JP6135084B2 - Method for producing fluorine-containing block copolymer - Google Patents
Method for producing fluorine-containing block copolymer Download PDFInfo
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- JP6135084B2 JP6135084B2 JP2012219225A JP2012219225A JP6135084B2 JP 6135084 B2 JP6135084 B2 JP 6135084B2 JP 2012219225 A JP2012219225 A JP 2012219225A JP 2012219225 A JP2012219225 A JP 2012219225A JP 6135084 B2 JP6135084 B2 JP 6135084B2
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- tfe
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- polymerization
- block copolymer
- fluorine
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- 229920001400 block copolymer Polymers 0.000 title claims description 83
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims description 75
- 239000011737 fluorine Substances 0.000 title claims description 75
- 229910052731 fluorine Inorganic materials 0.000 title claims description 75
- 238000004519 manufacturing process Methods 0.000 title claims description 26
- 238000006116 polymerization reaction Methods 0.000 claims description 130
- 239000000178 monomer Substances 0.000 claims description 79
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 28
- 239000005977 Ethylene Substances 0.000 claims description 28
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 27
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 20
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 16
- 150000002497 iodine compounds Chemical class 0.000 claims description 13
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- 239000007870 radical polymerization initiator Substances 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 description 62
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 38
- 239000004816 latex Substances 0.000 description 30
- 229920000126 latex Polymers 0.000 description 30
- 239000007864 aqueous solution Substances 0.000 description 28
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 19
- 239000007789 gas Substances 0.000 description 18
- -1 polytetrafluoroethylene Polymers 0.000 description 15
- 239000003995 emulsifying agent Substances 0.000 description 14
- 230000008018 melting Effects 0.000 description 14
- 238000002844 melting Methods 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 230000004580 weight loss Effects 0.000 description 12
- 239000012736 aqueous medium Substances 0.000 description 11
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 10
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 10
- 238000009826 distribution Methods 0.000 description 10
- 230000008014 freezing Effects 0.000 description 10
- 238000007710 freezing Methods 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 238000010257 thawing Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 229920001973 fluoroelastomer Polymers 0.000 description 9
- 238000002834 transmittance Methods 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- JILAKKYYZPDQBE-UHFFFAOYSA-N 1,1,2,2,3,3,4,4-octafluoro-1,4-diiodobutane Chemical compound FC(F)(I)C(F)(F)C(F)(F)C(F)(F)I JILAKKYYZPDQBE-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 4
- 229920000428 triblock copolymer Polymers 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000002738 chelating agent Substances 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 3
- 238000010556 emulsion polymerization method Methods 0.000 description 3
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000003002 pH adjusting agent Substances 0.000 description 3
- 239000006179 pH buffering agent Substances 0.000 description 3
- 239000012966 redox initiator Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000001542 size-exclusion chromatography Methods 0.000 description 3
- SUTQSIHGGHVXFK-UHFFFAOYSA-N 1,2,2-trifluoroethenylbenzene Chemical compound FC(F)=C(F)C1=CC=CC=C1 SUTQSIHGGHVXFK-UHFFFAOYSA-N 0.000 description 2
- SKYXLDSRLNRAPS-UHFFFAOYSA-N 1,2,4-trifluoro-5-methoxybenzene Chemical compound COC1=CC(F)=C(F)C=C1F SKYXLDSRLNRAPS-UHFFFAOYSA-N 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 2
- OVBJJZOQPCKUOR-UHFFFAOYSA-L EDTA disodium salt dihydrate Chemical compound O.O.[Na+].[Na+].[O-]C(=O)C[NH+](CC([O-])=O)CC[NH+](CC([O-])=O)CC([O-])=O OVBJJZOQPCKUOR-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- QDGONURINHVBEW-UHFFFAOYSA-N dichlorodifluoroethylene Chemical group FC(F)=C(Cl)Cl QDGONURINHVBEW-UHFFFAOYSA-N 0.000 description 2
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 159000000014 iron salts Chemical class 0.000 description 2
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229920002223 polystyrene Polymers 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
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 2
- 229910000367 silver sulfate Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000010558 suspension polymerization method Methods 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- SRDQTCUHAMDAMG-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-hexadecafluoro-1,8-diiodooctane Chemical compound FC(F)(I)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)I SRDQTCUHAMDAMG-UHFFFAOYSA-N 0.000 description 1
- JOQDDLBOAIKFQX-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluoro-1,6-diiodohexane Chemical compound FC(F)(I)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)I JOQDDLBOAIKFQX-UHFFFAOYSA-N 0.000 description 1
- 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 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- AAAXMNYUNVCMCJ-UHFFFAOYSA-N 1,3-diiodopropane Chemical compound ICCCI AAAXMNYUNVCMCJ-UHFFFAOYSA-N 0.000 description 1
- ROUYUBHVBIKMQO-UHFFFAOYSA-N 1,4-diiodobutane Chemical compound ICCCCI ROUYUBHVBIKMQO-UHFFFAOYSA-N 0.000 description 1
- QLIMAARBRDAYGQ-UHFFFAOYSA-N 1,6-diiodohexane Chemical compound ICCCCCCI QLIMAARBRDAYGQ-UHFFFAOYSA-N 0.000 description 1
- KZDTZHQLABJVLE-UHFFFAOYSA-N 1,8-diiodooctane Chemical compound ICCCCCCCCI KZDTZHQLABJVLE-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- 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 1
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 1
- FPFSGDXIBUDDKZ-UHFFFAOYSA-N 3-decyl-2-hydroxycyclopent-2-en-1-one Chemical compound CCCCCCCCCCC1=C(O)C(=O)CC1 FPFSGDXIBUDDKZ-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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000012874 anionic emulsifier Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- YOALFLHFSFEMLP-UHFFFAOYSA-N azane;2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoic acid Chemical compound [NH4+].[O-]C(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YOALFLHFSFEMLP-UHFFFAOYSA-N 0.000 description 1
- OWCNWICUDXNCTI-UHFFFAOYSA-N azanium;2,2,3,3,4,4,5,5,6,6,6-undecafluorohexanoate Chemical compound N.OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F OWCNWICUDXNCTI-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- KDQPSPMLNJTZAL-UHFFFAOYSA-L disodium hydrogenphosphate dihydrate Chemical compound O.O.[Na+].[Na+].OP([O-])([O-])=O KDQPSPMLNJTZAL-UHFFFAOYSA-L 0.000 description 1
- DGLRDKLJZLEJCY-UHFFFAOYSA-L disodium hydrogenphosphate dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].OP([O-])([O-])=O DGLRDKLJZLEJCY-UHFFFAOYSA-L 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- SBGKURINHGJRFN-UHFFFAOYSA-M hydroxymethanesulfinate Chemical compound OCS([O-])=O SBGKURINHGJRFN-UHFFFAOYSA-M 0.000 description 1
- SBGKURINHGJRFN-UHFFFAOYSA-N hydroxymethanesulfinic acid Chemical class OCS(O)=O SBGKURINHGJRFN-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000006551 perfluoro alkylene group Chemical group 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- UCWBKJOCRGQBNW-UHFFFAOYSA-M sodium;hydroxymethanesulfinate;dihydrate Chemical compound O.O.[Na+].OCS([O-])=O UCWBKJOCRGQBNW-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
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- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
Description
本発明は、含フッ素ブロックコポリマーおよびその製造方法に関する。 The present invention relates to a fluorine-containing block copolymer and a method for producing the same.
フッ素樹脂は、耐熱性、耐候性、耐薬品性などに優れることから、一般の炭化水素系材料が使用できないような過酷な環境下にも用いられる。フッ素樹脂としては、例えば、ポリテトラフルオロエチレン（以下、ＰＴＦＥという場合がある。）、テトラフルオロエチレン／ヘキサフルオロプロピレン共重合体、テトラフルオロエチレン／パーフルオロ（アルキルビニルエーテル）共重合体、テトラフルオロエチレン／エチレン共重合体（以下、ＥＴＦＥという場合がある。）、ポリフッ化ビニリデン（以下、ＰＶｄＦという場合がある。）等がある。 Since the fluororesin is excellent in heat resistance, weather resistance, chemical resistance, etc., it is also used in a harsh environment where general hydrocarbon materials cannot be used. Examples of the fluororesin include polytetrafluoroethylene (hereinafter sometimes referred to as PTFE), tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer, tetrafluoroethylene. / Ethylene copolymer (hereinafter sometimes referred to as ETFE), polyvinylidene fluoride (hereinafter sometimes referred to as PVdF), and the like.
フッ素樹脂は、例えば、高温環境下に配線される電線の被覆材に用いられる。ところが、フッ素樹脂は柔軟性が不充分なため、フッ素樹脂を被覆材として用いた電線を自由に曲げて、自動車のエンジン周りなどの狭い空間に配線することは困難であった。
また、例えばＥＴＦＥは、その優れた耐候性、透明性から、ビニールハウス等の農業用フィルムとして使用されている。ところが、ＥＴＦＥは、一般の農業用ポリオレフィンフィルムに比較して硬く、展張が容易でない。
これらの点から、より軟質なフッ素樹脂が求められている。
A fluororesin is used for the coating | covering material of the electric wire wired in a high temperature environment, for example. However, since the fluororesin has insufficient flexibility, it has been difficult to bend an electric wire using the fluororesin as a coating material and to wire it in a narrow space such as around an automobile engine.
Further, for example, ETFE is used as an agricultural film such as a greenhouse because of its excellent weather resistance and transparency. However, ETFE is harder than general polyolefin film for agriculture and is not easy to stretch.
From these points, a softer fluororesin is required.
フッ素樹脂よりも軟質な材料として、フッ素ゴムセグメントとフッ素樹脂セグメントとを有するブロックコポリマーが検討されている。
例えば、特許文献１の実施例１２には、連鎖移動剤であるヨウ素化合物の存在下に、ヘキサフルオロプロピレン（以下、ＨＦＰという場合がある。）とフッ化ビニリデン（以下、ＶｄＦという場合がある。）とを共重合させて、フッ素ゴムセグメントを形成した後、さらにテトラフルオロエチレン（以下、ＴＦＥという場合がある。）とエチレン（以下、Ｅという場合がある。）とを共重合させてフッ素樹脂セグメントを形成することにより、フッ素ゴムセグメントとフッ素樹脂セグメントとを有するブロックコポリマーを得ることが記載されている。
As a softer material than a fluororesin, a block copolymer having a fluororubber segment and a fluororesin segment has been studied.
For example, in Example 12 of Patent Document 1, hexafluoropropylene (hereinafter sometimes referred to as HFP) and vinylidene fluoride (hereinafter referred to as VdF) in the presence of an iodine compound that is a chain transfer agent. ) To form a fluororubber segment, and then tetrafluoroethylene (hereinafter sometimes referred to as TFE) and ethylene (hereinafter sometimes referred to as E) are further copolymerized to form a fluororesin. It is described that a block copolymer having a fluororubber segment and a fluororesin segment is obtained by forming the segment.
しかしながら、該ブロックコポリマーは、フッ素ゴムセグメントがＨＦＰ／ＶｄＦセグメントであり、ＶｄＦに基く単位を有するため、耐薬品性が不充分である。耐薬品性を向上させるためには、フッ素ゴムセグメントとして、ＨＦＰ／ＶｄＦセグメントに代えてＴＦＥ／プロピレンセグメントを採用することが考えられる。ところが、特許文献１に記載の方法で、フッ素ゴムセグメントとしてＴＦＥ／プロピレンセグメントを有するブロックコポリマーを製造した場合、該ブロックコポリマーは機械物性が不充分であった。以下、プロピレンのことをＰという場合がある。 However, the block copolymer has insufficient chemical resistance because the fluororubber segment is an HFP / VdF segment and has units based on VdF. In order to improve the chemical resistance, it is conceivable to adopt a TFE / propylene segment as the fluororubber segment instead of the HFP / VdF segment. However, when a block copolymer having a TFE / propylene segment as a fluororubber segment is produced by the method described in Patent Document 1, the block copolymer has insufficient mechanical properties. Hereinafter, propylene may be referred to as P.
本発明の目的は、フッ素ゴムセグメントとしてＴＦＥ／Ｐ系セグメントを有し、フッ素樹脂セグメントとしてＴＦＥ／Ｅ系セグメントを有し、軟質性、耐熱性、耐薬品性に加えて、機械物性、光透過性などの物性に優れた含フッ素ブロックコポリマーの製造方法を提供することである。 The object of the present invention is to have a TFE / P segment as a fluororubber segment and a TFE / E segment as a fluororesin segment. In addition to softness, heat resistance and chemical resistance, mechanical properties and light transmission It is to provide a method for producing a fluorine-containing block copolymer having excellent physical properties such as properties.
