のフルオロアルキルリン酸エステルである乳化重合法。
- 前記分散剤が、式CF3CF2CF2OCF(CF3)CH2OPO(OM)2のものである請求項1に記載の方法。
- 前記分散剤が、CF3CF2CF2OCF(CF3)CH2OPO(OH)2およびCF3CF2CF2OCF(CF3)CH2OPO(OH)(ONH4)からなる群から選択される請求項2に記載の方法。
- 前記分散剤が、式H−(CF2)6−CH2−O−P(O)(OM)2のものである請求項1に記載の方法。
- 前記分散剤が、式F−(CF2)5−CH2−O−P(O)(OM)2のものである請求項1に記載の方法。
- 前記少なくとも1つのフルオロモノマーが、テトラフルオロエチレン、ヘキサフルオロプロピレン、クロロトリフルオロエチレン、トリフルオロエチレン、ヘキサフルオロイソブチレン、パーフルオロアルキルエチレン、フルオロビニルエーテル、フッ化ビニル、フッ化ビニリデン、パーフルオロ−2,2−ジメチル−1,3−ジオキソールおよびパーフルオロ−2−メチレン−4−メチル−1,3−ジオキソランからなる群から選択される請求項1に記載の方法。
- 前記フルオロポリマーが、ポリテトラフルオロエチレン、ポリクロロトリフルオロエチレンおよびポリフッ化ビニリデンからなる群から選択される請求項1に記載の方法。
- 前記フルオロポリマーが、i)テトラフルオロエチレンおよびヘキサフルオロプロピレン、ii)テトラフルオロエチレンおよびパーフルオロ(プロピルビニルエーテル)、iii)テトラフルオロエチレン、ヘキサフルオロプロピレンおよびフッ化ビニリデン、iv)エチレンおよびテトラフルオロエチレン、v)エチレンおよびクロロトリフルオロエチレン、ならびにvi)プロピレンおよびクロロトリフルオロエチレンからなる群から選択される共重合単位を含む請求項1に記載の方法。
- 第2の分散剤の導入をさらに含む請求項1に記載の乳化重合法であって、前記第2の分散剤がカルボン酸、カルボン酸塩、スルホン酸、スルホン酸塩、リン酸およびリン酸塩からなる群から選択される少なくとも1つの末端基を有するパーフルオロポリエーテルである乳化重合法。
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EP2231725B1 (en) | 2011-06-22 |
US20090186997A1 (en) | 2009-07-23 |
US7999049B2 (en) | 2011-08-16 |
ATE513859T1 (de) | 2011-07-15 |
US7989566B2 (en) | 2011-08-02 |
CN101925618A (zh) | 2010-12-22 |
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JP5368480B2 (ja) | 2013-12-18 |
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CN101925619A (zh) | 2010-12-22 |
WO2009094346A1 (en) | 2009-07-30 |
EP2235073A1 (en) | 2010-10-06 |
CN101925618B (zh) | 2013-05-08 |
EP2235073B1 (en) | 2011-06-08 |
ATE512166T1 (de) | 2011-06-15 |
WO2009094344A1 (en) | 2009-07-30 |
JP5368479B2 (ja) | 2013-12-18 |
JP2011510159A (ja) | 2011-03-31 |
CN104844737A (zh) | 2015-08-19 |
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