本発明は、以下の構成を有する。
［１］ラジカル重合開始剤と、一般式ＲＩ２（式中、Ｒは炭素数３以上のアルキレン基またはフルオロアルキレン基である。）で表されるヨウ素化合物の存在下に、ＴＦＥとプロピレンとを主成分とする第１のモノマー成分を０〜５０℃の重合温度で共重合し、ＴＦＥ／Ｐ系セグメントを製造する第１の工程と、
前記ＴＦＥ／Ｐ系セグメントの存在下に、ＴＦＥとエチレンとを主成分とする第２のモノマー成分を共重合し、前記ＴＦＥ／Ｐ系セグメントに、ＴＦＥ／Ｅ系セグメントを結合する第２の工程とを有し、
前記第２の工程において、前記テトラフルオロエチレン／プロピレン系セグメントと、前記テトラフルオロエチレン／エチレン系セグメントとの質量比が、３０：７０〜７０：３０となるように、前記テトラフルオロエチレン／プロピレン系セグメントおよび前記第２のモノマー成分を供給することを特徴とする含フッ素ブロックコポリマーの製造方法。
［２］前記第２の工程の重合温度が０〜５０℃である、［１］に記載の含フッ素ブロックコポリマーの製造方法。
［３］前記第１の工程および前記第２の工程の共重合がいずれも乳化重合である、［１］または［２］に記載の含フッ素ブロックコポリマーの製造方法。
The present invention has the following configuration.
[1] TFE and propylene in the presence of a radical polymerization initiator and an iodine compound represented by the general formula RI 2 (wherein R is an alkylene group or fluoroalkylene group having 3 or more carbon atoms). A first step of copolymerizing a first monomer component as a main component at a polymerization temperature of 0 to 50 ° C. to produce a TFE / P segment;
Second step of copolymerizing a second monomer component mainly composed of TFE and ethylene in the presence of the TFE / P-based segment, and bonding the TFE / E-based segment to the TFE / P-based segment. It has a door,
In the second step, the tetrafluoroethylene / propylene-based segment so that the mass ratio of the tetrafluoroethylene / propylene-based segment and the tetrafluoroethylene / ethylene-based segment is 30:70 to 70:30. A method for producing a fluorine-containing block copolymer, comprising supplying a segment and the second monomer component .
[2] The method for producing a fluorinated block copolymer according to [1], wherein the polymerization temperature in the second step is 0 to 50 ° C.
[3] The method for producing a fluorinated block copolymer according to [1] or [2], wherein the copolymerization in the first step and the second step is emulsion polymerization .
本発明によれば、フッ素ゴムセグメントとしてＴＦＥ／Ｐ系セグメントを有し、フッ素樹脂セグメントとしてＴＦＥ／Ｅ系セグメントを有し、軟質性、耐熱性、耐薬品性に加えて、機械物性、光透過性などの物性に優れた含フッ素ブロックコポリマーを製造できる。 According to the present invention, the fluororubber segment has a TFE / P segment and the fluororesin segment has a TFE / E segment. In addition to softness, heat resistance and chemical resistance, mechanical properties and light transmission Fluorine-containing block copolymers having excellent physical properties such as properties can be produced.
＜含フッ素ブロックコポリマーの製造方法＞
本発明の含フッ素ブロックコポリマーの製造方法は、フッ素ゴムセグメントとしてＴＦＥ／Ｐ系セグメントを有し、フッ素樹脂セグメントとしてＴＦＥ／Ｅ系セグメントを有する含フッ素ブロックコポリマーの製造方法である。
該製造方法は、ＴＦＥ／Ｐ系セグメントを製造する第１の工程と、ＴＦＥ／Ｐ系セグメントにＴＦＥ／Ｅ系セグメントを結合する第２の工程とを有する。
<Method for producing fluorine-containing block copolymer>
The method for producing a fluorinated block copolymer of the present invention is a method for producing a fluorinated block copolymer having a TFE / P-based segment as a fluororubber segment and a TFE / E-based segment as a fluororesin segment.
The manufacturing method includes a first step of manufacturing a TFE / P-based segment and a second step of coupling the TFE / E-based segment to the TFE / P-based segment.
第１の工程では、ラジカル重合開始剤と、一般式ＲＩ２（式中、Ｒは炭素数３以上のアルキレン基またはフルオロアルキレン基である。）で表されるヨウ素化合物の存在下に、ＴＦＥとプロピレンとを主成分とする第１のモノマー成分を０〜５０℃の重合温度で共重合する。ヨウ素化合物は、連鎖移動剤として作用する。これにより、分子鎖の末端にヨウ素原子を有するＴＦＥ／Ｐ系セグメントが得られる。 In the first step, in the presence of a radical polymerization initiator and an iodine compound represented by the general formula RI 2 (wherein R is an alkylene group or fluoroalkylene group having 3 or more carbon atoms), TFE and A first monomer component mainly composed of propylene is copolymerized at a polymerization temperature of 0 to 50 ° C. The iodine compound acts as a chain transfer agent. As a result, a TFE / P segment having an iodine atom at the end of the molecular chain is obtained.
第１のモノマー成分は、モノマーとしてＴＦＥとプロピレンを主成分とし、必要に応じてその他のモノマーを含有することも好ましい。第１のモノマー成分（１００モル％）中のＴＦＥとプロピレンとの合計割合は、第１の工程で製造するＴＦＥ／Ｐ系セグメントにおける、ＴＦＥに基く単位とプロピレンに基く単位との合計割合に応じて設定する。
第１の工程で製造するＴＦＥ／Ｐ系セグメントにおける、ＴＦＥに基く単位とプロピレンに基く単位との合計割合は、耐薬品性に優れ、軟質な含フッ素ブロックコポリマーが得られる点から、７０モル％以上が好ましく、９０モル％以上がより好ましい。
It is also preferable that the first monomer component contains TFE and propylene as main components and other monomers as required. The total proportion of TFE and propylene in the first monomer component (100 mol%) depends on the total proportion of units based on TFE and units based on propylene in the TFE / P segment produced in the first step. To set.
In the TFE / P segment produced in the first step, the total ratio of TFE-based units and propylene-based units is 70 mol% because it is excellent in chemical resistance and a soft fluorine-containing block copolymer is obtained. The above is preferable, and 90 mol% or more is more preferable.
なお、本明細書において、セグメントにおける単位の割合は、全フッ素含有量の分析および核磁気共鳴分光法（ＮＭＲ）により求められる。 In the present specification, the proportion of units in the segment is determined by analyzing the total fluorine content and nuclear magnetic resonance spectroscopy (NMR).
第１のモノマー成分中のＴＦＥとプロピレンとのモル比は、第１の工程で製造するＴＦＥ／Ｐ系セグメントにおける、ＴＦＥに基く単位とプロピレンに基く単位とのモル比に応じて設定する。
第１の工程で製造するＴＦＥ／Ｐ系セグメントにおける、ＴＦＥに基く単位とプロピレンに基く単位とのモル比は、軟質性、耐熱性、耐薬品性の点から、３０：７０〜７０：３０が好ましく、４０：６０〜６０：４０がより好ましく、５０：５０〜６０：４０が最も好ましい。
The molar ratio of TFE and propylene in the first monomer component is set according to the molar ratio of units based on TFE and units based on propylene in the TFE / P-based segment produced in the first step.
In the TFE / P segment produced in the first step, the molar ratio of TFE-based units to propylene-based units is 30:70 to 70:30 in terms of softness, heat resistance, and chemical resistance. Preferably, 40:60 to 60:40 is more preferable, and 50:50 to 60:40 is most preferable.
その他のモノマーとしては、モノフルオロエチレン、トリフルオロエチレン、トリフルオロプロピレン、ペンタフルオロプロピレン、ヘキサフルオロプロピレン、ヘキサフルオロイソブチレン、ジクロロジフルオロエチレン等のフッ素化オレフィン；パーフルオロ（メチルビニルエーテル）等のパーフルオロ（アルキルビニルエーテル）；エチレン、１−ブテン、イソブチレン等の炭化水素オレフィン；メチルビニルエーテル、エチルビニルエーテル、ブチルビニルエーテル、シクロヘキシルビニルエーテル等のアルキルビニルエーテル、酢酸ビニル、プロピオン酸ビニル等のビニルエステル、塩化ビニル、塩化ビニリデン、トリフルオロスチレン等が挙げられる。その他のモノマーは１種以上を使用できる。 Other monomers include fluorinated olefins such as monofluoroethylene, trifluoroethylene, trifluoropropylene, pentafluoropropylene, hexafluoropropylene, hexafluoroisobutylene and dichlorodifluoroethylene; perfluoro (methyl vinyl ether) Alkyl vinyl ether); hydrocarbon olefins such as ethylene, 1-butene and isobutylene; alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether and cyclohexyl vinyl ether, vinyl esters such as vinyl acetate and vinyl propionate, vinyl chloride, vinylidene chloride, Examples thereof include trifluorostyrene. One or more other monomers can be used.
第１のモノマー成分中のその他のモノマーの割合は、第１の工程で製造するＴＦＥ／Ｐ系セグメントにおける、その他のモノマーに基く単位の割合に応じて設定する。第１の工程で製造するＴＦＥ／Ｐ系セグメントにおける、その他のモノマーに基く単位の割合は、３０モル％以下が好ましく、１０モル％以下がより好ましい。 The proportion of other monomers in the first monomer component is set according to the proportion of units based on other monomers in the TFE / P segment produced in the first step. The proportion of units based on other monomers in the TFE / P-based segment produced in the first step is preferably 30 mol% or less, and more preferably 10 mol% or less.
第１の工程で使用されるヨウ素化合物は、一般式ＲＩ２（式中、Ｒは炭素数３以上のアルキレン基またはフルオロアルキレン基である。）で表され、Ｒの両末端にヨウ素原子が結合したヨウ素化合物である。 The iodine compound used in the first step is represented by the general formula RI 2 (wherein R is an alkylene group or fluoroalkylene group having 3 or more carbon atoms), and iodine atoms are bonded to both ends of R. Iodine compound.
一般式ＲＩ２で表されるヨウ素化合物の具体例としては、１，３−ジヨードプロパン、１，４−ジヨードブタン、１，６−ジヨードヘキサン、１，８−ジヨードオクタン、１，３−ジヨードパーフルオロプロパン、１，４−ジヨードパーフルオロブタン、１，６−ジヨードパーフルオロヘキサン、１，８−ジヨードパーフルオロオクタン等が挙げられる。Ｒの炭素数は３〜８が好ましい。一般式ＲＩ２で表されるヨウ素化合物としては、パーフルオロアルキレン基を有するヨウ素化合物がより好ましく、１，４−ジヨードパーフルオロブタンが特に好ましい。ヨウ素化合物は１種以上を使用できる。 Specific examples of the iodine compound represented by the general formula RI 2 include 1,3-diiodopropane, 1,4-diiodobutane, 1,6-diiodohexane, 1,8-diiodooctane, 1,3- Examples include diiodoperfluoropropane, 1,4-diiodoperfluorobutane, 1,6-diiodoperfluorohexane, 1,8-diiodoperfluorooctane, and the like. The carbon number of R is preferably 3-8. The general formula iodine compound represented by RI 2, an iodine compound having a perfluoroalkylene group is more preferred, 1,4-diiodoperfluorobutane is particularly preferred. One or more iodine compounds can be used.
一般式ＲＩ２で表されるヨウ素化合物は、第１の工程で製造するＴＦＥ／Ｐ系セグメント中のヨウ素原子含有量が０．０１〜５．０質量％となるよう添加されることが好ましく、０．１〜１．０質量％となるよう添加されることがより好ましい。 The iodine compound represented by the general formula RI 2 is preferably added so that the iodine atom content in the TFE / P segment produced in the first step is 0.01 to 5.0% by mass, It is more preferable to add so that it may become 0.1-1.0 mass%.
第１の工程における重合方法としては、乳化重合法、溶液重合法、懸濁重合法、塊状重合法が挙げられ、ＴＦＥ／Ｐ系セグメントの分子量および共重合組成の調整がしやすく、生産性に優れる点から、ガス状の第１のモノマー成分を乳化剤の存在下に水性媒体中で重合する乳化重合が好ましい。
水性媒体としては、水、または水溶性有機溶媒を含む水が好ましく、水溶性有機溶媒を含む水がより好ましい。
水溶性有機溶媒としては、ｔｅｒｔ−ブタノール、プロピレングリコール、ジプロピレングリコール、ジプロピレングリコールモノメチルエーテル、トリプロピレングリコール等が挙げられ、ｔｅｒｔ−ブタノールが好ましい。水溶性有機溶媒は１種以上を使用できる。
水性媒体中における水溶性有機溶媒の含有量は、水１００質量部に対して１〜５０質量部が好ましく、３〜２０質量部がより好ましい。
Examples of the polymerization method in the first step include an emulsion polymerization method, a solution polymerization method, a suspension polymerization method, and a bulk polymerization method, and it is easy to adjust the molecular weight and copolymer composition of the TFE / P-based segment. From the viewpoint of superiority, emulsion polymerization is preferred in which the gaseous first monomer component is polymerized in an aqueous medium in the presence of an emulsifier.
As the aqueous medium, water or water containing a water-soluble organic solvent is preferable, and water containing a water-soluble organic solvent is more preferable.
Examples of the water-soluble organic solvent include tert-butanol, propylene glycol, dipropylene glycol, dipropylene glycol monomethyl ether, and tripropylene glycol, and tert-butanol is preferable. One or more water-soluble organic solvents can be used.
1-50 mass parts is preferable with respect to 100 mass parts of water, and, as for content of the water-soluble organic solvent in an aqueous medium, 3-20 mass parts is more preferable.
第１の工程で使用されるラジカル重合開始剤としては、水溶性開始剤が好ましい。
水溶性開始剤としては、過硫酸塩（過硫酸アンモニウム、過硫酸ナトリウム、過硫酸カリウム等の過硫酸アルカリ金属塩等。）；有機系開始剤（ジコハク酸過酸化物、アゾビスイソブチルアミジン二塩酸塩等。）；過硫酸塩と還元剤（チオ硫酸塩、亜硫酸塩、亜硫酸水素塩、ピロ亜硫酸塩、ヒドロキシメタンスルフィン酸塩等。）とを組み合わせたレドックス開始剤等が挙げられ、レドックス開始剤が好ましい。第１の工程の重合温度である０〜５０℃において、第１のモノマー成分を重合可能にする点から、過硫酸塩としては過硫酸アンモニウムを用いることが好ましい。還元剤としてはヒドロキシメタンスルフィン酸塩を用いることが好ましく、ヒドロキシメタンスルフィン酸ナトリウム塩を用いることがより好ましい。
The radical polymerization initiator used in the first step is preferably a water-soluble initiator.
Water-soluble initiators include persulfates (alkali metal persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate); organic initiators (disuccinic acid peroxide, azobisisobutylamidine dihydrochloride) Etc.); redox initiators combined with persulfates and reducing agents (thiosulfates, sulfites, hydrogen sulfites, pyrosulfites, hydroxymethanesulfinates, etc.), and the like. preferable. From the viewpoint of allowing the first monomer component to be polymerized at 0 to 50 ° C. which is the polymerization temperature in the first step, it is preferable to use ammonium persulfate as the persulfate. As the reducing agent, hydroxymethanesulfinate is preferably used, and hydroxymethanesulfinate sodium salt is more preferably used.
ラジカル重合開始剤の使用量は、第１のモノマー成分１００質量部に対して、ラジカル重合開始剤を０．００１〜１０質量部使用することが好ましく、０．０１〜５質量部がより好ましい。 As for the usage-amount of a radical polymerization initiator, it is preferable to use 0.001-10 mass parts of radical polymerization initiators with respect to 100 mass parts of 1st monomer components, and 0.01-5 mass parts is more preferable.
レドックス開始剤を使用する場合には、第３成分として、少量の鉄、第一鉄塩などの鉄塩、硫酸銀等を共存させることが好ましく、水溶性鉄塩を共存させることがより好ましい。水溶性鉄塩の具体例としては硫酸第一鉄、硫酸第二鉄、硝酸第一鉄、硝酸第二鉄、塩化第一鉄、塩化第二鉄、硫酸第一鉄アンモニウム、硫酸第二鉄アンモニウムなどが挙げられる。
また、レドックス開始剤を使用する場合には、キレート剤を加えることが好ましい。キレート剤としては、エチレンジアミン四酢酸二ナトリウム塩が好ましい。
When a redox initiator is used, it is preferable that a small amount of iron, a ferrous salt such as ferrous salt, silver sulfate, etc. coexist as a third component, and a water-soluble iron salt is more preferable. Specific examples of water-soluble iron salts include ferrous sulfate, ferric sulfate, ferrous nitrate, ferric nitrate, ferrous chloride, ferric chloride, ferrous ammonium sulfate, ferric ammonium sulfate Etc.
Moreover, when using a redox initiator, it is preferable to add a chelating agent. As the chelating agent, ethylenediaminetetraacetic acid disodium salt is preferred.
過硫酸塩の使用量は、水性媒体の１００質量部に対して０．００１〜３質量部が好ましく、０．０１〜１質量部がより好ましく、０．０５〜０．５質量部が特に好ましい。
還元剤の使用量は、水性媒体の１００質量部に対して０．００１〜３質量部が好ましく、０．０１〜１質量部がより好ましく、０．０５〜０．５質量部が特に好ましい。
鉄、第一鉄塩などの鉄塩、硫酸銀等の第３成分の使用量は、水性媒体の１００質量部に対して０．０００１〜０．３質量部が好ましく、０．００１〜０．１質量部がより好ましく、０．０１〜０．１質量部が特に好ましい。
キレート剤は、水性媒体の１００質量部に対して０．０００１〜０．３質量部が好ましく、０．００１〜０．１質量部がより好ましく、０．０１〜０．１質量部が特に好ましい。
The amount of persulfate used is preferably 0.001 to 3 parts by mass, more preferably 0.01 to 1 part by mass, and particularly preferably 0.05 to 0.5 parts by mass with respect to 100 parts by mass of the aqueous medium. .
The amount of the reducing agent used is preferably 0.001 to 3 parts by mass, more preferably 0.01 to 1 part by mass, and particularly preferably 0.05 to 0.5 part by mass with respect to 100 parts by mass of the aqueous medium.
As for the usage-amount of 3rd components, such as iron and iron salts, such as iron and a ferrous salt, and silver sulfate, 0.0001-0.3 mass part is preferable with respect to 100 mass parts of an aqueous medium, and 0.001-0. 1 part by mass is more preferable, and 0.01 to 0.1 part by mass is particularly preferable.
The chelating agent is preferably 0.0001 to 0.3 parts by mass, more preferably 0.001 to 0.1 parts by mass, and particularly preferably 0.01 to 0.1 parts by mass with respect to 100 parts by mass of the aqueous medium. .
第１の工程の重合温度は０〜５０℃であり、１０〜４０℃が好ましく、２０〜３０℃がより好ましい。重合温度が上記範囲内であると、該第１の工程の後に第２の工程を経て得られる含フッ素ブロックコポリマーは、機械物性、透明性などが優れる。具体的には、該含フッ素ブロックコポリマーは、引張弾性率が低く、引張破断強度、引張破断伸度が高い。また、光透過性が高い。 The polymerization temperature in the first step is 0 to 50 ° C, preferably 10 to 40 ° C, and more preferably 20 to 30 ° C. When the polymerization temperature is within the above range, the fluorine-containing block copolymer obtained through the second step after the first step is excellent in mechanical properties, transparency and the like. Specifically, the fluorine-containing block copolymer has a low tensile elastic modulus, a high tensile breaking strength, and a high tensile breaking elongation. Moreover, the light transmittance is high.
これは、以下の理由によるものと考えられる。
第１の工程の重合温度が上記範囲内であると、第１の工程により、分子鎖の両末端にヨウ素原子を有するＴＦＥ／Ｐ系セグメントが高い収率で得られる。分子鎖の両末端にヨウ素原子を有するＴＦＥ／Ｐ系セグメントの存在下に、第２の工程でＴＦＥとエチレンとを主成分とする第２のモノマー成分を共重合すると、ＴＦＥ／Ｐ系セグメント［Ｐ］の両側にＴＦＥ／Ｅ系セグメント［Ｑ］が結合した［Ｑ］−［Ｐ］−［Ｑ］型のトリブロックコポリマーが得られやすい。そのため、第１の工程の重合温度が上記範囲内であると、第１の工程と第２の工程を経て得られる含フッ素ブロックコポリマーの機械物性、透明性などが優れるものと考えられる。
This is considered to be due to the following reasons.
When the polymerization temperature in the first step is within the above range, the TFE / P segment having iodine atoms at both ends of the molecular chain can be obtained in high yield by the first step. In the presence of the TFE / P-based segment having iodine atoms at both ends of the molecular chain, the second monomer component having TFE and ethylene as main components in the second step is copolymerized to produce a TFE / P-based segment [ It is easy to obtain a [Q]-[P]-[Q] type triblock copolymer in which TFE / E segment [Q] is bonded to both sides of P]. Therefore, when the polymerization temperature in the first step is within the above range, it is considered that the mechanical properties and transparency of the fluorine-containing block copolymer obtained through the first step and the second step are excellent.
これに対して、第１の工程の重合温度が上記範囲を超えると、第１の工程において、分子鎖の末端がヨウ素原子以外であるＴＦＥ／Ｐ系セグメントの収率が増加する。分子鎖の末端がヨウ素原子以外であるＴＦＥ／Ｐ系セグメントの存在下に、第２の工程でＴＦＥとエチレンとを主成分とする第２のモノマー成分を共重合した場合には、優れた機械物性、透明性などを示す上述の［Ｑ］−［Ｐ］−［Ｑ］型のトリブロックコポリマーは得られにくい。
一方、第１の工程の重合温度が上記範囲未満であると、充分な重合速度が得られない。
In contrast, when the polymerization temperature in the first step exceeds the above range, in the first step, the yield of TFE / P-based segments whose molecular chain ends are other than iodine atoms increases. In the presence of a TFE / P-based segment whose molecular chain end is other than an iodine atom, in the second step, when a second monomer component mainly composed of TFE and ethylene is copolymerized, an excellent machine The above-mentioned [Q]-[P]-[Q] type triblock copolymers exhibiting physical properties and transparency are difficult to obtain.
On the other hand, when the polymerization temperature in the first step is less than the above range, a sufficient polymerization rate cannot be obtained.
第１の工程の重合圧力（ゲージ圧）は、０．５〜１０ＭＰａＧが好ましく、１．０〜５．０ＭＰａＧがより好ましく、１．０〜３．０ＭＰａＧが最も好ましい。重合圧力は、第１のモノマー成分の反応器への供給量（圧入量）により調整できる。重合圧力が上記範囲内であると、重合速度が適切で制御しやすく、生産性にも優れる。 The polymerization pressure (gauge pressure) in the first step is preferably 0.5 to 10 MPaG, more preferably 1.0 to 5.0 MPaG, and most preferably 1.0 to 3.0 MPaG. The polymerization pressure can be adjusted by the supply amount (injection amount) of the first monomer component to the reactor. When the polymerization pressure is within the above range, the polymerization rate is appropriate and easy to control, and the productivity is excellent.
乳化重合法において、水性媒体のｐＨは７〜１４が好ましく、７〜１１がより好ましく、７．５〜１１がさらに好ましく、８〜１０．５が最も好ましい。ｐＨが７以上であると重合性に優れる。
水性媒体のｐＨは、第１の工程における乳化重合の重合開始から重合終了の間の全期間のうち８０％以上が上記範囲内であることが好ましく、９０％以上が上記範囲内であることがより好ましく、９５％以上であることがさらに好ましく、全期間が上記範囲内であることが最も好ましい。
In the emulsion polymerization method, the pH of the aqueous medium is preferably 7 to 14, more preferably 7 to 11, further preferably 7.5 to 11, and most preferably 8 to 10.5. When the pH is 7 or more, the polymerizability is excellent.
As for the pH of the aqueous medium, it is preferable that 80% or more of the total period from the start of polymerization to the end of polymerization in the first step is within the above range, and 90% or more is within the above range. More preferably, it is more preferably 95% or more, and most preferably the entire period is within the above range.
ｐＨの調整にはｐＨ調整剤およびｐＨ緩衝剤を用いることが好ましい。ｐＨ調整剤としては、水酸化ナトリウム、水酸化カリウム等などのアルカリ金属の水酸化物が挙げられる。ｐＨ緩衝剤としては、無機塩類等が挙げられる。無機塩類としては、リン酸水素二ナトリウム、リン酸二水素ナトリウム等のリン酸塩；炭酸水素ナトリウム、炭酸ナトリウム等の炭酸塩；等が挙げられる。リン酸塩のより好ましい具体例としては、リン酸水素二ナトリウム２水和物、リン酸水素二ナトリウム１２水和物等が挙げられる。ｐＨ調整剤およびｐＨ緩衝剤は１種以上を使用できる。 It is preferable to use a pH adjusting agent and a pH buffering agent for adjusting the pH. Examples of the pH adjuster include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. Examples of pH buffering agents include inorganic salts. Examples of inorganic salts include phosphates such as disodium hydrogen phosphate and sodium dihydrogen phosphate; carbonates such as sodium hydrogen carbonate and sodium carbonate; and the like. More preferable specific examples of the phosphate include disodium hydrogen phosphate dihydrate and disodium hydrogen phosphate dodecahydrate. One or more pH adjusting agents and pH buffering agents can be used.
乳化剤としては、得られるＴＦＥ／Ｐ系セグメントや含フッ素ブロックコポリマーのラテックスの機械的安定性および化学的安定性が優れることから、イオン性乳化剤が好ましく、アニオン性乳化剤がより好ましい。
アニオン性乳化剤としては、公知のものが使用できる。具体例としては、ラウリル硫酸ナトリウム、ドデシルベンゼンスルホン酸ナトリウム等の炭化水素乳化剤；パーフルオロオクタン酸アンモニウム、パーフルオロヘキサン酸アンモニウム等の含フッ素アルカン酸塩：一般式（α）Ｒｆ１ＯＲｆ２ＣＯＯＡ（Ｒｆ１は炭素数１〜８のパーフルオロアルキル基であり、Ｒｆ２は、直鎖状の含フッ素アルキレン基であり、該含フッ素アルキレン基にはエーテル性の酸素原子を含有してもよく、該含フッ素アルキレン基は炭素数１〜３のパーフルオロアルキル基の側鎖を有してもよく、Ａは水素原子、アルカリ金属またはＮＨ４である。）で表される含フッ素エーテルカルボン酸化合物（以下、一般式（α）の乳化剤という。）が挙げられる。なお、Ｒｆ２の炭素数は１〜１２が好ましく、１〜８がより好ましい。
第１の工程で使用する乳化剤としては、含フッ素乳化剤が好ましく、含フッ素アルカン酸塩または一般式（α）の乳化剤がより好ましい。乳化剤は１種以上を使用できる。
As the emulsifier, an ionic emulsifier is preferable, and an anionic emulsifier is more preferable, because the mechanical stability and chemical stability of the obtained TFE / P segment and the fluorine-containing block copolymer latex are excellent.
Known anionic emulsifiers can be used. Specific examples include hydrocarbon emulsifiers such as sodium lauryl sulfate and sodium dodecylbenzenesulfonate; fluorine-containing alkane salts such as ammonium perfluorooctanoate and ammonium perfluorohexanoate: general formula (α) R f1 OR f2 COOA ( R f1 is a C 1-8 perfluoroalkyl group, R f2 is a linear fluorine-containing alkylene group, and the fluorine-containing alkylene group may contain an etheric oxygen atom, The fluorinated alkylene group may have a side chain of a C 1-3 perfluoroalkyl group, and A is a hydrogen atom, an alkali metal or NH 4 ). (Hereinafter referred to as an emulsifier of the general formula (α)). The number of carbon atoms in R f2 is preferably 1 to 12, 1 to 8 is more preferable.
The emulsifier used in the first step is preferably a fluorinated emulsifier, more preferably a fluorinated alkane salt or an emulsifier of the general formula (α). One or more emulsifiers can be used.
乳化剤の使用量は、水性媒体の１００質量部に対して、０．０１〜１５質量部が好ましく、０．１〜１０質量部がより好ましく、０．１〜３質量部が最も好ましい。 The amount of the emulsifier used is preferably 0.01 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, and most preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the aqueous medium.
上述の第１の工程の後、該第１の工程で生成したＴＦＥ／Ｐ系セグメントの存在下に、ＴＦＥとエチレンを主成分とする第２のモノマー成分を共重合する第２の工程を行う。これにより、ＴＦＥ／Ｐ系セグメントとＴＦＥ／Ｅ系セグメントとが結合した含フッ素ブロックコポリマーが得られる。該含フッ素ブロックコポリマーは、ＴＦＥ／Ｐ系セグメント［Ｐ］の両側にＴＦＥ／Ｅ系セグメント［Ｑ］が結合した［Ｑ］−［Ｐ］−［Ｑ］型のトリブロックコポリマーを主成分とする混合物である。 After the first step described above, a second step of copolymerizing a second monomer component mainly composed of TFE and ethylene in the presence of the TFE / P-based segment generated in the first step is performed. . Thereby, the fluorine-containing block copolymer which the TFE / P type segment and the TFE / E type segment couple | bonded is obtained. The fluorine-containing block copolymer has a [Q]-[P]-[Q] type triblock copolymer in which a TFE / E segment [Q] is bonded to both sides of a TFE / P segment [P] as a main component. It is a mixture.
第２のモノマー成分は、ＴＦＥとエチレンを主成分とし、必要に応じてその他のモノマーを含有する。第２のモノマー成分（１００モル％）中のＴＦＥとエチレンとの合計割合は、第２の工程で製造するＴＦＥ／Ｅ系セグメントにおける、ＴＦＥに基く単位とエチレンに基く単位との合計割合に応じて設定する。
第２の工程で製造するＴＦＥ／Ｅ系セグメントにおける、ＴＦＥに基く単位とエチレンに基く単位との合計割合は、物性に優れる含フッ素ブロックコポリマーが得られる点から、７０モル％以上が好ましく、９０モル％以上がより好ましい。
A 2nd monomer component has TFE and ethylene as a main component, and contains another monomer as needed. The total proportion of TFE and ethylene in the second monomer component (100 mol%) depends on the total proportion of units based on TFE and units based on ethylene in the TFE / E segment produced in the second step. To set.
In the TFE / E segment produced in the second step, the total ratio of TFE-based units and ethylene-based units is preferably 70 mol% or more from the viewpoint of obtaining a fluorine-containing block copolymer having excellent physical properties, Mole% or more is more preferable.
第２のモノマー成分中のＴＦＥとエチレンとのモル比は、第２の工程で製造するＴＦＥ／Ｅ系セグメントにおける、ＴＦＥに基く単位とエチレンに基く単位とのモル比に応じて設定する。
第２の工程で製造するＴＦＥ／Ｅ系セグメントにおける、ＴＦＥに基く単位とエチレンに基く単位とのモル比は、耐熱性、重合性の点から、３０：７０〜７０：３０が好ましく、４５：５５〜６５：３５がより好ましく、５０：５０〜６５：３５が最も好ましい。
The molar ratio of TFE and ethylene in the second monomer component is set in accordance with the molar ratio of units based on TFE and units based on ethylene in the TFE / E segment produced in the second step.
In the TFE / E segment produced in the second step, the molar ratio of the TFE-based unit to the ethylene-based unit is preferably 30:70 to 70:30 from the viewpoint of heat resistance and polymerizability, and 45: 55 to 65:35 is more preferable, and 50:50 to 65:35 is most preferable.
その他のモノマーとしては、モノフルオロエチレン、トリフルオロエチレン、トリフルオロプロピレン、ペンタフルオロプロピレン、ヘキサフルオロプロピレン、ヘキサフルオロイソブチレン、ジクロロジフルオロエチレン等のフッ素化オレフィン；パーフルオロ（メチルビニルエーテル）等のパーフルオロ（アルキルビニルエーテル）；パーフルオロブチルエチレン等のパーフルオロアルキルエチレン；Ｐ、１−ブテン、イソブチレン等の炭化水素オレフィン；メチルビニルエーテル、エチルビニルエーテル、ブチルビニルエーテル、シクロヘキシルビニルエーテル等のアルキルビニルエーテル、酢酸ビニル、プロピオン酸ビニル等のビニルエステル、塩化ビニル、塩化ビニリデン、トリフルオロスチレン等が挙げられる。その他のモノマーは１種以上を使用できる。 Other monomers include fluorinated olefins such as monofluoroethylene, trifluoroethylene, trifluoropropylene, pentafluoropropylene, hexafluoropropylene, hexafluoroisobutylene and dichlorodifluoroethylene; perfluoro (methyl vinyl ether) Alkyl vinyl ethers); perfluoroalkyl ethylenes such as perfluorobutyl ethylene; hydrocarbon olefins such as P, 1-butene and isobutylene; alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether and cyclohexyl vinyl ether, vinyl acetate, vinyl propionate And vinyl esters, vinyl chloride, vinylidene chloride, trifluorostyrene and the like. One or more other monomers can be used.
第２のモノマー成分中のその他のモノマーの量は、第２の工程で製造するＴＦＥ／Ｅ系セグメントにおける、その他のモノマーに基く単位の割合に応じて設定する。第２の工程で製造するＴＦＥ／Ｅ系セグメントにおける、その他のモノマーに基く単位の割合は、３０モル％以下が好ましく、１０モル％以下がより好ましく、５モル％以下が最も好ましい。 The amount of the other monomer in the second monomer component is set in accordance with the proportion of units based on the other monomer in the TFE / E segment produced in the second step. The proportion of units based on other monomers in the TFE / E segment produced in the second step is preferably 30 mol% or less, more preferably 10 mol% or less, and most preferably 5 mol% or less.
第１の工程で重合圧力一定の状態で供給する第１のモノマー成分と、第２の工程で重合圧力一定の状態で供給する第２のモノマー成分との質量比は、製造する含フッ素ブロックコポリマーにおける、ＴＦＥ／Ｐ系セグメントとＴＦＥ／Ｅ系セグメントとの質量比とほぼ一致する。
本発明で製造する含フッ素ブロックコポリマーにおけるＴＦＥ／Ｐ系セグメントとＴＦＥ／Ｅ系セグメントとの質量比は、軟質性、耐熱性、機械強度、透明性の点から、１０：９０〜９０：１０が好ましく、２０：８０〜８０：２０がより好ましく、３０：７０〜７０：３０がさらに好ましい。
The mass ratio of the first monomer component supplied at a constant polymerization pressure in the first step and the second monomer component supplied at a constant polymerization pressure in the second step is the fluorine-containing block copolymer to be produced. The mass ratio of the TFE / P segment to the TFE / E segment in FIG.
The mass ratio of the TFE / P segment to the TFE / E segment in the fluorine-containing block copolymer produced in the present invention is 10:90 to 90:10 from the viewpoint of softness, heat resistance, mechanical strength, and transparency. Preferably, 20:80 to 80:20 are more preferable, and 30:70 to 70:30 are more preferable.
第２の工程における重合方法としては、乳化重合法、溶液重合法、懸濁重合法、塊状重合法が挙げられる。第１の工程と同様に、ガス状の第２のモノマー成分を乳化剤の存在下に水性媒体中で重合する乳化重合が、分子量および共重合組成の調整の点から好ましい。第２の工程は、第１の工程により得られたＴＦＥ／Ｐ系セグメントを含むラテックス中に、第２のモノマー成分を供給して、共重合する方法が好ましい。具体的には、第１の工程後、未反応モノマーを反応器から空放した後に、第２のモノマー成分を反応器に仕込み、重合を継続させる。または、第１の工程で製造されたＴＦＥ／Ｐ系セグメントを含むラテックスを反応器から一旦取り出した後、再度、反応器に仕込み、ついで、第２のモノマー成分を反応器に仕込んで重合を継続させてもよい。 Examples of the polymerization method in the second step include an emulsion polymerization method, a solution polymerization method, a suspension polymerization method, and a bulk polymerization method. As in the first step, emulsion polymerization in which the gaseous second monomer component is polymerized in an aqueous medium in the presence of an emulsifier is preferable from the viewpoint of adjusting the molecular weight and copolymer composition. The second step is preferably a method in which the second monomer component is supplied to the latex containing the TFE / P segment obtained in the first step and copolymerized. Specifically, after the first step, unreacted monomer is discharged from the reactor, and then the second monomer component is charged into the reactor to continue the polymerization. Alternatively, the latex containing the TFE / P segment produced in the first step is once taken out from the reactor and then charged again, and then the second monomer component is charged into the reactor and polymerization is continued. You may let them.
第２の工程の重合温度は０〜５０℃が好ましく、１０〜４０℃がより好ましく、２０〜３０℃がさらに好ましい。重合温度が上記範囲内であると、第１の工程で得られたＴＦＥ／Ｐ系セグメント［Ｐ］の両側にＴＦＥ／Ｅ系セグメント［Ｑ］が結合した［Ｑ］−［Ｐ］−［Ｑ］型のトリブロックコポリマーを主成分とする含フッ素ブロックコポリマーが得られやすい。そのため、得られた含フッ素ブロックコポリマーは、機械特性、透明性などに優れる。 The polymerization temperature in the second step is preferably 0 to 50 ° C, more preferably 10 to 40 ° C, and further preferably 20 to 30 ° C. When the polymerization temperature is within the above range, [Q]-[P]-[Q in which the TFE / E segment [Q] is bonded to both sides of the TFE / P segment [P] obtained in the first step. It is easy to obtain a fluorine-containing block copolymer mainly composed of a triblock copolymer. Therefore, the obtained fluorine-containing block copolymer is excellent in mechanical properties, transparency and the like.
第２の工程の重合条件（重合圧力（ゲージ圧）、ｐＨ等。）は、第１の工程と同様に設定できる。 The polymerization conditions (polymerization pressure (gauge pressure), pH, etc.) in the second step can be set in the same manner as in the first step.
第２の工程後、得られたラテックスを公知の方法で凝集させることにより、含フッ素ブロックコポリマーを単離する。凝集方法としては、金属塩を添加して塩析する方法、塩酸等の無機酸を添加する方法、機械的せん断による方法、凍結および解凍による方法等が挙げられる。 After the second step, the resulting latex is agglomerated by a known method to isolate the fluorine-containing block copolymer. Examples of the aggregation method include a method of salting out by adding a metal salt, a method of adding an inorganic acid such as hydrochloric acid, a method by mechanical shearing, a method by freezing and thawing, and the like.
本発明の製造方法における重合速度は、反応器の単位体積および単位時間あたりの含フッ素ブロックコポリマーの生成量として、１〜１００ｇ／Ｌ・時間が好ましく、３〜５０ｇ／Ｌ・時間がより好ましく、５〜３０ｇ／Ｌ・時間がさらに好ましい。重合速度が上記範囲内であると、生産性が優れるとともに、充分な分子量を備えた含フッ素ブロックコポリマーが得られやすい。重合速度は、重合圧力、仕込むラジカル重合開始剤量などにより制御できる。 The polymerization rate in the production method of the present invention is preferably 1 to 100 g / L · hour, more preferably 3 to 50 g / L · hour as the amount of the fluorine-containing block copolymer produced per unit volume and unit time of the reactor. 5 to 30 g / L · hour is more preferable. When the polymerization rate is within the above range, productivity is excellent and a fluorine-containing block copolymer having a sufficient molecular weight is easily obtained. The polymerization rate can be controlled by the polymerization pressure, the amount of radical polymerization initiator charged, and the like.
＜含フッ素ブロックコポリマー＞
本発明の含フッ素ブロックコポリマーは、上述した製造方法により製造される。該含フッ素ブロックコポリマーの分子量はＱ値を用いて目安にすることができる。Ｑ値は、後述する方法で測定される溶融時の流れ性を示す値であり、この値が大きいと分子量が小さく、小さいと分子量が大きいことを示す。３００℃におけるＱ値は、０．１〜２００ｍｍ３／ｓが好ましく、０．３〜１００ｍｍ３／ｓがより好ましい。Ｑ値が上記範囲内であると、含フッ素ブロックコポリマーは、より優れた耐薬品性と物性とを示す。Ｑ値は、重合速度、ヨウ素化合物の使用量、重合圧力、重合圧力一定の状態で仕込んだモノマー量などにより制御できる。
また、比較的分子量が小さいポリマーについては、質量平均分子量（Ｍｗ）および数平均分子量（Ｍｎ）を測定することが可能である。本明細書においてＭｗ及びＭｎは、分子量既知の標準ポリスチレン試料を用いて作成した検量線を用い、サイズ排除クロマトグラフィーで測定することによって得られるポリスチレン換算分子量である。
<Fluorine-containing block copolymer>
The fluorine-containing block copolymer of the present invention is produced by the production method described above. The molecular weight of the fluorine-containing block copolymer can be used as a guide using the Q value. The Q value is a value indicating the flowability at the time of melting measured by a method described later. When this value is large, the molecular weight is small, and when it is small, the molecular weight is large. Q value at 300 ° C. is preferably 0.1~200mm 3 / s, 0.3~100mm 3 / s is more preferable. When the Q value is within the above range, the fluorine-containing block copolymer exhibits more excellent chemical resistance and physical properties. The Q value can be controlled by the polymerization rate, the amount of iodine compound used, the polymerization pressure, the amount of monomer charged at a constant polymerization pressure, and the like.
Moreover, about a polymer with comparatively small molecular weight, it is possible to measure a mass average molecular weight (Mw) and a number average molecular weight (Mn). In the present specification, Mw and Mn are polystyrene-converted molecular weights obtained by measuring with size exclusion chromatography using a calibration curve prepared using a standard polystyrene sample having a known molecular weight.
また、本発明の含フッ素ブロックコポリマーは、第１の工程を上述の重合温度で実施しているために、分子鎖の両末端にヨウ素原子を有するＴＦＥ／Ｐ系セグメントが高い収率で得られる。そのため、第１の工程で得られたＴＦＥ／Ｐ系セグメントのＭｎを該ＴＦＥ／Ｐ系セグメントの質量（収量）で割った値（Ｓ）と、第２の工程後に得られた含フッ素ブロックポリマーのＭｎを該含フッ素ブロックコポリマーの質量（収量）で割った値（Ｔ）とがほぼ等しく、これらの比、すなわちＳ：Ｔが１：０．８〜１：１．２の範囲にある。第１の工程を高温で行うと、分子鎖の末端がヨウ素原子以外であるＴＦＥ／Ｐ系セグメントの収率が増加し、その結果、Ｓ：Ｔは上記範囲外となる。 Moreover, since the fluorine-containing block copolymer of the present invention is carried out at the polymerization temperature described above, a TFE / P segment having iodine atoms at both ends of the molecular chain can be obtained in high yield. . Therefore, the value (S) obtained by dividing Mn of the TFE / P-based segment obtained in the first step by the mass (yield) of the TFE / P-based segment, and the fluorine-containing block polymer obtained after the second step The value (T) obtained by dividing the Mn by the mass (yield) of the fluorine-containing block copolymer is approximately equal, and these ratios, that is, S: T is in the range of 1: 0.8 to 1: 1.2. When the first step is performed at a high temperature, the yield of TFE / P-based segments whose molecular chain ends are other than iodine atoms increases, and as a result, S: T falls outside the above range.
本発明の含フッ素ブロックコポリマーは、軟質性、耐熱性、耐薬品性に加えて、機械物性、光透過性などの物性に優れる。そのため、該含フッ素ブロックコポリマーは、自動車の配線等に用いられる軟質電線の被覆材、農業用フィルム等に好適に用いられる。 The fluorine-containing block copolymer of the present invention is excellent in physical properties such as mechanical properties and light transmittance in addition to softness, heat resistance and chemical resistance. Therefore, the fluorine-containing block copolymer is suitably used for a soft wire covering material, agricultural film, and the like used for automobile wiring and the like.
以下、本発明について、実施例および比較例を用いて具体的に説明する。
＜評価＞
（１）セグメントにおける各単位のモル比
各セグメントにおける各単位のモル比は第１の工程及び第２の工程で得られたポリマーの全フッ素含有量を測定することにより求めることができる。なお、以下の例では、その他のモノマーを共重合していないので、ＮＭＲ分析を実施しなかった。
（２）Ｑ値（流れ性）
フローテスター（島津製作所製）を用いて測定した。ダイスは、直径２．０９５ｍｍ、長さ８ｍｍのものを用いた。荷重７ｋｇ重、温度３００℃で測定対象のポリマーを押出し、流出する速度（ｍｍ３／ｓ）をＱ値とした。
（３）分子量および分子量分布
サイズ排除クロマトグラフィー（ＳＥＣ）装置（ポリマーラボラトリーズ社製、ＰＬ−ＧＰＣ２２０）を用いて測定した。検出器には粘度検出器を用い、カラムには昭和電工社製Ｓｈｏｄｅｘ ＵＴ８０６Ｍ×２本（直列）を用いた。
測定対象のポリマーの４ｍｇを２ｍｌのイソホロンに２００℃で溶解し、カラム温度を２００℃、移動相の流量を１．０ｍｌ／分として、ポリスチレン換算の分子量（質量平均分子量（Ｍｗ）および数平均分子量（Ｍｎ））と、分子量分布（Ｍｗ／Ｍｎ）とを求めた。但し、ＴＦＥ／エチレンセグメントの分子量が高すぎるとブロックコポリマーは溶媒に完全には溶解しないため、低分子量体（質量平均分子量が約１５００００以下）のポリマーに対してのみ測定を行った。
（４）融点および５％重量減少温度
エスアイアイ・ナノテクノロジー社製ＴＧ／ＤＴＡ６３００を用いて、窒素雰囲気下１０℃／分の昇温速度で測定し、吸熱ピークの頂点の温度を融点とし、重量が５％減少した温度を５％重量減少温度とした。
（５）引張破断強度、引張破断伸度
３００℃で溶融プレス成形した厚み０．３ｍｍのシートを打ち抜いてミクロダンベル形状の試料を作成した。この試料を用いてオリエンテック製テンシロンＲＴＣ−２１０で引張速度２００ｍｍ／分で引張破断強度、引張破断伸度を測定した。
（６）引張弾性率
３００℃で溶融プレス成形した厚み０．３ｍｍのシートを打ち抜いて幅５．０ｍｍ長さ３０ｍｍの試料を作成した。この試料を用いて、アイティー計測社製動的粘弾性測定装置ＤＶＡ-２００で周波数１０Ｈｚで動的引張弾性率を測定した。
（７）光透過率
３００℃で溶融プレス成形した厚み０．１ｍｍのシートを用いて、島津製作所社製分光光度計ＵＶ−３１００で測定した（波長：８００ｎｍ）。
Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.
<Evaluation>
(1) Molar ratio of each unit in the segment The molar ratio of each unit in each segment can be determined by measuring the total fluorine content of the polymer obtained in the first step and the second step. In the following examples, no other monomer was copolymerized, so NMR analysis was not performed.
(2) Q value (flowability)
It measured using the flow tester (made by Shimadzu Corporation). A die having a diameter of 2.095 mm and a length of 8 mm was used. The polymer to be measured was extruded at a load of 7 kg and a temperature of 300 ° C., and the outflow speed (mm 3 / s) was defined as the Q value.
(3) Molecular weight and molecular weight distribution It measured using the size exclusion chromatography (SEC) apparatus (The polymer laboratory company make, PL-GPC220). A viscosity detector was used as a detector, and Shodex UT806M × 2 (in series) manufactured by Showa Denko KK was used as a column.
4 mg of the polymer to be measured is dissolved in 2 ml of isophorone at 200 ° C., the column temperature is 200 ° C., the flow rate of the mobile phase is 1.0 ml / min, and the molecular weight in terms of polystyrene (mass average molecular weight (Mw) and number average molecular weight). (Mn)) and molecular weight distribution (Mw / Mn) were determined. However, since the block copolymer is not completely dissolved in the solvent if the molecular weight of the TFE / ethylene segment is too high, the measurement was performed only for the polymer having a low molecular weight (mass average molecular weight of about 150,000 or less).
(4) Melting point and 5% weight reduction temperature Using a TG / DTA6300 manufactured by SII Nanotechnology, measured at a heating rate of 10 ° C / min in a nitrogen atmosphere, and the temperature at the top of the endothermic peak was taken as the melting point. Was a 5% weight loss temperature.
(5) Tensile rupture strength, tensile rupture elongation A 0.3 mm thick sheet formed by melt press molding at 300 ° C. was punched to prepare a micro dumbbell-shaped sample. Using this sample, the tensile breaking strength and the tensile breaking elongation were measured with Tensilon RTC-210 manufactured by Orientec Co., Ltd. at a tensile speed of 200 mm / min.
(6) Tensile elastic modulus A 0.3 mm thick sheet formed by melt press molding at 300 ° C. was punched out to prepare a sample having a width of 5.0 mm and a length of 30 mm. Using this sample, the dynamic tensile elastic modulus was measured at a frequency of 10 Hz with a dynamic viscoelasticity measuring apparatus DVA-200 manufactured by IT Measurement.
(7) Light transmittance Measured with a spectrophotometer UV-3100 manufactured by Shimadzu Corporation using a 0.1 mm thick sheet formed by melt press molding at 300 ° C (wavelength: 800 nm).
［重合例１］ ＴＦＥ／Ｐ共重合体（ＴＦＥ／Ｐ系セグメント）の製造（第１の工程）：重合温度２５℃；分子量及び分子量分布が測定できるような低分子量体。
攪拌用アンカー翼を備えた内容積２００ｍｌのステンレス鋼製の耐圧反応器の内部を脱気した後、該反応器に、イオン交換水の８５ｇ、リン酸水素二ナトリウムの２．４ｇ、水酸化ナトリウムの０．０４ｇ、ｔｅｒｔ−ブタノールの１２．２ｇ、含フッ素乳化剤としてＣ２Ｆ５ＯＣＦ２ＣＦ２ＯＣＦ２ＣＯＯＮＨ４の０．８３ｇ、過硫酸アンモニウムの０．６ｇ、１，４−ジヨードパーフルオロブタンの０．６２ｇを添加した。さらに、イオン交換水の１８．４ｇに、エチレンジアミン四酢酸二ナトリウム塩二水和物の０．０２２ｇと、硫酸第一鉄７水和物の０．０１７ｇとを溶解させた水溶液を反応器に加えた。ついで、２５℃でＴＦＥ／Ｐ＝８８／１２（モル比）のモノマー混合ガス（第１のモノマー成分）を、反応器の内圧が１．５５ＭＰａＧになるように圧入した。アンカー翼を２８０ｒｐｍで回転させ、水酸化ナトリウムでｐＨを１０．０に調整したヒドロキシメタンスルフィン酸ナトリウム２水和物（以下、ロンガリットと記す。）の１．２質量％水溶液（以下、ロンガリット１．２質量％水溶液と記す。）を反応器に加え、重合反応を開始させた。以降、ロンガリット１．２質量％水溶液を断続的に反応器に圧入した。
重合温度を２５℃に維持して重合を進行させ、重合の進行に伴い、反応器内の圧力が低下するので、反応器の内圧が１．５５ＭＰａＧに維持するようにＴＦＥ／Ｐ＝５６／４４（モル比）のモノマー混合ガス（第１のモノマー成分）を連続的に圧入して重合反応を続けた。ＴＦＥとプロピレンからなるモノマー混合ガスの圧入量の総量が９．４ｇとなった時点で、ロンガリット１．２質量％水溶液の添加を停止し、反応器の内温を１０℃まで冷却し、重合反応を停止し、ＴＦＥ／Ｐ共重合体Ａのラテックスを得た。
得られたラテックスのｐＨは８．０であった。ロンガリット１．２質量％水溶液の添加量は６．５ｇであった。重合時間は４時間３０分であった。ＴＦＥ／Ｐ共重合体Ａのラテックスを冷凍庫に一晩入れて凍結後、解凍し、ＴＦＥ／Ｐ共重合体Ａを得た。その後、ＴＦＥ／Ｐ共重合体Ａをろ過、イオン交換水により洗浄し、１００℃のオーブンで１２時間乾燥させ、白色のＴＦＥ／Ｐ共重合体Ａの９．４ｇを得た。ＴＦＥ／Ｐ共重合体Ａ中のＴＦＥに基づく単位とプロピレンに基づく単位との比率は、５６：４４（モル比）であった。ＴＦＥ／Ｐ共重合体Ａの数平均分子量（Ｍｎ）は２３０００、質量平均分子量（Ｍｗ）は３５０００、分子量分布（Ｍｗ／Ｍｎ）は１．５であった。ＴＦＥ／Ｐ共重合体Ａの融点は無く、５％重量減少温度は４０３℃であった。ＴＦＥ／Ｐ共重合体Ａは流動性が大きすぎて、３００℃でのＱ値を測定できなかった。
[Polymerization Example 1] Production of TFE / P copolymer (TFE / P-based segment) (first step): polymerization temperature 25 ° C; low molecular weight material capable of measuring molecular weight and molecular weight distribution.
After degassing the interior of a 200 ml stainless steel pressure-resistant reactor equipped with a stirring anchor blade, 85 g of ion-exchanged water, 2.4 g of disodium hydrogen phosphate, sodium hydroxide were added to the reactor. 0.04 g of tert-butanol, 12.2 g of tert-butanol, 0.83 g of C 2 F 5 OCF 2 CF 2 OCF 2 COONH 4 as a fluorine-containing emulsifier, 0.6 g of ammonium persulfate, 1,4-diiodoperfluorobutane Of 0.62 g was added. Furthermore, an aqueous solution in which 0.022 g of ethylenediaminetetraacetic acid disodium salt dihydrate and 0.017 g of ferrous sulfate heptahydrate were dissolved in 18.4 g of ion-exchanged water was added to the reactor. It was. Next, a monomer mixed gas (first monomer component) of TFE / P = 88/12 (molar ratio) at 25 ° C. was injected so that the internal pressure of the reactor was 1.55 MPaG. A 1.2 mass% aqueous solution of sodium hydroxymethanesulfinate dihydrate (hereinafter referred to as Rongalite) whose pH was adjusted to 10.0 with sodium hydroxide by rotating the anchor blade at 280 rpm (hereinafter referred to as Rongalit 1. 2% by weight aqueous solution) was added to the reactor to initiate the polymerization reaction. Thereafter, Rongalite 1.2 mass% aqueous solution was intermittently injected into the reactor.
The polymerization is carried out while maintaining the polymerization temperature at 25 ° C. As the polymerization proceeds, the pressure in the reactor decreases, so that the internal pressure of the reactor is maintained at 1.55 MPaG. TFE / P = 56/44 (Molar ratio) monomer mixture gas (first monomer component) was continuously injected to continue the polymerization reaction. When the total amount of the monomer mixture gas consisting of TFE and propylene reached 9.4 g, the addition of Rongalite 1.2 mass% aqueous solution was stopped, the internal temperature of the reactor was cooled to 10 ° C., and the polymerization reaction And latex of TFE / P copolymer A was obtained.
The obtained latex had a pH of 8.0. The amount of Rongalite 1.2 mass% aqueous solution added was 6.5 g. The polymerization time was 4 hours 30 minutes. The latex of TFE / P copolymer A was placed in a freezer overnight, frozen, and then thawed to obtain TFE / P copolymer A. Thereafter, the TFE / P copolymer A was filtered, washed with ion-exchanged water, and dried in an oven at 100 ° C. for 12 hours to obtain 9.4 g of a white TFE / P copolymer A. The ratio of units based on TFE and units based on propylene in TFE / P copolymer A was 56:44 (molar ratio). The number average molecular weight (Mn) of the TFE / P copolymer A was 23000, the mass average molecular weight (Mw) was 35000, and the molecular weight distribution (Mw / Mn) was 1.5. The TFE / P copolymer A had no melting point and the 5% weight loss temperature was 403 ° C. The TFE / P copolymer A was too fluid and the Q value at 300 ° C. could not be measured.
［重合例２］ＴＦＥ／Ｐ共重合体（ＴＦＥ／Ｐ系セグメント）の製造（第１の工程）：重合温度２５℃。
１，４−ジヨードパーフルオロブタンの０．１７ｇを使用した以外は、重合例１と同様の操作を行って、ＴＦＥ／Ｐ共重合体Ｂのラテックスを得た（第１の工程）。得られたラテックスのｐＨは８．０であった。ロンガリット１．２質量％水溶液の添加量は６．５ｇであった。重合時間は４時間１５分であった。重合例１と同様に凍結、解凍、洗浄、乾燥を行い、白色のＴＦＥ／Ｐ共重合体Ｂの９．７ｇを得た。ＴＦＥ／Ｐ共重合体Ｂ中のＴＦＥに基づく単位とプロピレンに基づく単位との比率は、５６：４４（モル比）であった。
ＴＦＥ／Ｐ共重合体Ｂの融点は無く、５％重量減少温度は４０５℃であった。ＴＦＥ／Ｐ共重合体Ｂは流動性が大きすぎて、３００℃でのＱ値を測定できなかった。
[Polymerization Example 2] Production of TFE / P copolymer (TFE / P segment) (first step): polymerization temperature 25 ° C.
A latex of TFE / P copolymer B was obtained by performing the same operation as in Polymerization Example 1 except that 0.17 g of 1,4-diiodoperfluorobutane was used (first step). The obtained latex had a pH of 8.0. The amount of Rongalite 1.2 mass% aqueous solution added was 6.5 g. The polymerization time was 4 hours and 15 minutes. Freezing, thawing, washing and drying were carried out in the same manner as in Polymerization Example 1 to obtain 9.7 g of white TFE / P copolymer B. The ratio of the units based on TFE and the units based on propylene in the TFE / P copolymer B was 56:44 (molar ratio).
TFE / P copolymer B had no melting point and the 5% weight loss temperature was 405 ° C. The TFE / P copolymer B was too fluid and the Q value at 300 ° C. could not be measured.
［重合例３］ＴＦＥ／Ｐ共重合体（ＴＦＥ／Ｐ系セグメント）の製造（第１の工程）：重合温度８０℃；分子量及び分子量分布が測定できるような低分子量体。
重合例１と同等の反応器の内部を脱気した後、該反応器に、イオン交換水の１０３．４ｇ、リン酸水素二ナトリウムの２．４ｇ、水酸化ナトリウムの０．０４ｇ、ｔｅｒｔ−ブタノールの１２．２ｇ、含フッ素乳化剤としてＣ２Ｆ５ＯＣＦ２ＣＦ２ＯＣＦ２ＣＯＯＮＨ４の０．８３ｇ、１，４−ジヨードパーフルオロブタンの０．６２ｇを添加した。ついで、８０℃でＴＦＥ／Ｐ＝８８／１２（モル比）のモノマー混合ガス（第１のモノマー成分）を、反応器の内圧が２．００ＭＰａＧになるように圧入した。アンカー翼を２８０ｒｐｍで回転させ、過硫酸アンモニウムの２．０質量％水溶液を反応器に圧入した。以降、過硫酸アンモニウムの２．０質量％の水溶液を断続的に圧入させた。重合温度を８０℃に維持して重合を進行させ、重合の進行に伴い、反応器内の圧力が低下するので、反応器の内圧が２．００ＭＰａＧに維持するようにＴＦＥ／Ｐ＝５６／４４（モル比）のモノマー混合ガス（第１のモノマー成分）を連続的に圧入して重合反応を続けた。ＴＦＥとプロピレンからなるモノマー混合ガスの圧入量の総量が９．４ｇとなった時点で、過硫酸アンモニウム２質量％水溶液の添加を停止し、反応器の内温を１０℃まで冷却し、重合反応を停止し、ＴＦＥ／Ｐ共重合体Ｃのラテックスを得た。
得られたラテックスのｐＨは８．２であった。過硫酸アンモニウム２質量％水溶液の添加量は１５ｇであった。重合時間は６時間３０分であった。重合例１と同様に凍結、解凍、洗浄、乾燥を行い、白色のＴＦＥ／Ｐ共重合体Ｃの９．５ｇを得た。ＴＦＥ／Ｐ共重合体Ｃ中のＴＦＥに基づく単位とプロピレンに基づく単位との比率は、５６：４４（モル比）であった。ＴＦＥ／Ｐ共重合体Ｃの数平均分子量（Ｍｎ）は１５０００、質量平均分子量（Ｍｗ）は２７０００、分子量分布（Ｍｗ／Ｍｎ）は１．８であった。ＴＦＥ／Ｐ共重合体Ｃの融点は無く、５％重量減少温度は４０２℃であった。ＴＦＥ／Ｐ共重合体Ｃは流動性が大きすぎて、３００℃でのＱ値を測定できなかった。
[Polymerization Example 3] Production of TFE / P copolymer (TFE / P segment) (first step): polymerization temperature of 80 ° C; low molecular weight material capable of measuring molecular weight and molecular weight distribution.
After degassing the inside of the reactor equivalent to Polymerization Example 1, 103.4 g of ion-exchanged water, 2.4 g of disodium hydrogen phosphate, 0.04 g of sodium hydroxide, tert-butanol were added to the reactor. As a fluorine-containing emulsifier, 0.83 g of C 2 F 5 OCF 2 CF 2 OCF 2 COONH 4 and 0.62 g of 1,4-diiodoperfluorobutane were added. Next, a monomer mixed gas (first monomer component) of TFE / P = 88/12 (molar ratio) at 80 ° C. was injected so that the internal pressure of the reactor became 2.00 MPaG. The anchor blade was rotated at 280 rpm, and a 2.0 mass% aqueous solution of ammonium persulfate was pressed into the reactor. Thereafter, a 2.0 mass% aqueous solution of ammonium persulfate was intermittently injected. The polymerization temperature is maintained at 80 ° C. and the polymerization proceeds. As the polymerization proceeds, the pressure in the reactor decreases, so that the internal pressure of the reactor is maintained at 2.00 MPaG. TFE / P = 56/44 (Molar ratio) monomer mixture gas (first monomer component) was continuously injected to continue the polymerization reaction. When the total amount of the monomer mixture gas composed of TFE and propylene reached 9.4 g, the addition of the 2% by weight ammonium persulfate aqueous solution was stopped, the internal temperature of the reactor was cooled to 10 ° C., and the polymerization reaction was performed. Then, a latex of TFE / P copolymer C was obtained.
The obtained latex had a pH of 8.2. The amount of ammonium persulfate 2% by mass aqueous solution added was 15 g. The polymerization time was 6 hours and 30 minutes. Freezing, thawing, washing and drying were carried out in the same manner as in Polymerization Example 1 to obtain 9.5 g of white TFE / P copolymer C. The ratio of units based on TFE and units based on propylene in TFE / P copolymer C was 56:44 (molar ratio). The number average molecular weight (Mn) of the TFE / P copolymer C was 15000, the mass average molecular weight (Mw) was 27000, and the molecular weight distribution (Mw / Mn) was 1.8. TFE / P copolymer C had no melting point and the 5% weight loss temperature was 402 ° C. The TFE / P copolymer C was too fluid and the Q value at 300 ° C. could not be measured.
［重合例４］ＴＦＥ／Ｐ共重合体（ＴＦＥ／Ｐ系セグメント）の製造（第１の工程）：重合温度８０℃。
１，４−ジヨードパーフルオロブタンの０．１０ｇを使用した以外は重合例３と同様な操作によって重合を行った。
得られたＴＦＥ／Ｐ共重合体ＤのラテックスのｐＨは８．２であった。過硫酸アンモニウム２質量％水溶液の添加量は１５ｇであった。重合時間は６時間１０分であった。重合例１と同様に凍結、解凍、洗浄、乾燥を行い、白色のＴＦＥ／Ｐ共重合体Ｄの９．５ｇを得た。ＴＦＥ／Ｐ共重合体Ｄ中のＴＦＥに基づく単位とプロピレンに基づく単位との比率は、５６：４４（モル比）であった。ＴＦＥ／Ｐ共重合体Ｄの融点は無く、５％重量減少温度は４０５℃であった。ＴＦＥ／Ｐ共重合体Ｄは流動性が大きすぎて、３００℃でのＱ値を測定できなかった。
[Polymerization Example 4] Production of TFE / P copolymer (TFE / P segment) (first step): polymerization temperature of 80 ° C.
Polymerization was carried out in the same manner as in Polymerization Example 3 except that 0.10 g of 1,4-diiodoperfluorobutane was used.
The latex of the obtained TFE / P copolymer D had a pH of 8.2. The amount of ammonium persulfate 2% by mass aqueous solution added was 15 g. The polymerization time was 6 hours and 10 minutes. Freezing, thawing, washing and drying were carried out in the same manner as in Polymerization Example 1 to obtain 9.5 g of white TFE / P copolymer D. The ratio of the units based on TFE and the units based on propylene in the TFE / P copolymer D was 56:44 (molar ratio). The TFE / P copolymer D had no melting point and the 5% weight loss temperature was 405 ° C. The TFE / P copolymer D was too fluid and the Q value at 300 ° C. could not be measured.
［実施例１］含フッ素ブロックコポリマーの製造：重合温度２５℃；分子量、分子量分布が測定できるような低分子量体。
重合例１と同様の操作を行って、ＴＦＥ／Ｐ共重合体Ａのラテックスを得た。反応器の内温を１０℃まで冷却し、重合反応を停止した後、アンカー翼の回転を止め、反応器内の未反応モノマーを大気圧まで空放した。
その後、アンカー翼を２８０ｒｐｍで回転させ、反応器の内温を２５℃としてＴＦＥ／Ｅ＝８３／１７（モル比）のモノマー混合ガス（第２のモノマー成分）を、反応器の内圧が１．１ＭＰａＧになるように圧入した。そして、ロンガリット１．２質量％水溶液を反応器に加え、重合反応を再開させた（第２の工程）。その後、断続的にロンガリット１．２％質量％水溶液を圧入した。重合の進行に伴い、反応器内の圧力が低下するので、反応器の内圧が１．１ＭＰａＧを維持するようにＴＦＥ／Ｅ＝５４／４６（モル比）のモノマー混合ガス（第２のモノマー成分）を連続的に圧入して、重合反応を続けた。ＴＦＥとエチレンからなるモノマー混合ガスの圧入量の総量が１１．５ｇとなった時点で、ロンガリット１．２質量％水溶液の添加を停止し、反応器の内温を１０℃まで冷却し、重合反応を停止し、含フッ素ブロックコポリマーＡ１のラテックスを得た。得られたラテックスのｐＨは８．０であった。重合反応を再開させた後のロンガリット１．２質量％の水溶液の添加量は、１６．０ｇであり、重合時間は４時間３０分であった。
重合例１と同様に凍結、解凍、洗浄、乾燥を行い、白色の含フッ素ブロックコポリマーＡ１の２１．２ｇを得た。ＴＦＥ／Ｐ系セグメントと、ＴＦＥ／Ｅ系セグメントとの質量比は、重合例１で得られたＴＦＥ／Ｐ共重合体Ａ量及び実施例１で得られた含フッ素ブロックコポリマーＡ１量よりの計算値４４：５６であった。またＴＦＥ／Ｅ系セグメント中のＴＦＥに基づく単位とエチレンに基づく単位との比率は、５４：４６（モル比）であった。
含フッ素ブロックコポリマーＡ１の数平均分子量（Ｍｎ）は５６０００、質量平均分子量（Ｍｗ）は１１００００、分子量分布（Ｍｗ／Ｍｎ）は２．０であった。重合例１のＴＦＥ／Ｐ共重合体Ａの収量は９．４ｇで、実施例１の含フッ素ブロックコポリマーＡ１の収量は２１．２ｇであった。重合例１の第１の工程で得られたＴＦＥ／Ｐ共重合体ＡのＭｎをＴＦＥ／Ｐ共重合体Ａの質量で割った値（Ｓ）と、実施例１で得られた含フッ素ブロックコポリマーＡ１のＭｎを含フッ素ブロックコポリマーＡ１の質量で割った値（Ｔ）との比Ｓ：Ｔは、（２３０００／９．４）：（５６０００／２１．２）＝１：１．０８であった。このことは、ＴＦＥ／Ｐ共重合体Ａ分子の数と含フッ素ブロックコポリマーＡ１分子の数がほぼ同じであることを示していて、含フッ素ブロックコポリマーＡ１にはＴＦＥ／Ｅセグメントのみを含むポリマーは殆ど存在していないことが示唆される。
含フッ素ブロックコポリマーＡ１の融点は２４９℃であり、５％重量減少温度は４３１℃であった。含フッ素ブロックコポリマーＡ１は流動性が大きすぎて、３００℃でのＱ値は測定できなかった。
[Example 1] Production of fluorine-containing block copolymer: Polymerization temperature 25 ° C; low molecular weight substance capable of measuring molecular weight and molecular weight distribution.
The same operation as in Polymerization Example 1 was performed to obtain a latex of TFE / P copolymer A. After the internal temperature of the reactor was cooled to 10 ° C. and the polymerization reaction was stopped, the rotation of the anchor blade was stopped and the unreacted monomer in the reactor was released to atmospheric pressure.
Thereafter, the anchor blade is rotated at 280 rpm, the internal temperature of the reactor is set to 25 ° C., a monomer mixed gas (second monomer component) of TFE / E = 83/17 (molar ratio), and the internal pressure of the reactor is 1. Press-fitting was performed to 1 MPaG. Then, Rongalite 1.2% by mass aqueous solution was added to the reactor to restart the polymerization reaction (second step). Then, Rongalite 1.2% mass% aqueous solution was intermittently injected. As the polymerization proceeds, the pressure in the reactor decreases. Therefore, a monomer mixed gas (second monomer component) of TFE / E = 54/46 (molar ratio) so that the internal pressure of the reactor is maintained at 1.1 MPaG. ) Was continuously injected to continue the polymerization reaction. When the total amount of the monomer mixture gas consisting of TFE and ethylene reached 11.5 g, the addition of Rongalite 1.2 mass% aqueous solution was stopped, the internal temperature of the reactor was cooled to 10 ° C., and the polymerization reaction Was stopped to obtain a latex of the fluorine-containing block copolymer A1. The obtained latex had a pH of 8.0. The amount of Rongalite 1.2 mass% aqueous solution added after resuming the polymerization reaction was 16.0 g, and the polymerization time was 4 hours and 30 minutes.
Freezing, thawing, washing and drying were carried out in the same manner as in Polymerization Example 1 to obtain 21.2 g of a white fluorine-containing block copolymer A1. The mass ratio of the TFE / P segment and the TFE / E segment was calculated from the amount of TFE / P copolymer A obtained in Polymerization Example 1 and the amount of fluorine-containing block copolymer A1 obtained in Example 1. The value was 44:56. The ratio of the units based on TFE to the units based on ethylene in the TFE / E segment was 54:46 (molar ratio).
The number average molecular weight (Mn) of the fluorine-containing block copolymer A1 was 56000, the mass average molecular weight (Mw) was 110000, and the molecular weight distribution (Mw / Mn) was 2.0. The yield of TFE / P copolymer A of Polymerization Example 1 was 9.4 g, and the yield of fluorine-containing block copolymer A1 of Example 1 was 21.2 g. The value (S) obtained by dividing Mn of the TFE / P copolymer A obtained in the first step of Polymerization Example 1 by the mass of the TFE / P copolymer A, and the fluorine-containing block obtained in Example 1 The ratio S: T of Mn of the copolymer A1 divided by the mass of the fluorine-containing block copolymer A1 (T) was (23000 / 9.4) :( 56000 / 21.2) = 1: 1.08. It was. This indicates that the number of TFE / P copolymer A molecules and the number of fluorine-containing block copolymer A1 molecules are almost the same, and the polymer containing only the TFE / E segment in the fluorine-containing block copolymer A1 is It is suggested that there is hardly any.
The melting point of the fluorinated block copolymer A1 was 249 ° C., and the 5% weight loss temperature was 431 ° C. The fluorine-containing block copolymer A1 was too fluid and the Q value at 300 ° C. could not be measured.
［比較例１］含フッ素ブロックコポリマーの製造：重合温度は第１の工程、第２の工程ともに８０℃；分子量、分子量分布が測定できるような低分子量体。
重合例３と同様の操作を行って、ＴＦＥ／Ｐ共重合体Ｃのラテックスを得た（第１の工程）。反応器の内温を１０℃まで冷却し、重合反応を停止した後、アンカー翼の回転を止め、反応器内の未反応モノマーを大気圧まで空放した。
その後、反応器の内温を８０℃としてＴＦＥ／Ｅ＝８３／１７（モル比）のモノマー混合ガス（第２のモノマー成分）を、反応器の内圧が１．６０ＭＰａＧになるように圧入した。そして、過硫酸アンモニウムの２．０質量％水溶液を断続的に圧入して、重合反応を再開させた（第２の工程）。重合の進行に伴い、反応器内の圧力が低下するので、反応器の内圧が１．６０ＭＰａＧを維持するようにＴＦＥ／Ｅ＝５４／４６（モル比）のモノマー混合ガス（第２のモノマー成分）を連続的に圧入して、重合反応を続けた。ＴＦＥとエチレンからなるモノマー混合ガスの圧入量の総量が１１．５ｇとなった時点で、過硫酸アンモニウムの２質量％水溶液の添加を停止し、反応器の内温を１０℃まで冷却し、重合反応を停止し、含フッ素ブロックコポリマーＣ１のラテックスを得た。得られたラテックスのｐＨは８．３であった。重合反応を再開させた後の過硫酸アンモニウム２質量％の水溶液の添加量は、１８．０ｇであり、重合時間は４時間３０分であった。
重合例１と同様に凍結、解凍、洗浄、乾燥を行い、白色の含フッ素ブロックコポリマーＣ１の２０．８ｇを得た。ＴＦＥ／Ｐ系セグメントと、ＴＦＥ／Ｅ系セグメントとの質量比は、重合例３で得られたＴＦＥ／Ｐ共重合体Ｃ量及び比較例１で得られた含フッ素ブロックコポリマーＣ１量よりの計算値４７：５３であった。またＴＦＥ／Ｅ系セグメント中のＴＦＥに基づく単位とエチレンに基づく単位との比率は、５４：４６（モル比）であった。
含フッ素ブロックコポリマーＣ１の数平均分子量（Ｍｎ）は２５０００、質量平均分子量（Ｍｗ）は６２０００、分子量分布（Ｍｗ／Ｍｎ）は２．５であった。重合例３の第１の工程で得られたＴＦＥ／Ｐ共重合体ＣのＭｎをＴＦＥ／Ｐ共重合体Ｃの質量で割った値（Ｓ）と、比較例１で得られた含フッ素ブロックコポリマーＣ１のＭｎを含フッ素ブロックコポリマーＣ１の質量で割った値（Ｔ）との比Ｓ：Ｔは、（１５０００／９．５）：（２５０００／２０．８）＝１：０．７６であった。このことは、重合例３で生成したＴＦＥ／Ｐ共重合体Ｃの分子数よりも比較例１で得られた含フッ素ブロックコポリマーＣ１の分子数の方が多いことを示していて、含フッ素ブロックコポリマーＣ１にはＴＦＥ／Ｅセグメントのみを含むポリマーがかなり存在していることが示唆される。重合例３の重合温度が高いためにプロピレン等にポリマーラジカルが連鎖移動してしまい、生成したＴＦＥ／Ｐ共重合体Ｃには末端がヨウ素でないものがかなり含まれているためと考えられる。
含フッ素ブロックコポリマーＣ１の融点は２４９℃であり、５％重量減少温度は４３０℃であった。含フッ素ブロックコポリマーＣ１は流動性が大きすぎて、３００℃でのＱ値は測定できなかった。
[Comparative Example 1] Production of fluorine-containing block copolymer: polymerization temperature is 80 ° C in both the first step and the second step; a low molecular weight substance capable of measuring molecular weight and molecular weight distribution.
The same operation as in Polymerization Example 3 was performed to obtain a latex of TFE / P copolymer C (first step). After the internal temperature of the reactor was cooled to 10 ° C. and the polymerization reaction was stopped, the rotation of the anchor blade was stopped and the unreacted monomer in the reactor was released to atmospheric pressure.
Thereafter, the internal temperature of the reactor was set to 80 ° C., and a monomer mixed gas (second monomer component) of TFE / E = 83/17 (molar ratio) was injected so that the internal pressure of the reactor became 1.60 MPaG. And the 2.0 mass% aqueous solution of ammonium persulfate was intermittently injected, and the polymerization reaction was restarted (2nd process). As the polymerization proceeds, the pressure in the reactor decreases, so that a monomer mixed gas (second monomer component) of TFE / E = 54/46 (molar ratio) so that the internal pressure of the reactor is maintained at 1.60 MPaG. ) Was continuously injected to continue the polymerization reaction. When the total amount of the monomer mixture gas consisting of TFE and ethylene reached 11.5 g, the addition of the 2 mass% aqueous solution of ammonium persulfate was stopped, the internal temperature of the reactor was cooled to 10 ° C., and the polymerization reaction Was stopped to obtain a latex of the fluorine-containing block copolymer C1. The pH of the obtained latex was 8.3. The amount of the aqueous solution of ammonium persulfate 2% by mass after resuming the polymerization reaction was 18.0 g, and the polymerization time was 4 hours 30 minutes.
Freezing, thawing, washing and drying were carried out in the same manner as in Polymerization Example 1 to obtain 20.8 g of a white fluorine-containing block copolymer C1. The mass ratio of the TFE / P segment and the TFE / E segment was calculated from the amount of TFE / P copolymer C obtained in Polymerization Example 3 and the amount of fluorine-containing block copolymer C1 obtained in Comparative Example 1. Value 47:53. The ratio of the units based on TFE to the units based on ethylene in the TFE / E segment was 54:46 (molar ratio).
The number average molecular weight (Mn) of the fluorine-containing block copolymer C1 was 25000, the mass average molecular weight (Mw) was 62000, and the molecular weight distribution (Mw / Mn) was 2.5. The value (S) obtained by dividing Mn of the TFE / P copolymer C obtained in the first step of Polymerization Example 3 by the mass of the TFE / P copolymer C, and the fluorine-containing block obtained in Comparative Example 1 The ratio S: T of Mn of the copolymer C1 divided by the mass of the fluorine-containing block copolymer C1 (T) was (15000 / 9.5) :( 25000 / 20.8) = 1: 0.76. It was. This indicates that the number of molecules of the fluorine-containing block copolymer C1 obtained in Comparative Example 1 is larger than the number of molecules of the TFE / P copolymer C produced in Polymerization Example 3. It is suggested that there is a significant amount of polymer containing only TFE / E segments in copolymer C1. This is probably because the polymerization temperature of Polymerization Example 3 is high, so that polymer radicals are chain-transferred to propylene or the like, and the produced TFE / P copolymer C contains a considerable amount of the terminal that is not iodine.
The melting point of the fluorinated block copolymer C1 was 249 ° C., and the 5% weight loss temperature was 430 ° C. The fluorine-containing block copolymer C1 was too fluid and the Q value at 300 ° C. could not be measured.
［実施例２］含フッ素ブロックコポリマーの製造：重合温度は第１の工程、第２の工程ともに２５℃。
重合例２と同様の操作を行って、ＴＦＥ／Ｐ共重合体Ｂのラテックスを得た（第１の工程）。反応器の内温を１０℃まで冷却し、重合反応を停止した後、アンカー翼の回転を止め、反応器内の未反応モノマーを大気圧まで空放した。
その後、実施例１と同様の操作により含フッ素ブロックコポリマーＢ１のラテックスを得た。得られたラテックスのｐＨは８．０であった。重合反応を再開させた後のロンガリット１．２質量％の水溶液の添加量は、１６．０ｇであり、重合時間は４時間１５分であった。重合例１と同様に凍結、解凍、洗浄、乾燥を行い、白色の含フッ素ブロックコポリマーＢ１の２０．６ｇを得た。
ＴＦＥ／Ｐ系セグメントと、ＴＦＥ／Ｅ系セグメントとの質量比は、重合例２で得られたＴＦＥ／Ｐ共重合体Ｂ量及び実施例２で得られた含フッ素ブロックコポリマーＢ１量よりの計算値４７：５３であった。またＴＦＥ／Ｅ系セグメント中のＴＦＥに基づく単位とエチレンに基づく単位との比率は、５４：４６（モル比）であった。含フッ素ブロックコポリマーＢ１の融点は２５２℃であり、５％重量減少温度は４３３℃であった。３００℃でのＱ値は１１．７ｍｍ３／ｓであった。２５℃周波数１０Ｈｚでの引張弾性率は１２０ＭＰａ、引張破断強度は１４．８ＭＰａ、引張破断伸度は４４０％、波長８００ｎｍの光透過率は９０．９％であった。これらの結果を表１に示す。
[Example 2] Production of fluorine-containing block copolymer: The polymerization temperature was 25 ° C in both the first step and the second step.
The same operation as in Polymerization Example 2 was performed to obtain a latex of TFE / P copolymer B (first step). After the internal temperature of the reactor was cooled to 10 ° C. and the polymerization reaction was stopped, the rotation of the anchor blade was stopped and the unreacted monomer in the reactor was released to atmospheric pressure.
Then, the latex of fluorine-containing block copolymer B1 was obtained by the same operation as Example 1. The obtained latex had a pH of 8.0. The amount of Rongalite 1.2 mass% aqueous solution after resuming the polymerization reaction was 16.0 g, and the polymerization time was 4 hours and 15 minutes. Freezing, thawing, washing, and drying were performed in the same manner as in Polymerization Example 1 to obtain 20.6 g of a white fluorine-containing block copolymer B1.
The mass ratio of the TFE / P segment and the TFE / E segment is calculated from the amount of TFE / P copolymer B obtained in Polymerization Example 2 and the amount of fluorine-containing block copolymer B1 obtained in Example 2. Value 47:53. The ratio of the units based on TFE to the units based on ethylene in the TFE / E segment was 54:46 (molar ratio). The melting point of the fluorinated block copolymer B1 was 252 ° C., and the 5% weight loss temperature was 433 ° C. The Q value at 300 ° C. was 11.7 mm 3 / s. The tensile elastic modulus at a frequency of 25 ° C. and a frequency of 10 Hz was 120 MPa, the tensile strength at break was 14.8 MPa, the tensile elongation at break was 440%, and the light transmittance at a wavelength of 800 nm was 90.9%. These results are shown in Table 1.
［実施例３］含フッ素ブロックコポリマーの製造：重合温度は第１の工程２５℃、第２の工程８０℃。
重合例２と同様の操作を行って、ＴＦＥ／Ｐ共重合体Ｂのラテックスを得た（第１の工程）。反応器の内温を１０℃まで冷却し、重合反応を停止した後、アンカー翼の回転を止め、反応器内の未反応モノマーを大気圧まで空放した。その後、アンカー翼を２８０ｒｐｍで回転させ、反応器の内温を８０℃としてＴＦＥ／Ｅ＝８３／１７（モル比）のモノマー混合ガス（第２のモノマー成分）を、反応器の内圧が１．６０ＭＰａＧになるように圧入した。そして、過硫酸アンモニウムの２質量％水溶液を反応器に加え、重合反応を再開させた（第２の工程）。その後、過硫酸アンモニウムの２質量％水溶液を断続的に反応器に加えた。重合の進行に伴い、反応器内の圧力が低下するので、反応器の内圧が１．６０ＭＰａＧを維持するようにＴＦＥ／Ｅ＝５４／４６（モル比）のモノマー混合ガス（第２のモノマー成分）を連続的に圧入して、重合反応を続けた。ＴＦＥとエチレンからなるモノマー混合ガスの圧入量の総量が１１．５ｇとなった時点で、過硫酸アンモニウムの２質量％水溶液の添加を停止し、反応器の内温を１０℃まで冷却し、重合反応を停止し、含フッ素ブロックコポリマーＢ２のラテックスを得た。得られたラテックスのｐＨは８．０であった。重合反応を再開させた後の過硫酸アンモニウムの２．０質量％の水溶液の添加量は、６．０ｇであり、重合時間は４時間３０分であった。
重合例１と同様に凍結、解凍、洗浄、乾燥を行い、白色の含フッ素ブロックコポリマーＢ２の２１．０ｇを得た。
ＴＦＥ／Ｐ系セグメントと、ＴＦＥ／Ｅ系セグメントとの質量比は、重合例２で得られたＴＦＥ／Ｐ共重合体Ｂ量及び実施例３で得られた含フッ素ブロックコポリマーＢ２量よりの計算値４６：５４であった。またＴＦＥ／Ｅ系セグメント中のＴＦＥに基づく単位とエチレンに基づく単位との比率は、５４：４６（モル比）であった。該含フッ素ブロックコポリマーＢ２の融点は２５０℃であり、５％重量減少温度は４３０℃であった。３００℃でのＱ値は１５．７ｍｍ３／ｓであった。２５℃周波数１０Ｈｚでの引張弾性率は１１５ＭＰａ、引張破断強度は１２．５ＭＰａ、引張破断伸度は４５０％、波長８００ｎｍの光透過率は９１．０％であった。これらの結果を表１に示す。
[Example 3] Production of fluorine-containing block copolymer: Polymerization temperature was 25 ° C in the first step and 80 ° C in the second step.
The same operation as in Polymerization Example 2 was performed to obtain a latex of TFE / P copolymer B (first step). After the internal temperature of the reactor was cooled to 10 ° C. and the polymerization reaction was stopped, the rotation of the anchor blade was stopped and the unreacted monomer in the reactor was released to atmospheric pressure. Thereafter, the anchor blade is rotated at 280 rpm, the internal temperature of the reactor is set to 80 ° C., a monomer mixed gas (second monomer component) of TFE / E = 83/17 (molar ratio), and the internal pressure of the reactor is 1. Press-fitting was performed to 60 MPaG. And the 2 mass% aqueous solution of ammonium persulfate was added to the reactor, and the polymerization reaction was restarted (2nd process). Thereafter, a 2% by weight aqueous solution of ammonium persulfate was intermittently added to the reactor. As the polymerization proceeds, the pressure in the reactor decreases, so that a monomer mixed gas (second monomer component) of TFE / E = 54/46 (molar ratio) so that the internal pressure of the reactor is maintained at 1.60 MPaG. ) Was continuously injected to continue the polymerization reaction. When the total amount of the monomer mixture gas consisting of TFE and ethylene reached 11.5 g, the addition of the 2 mass% aqueous solution of ammonium persulfate was stopped, the internal temperature of the reactor was cooled to 10 ° C., and the polymerization reaction And a latex of fluorine-containing block copolymer B2 was obtained. The obtained latex had a pH of 8.0. The amount of ammonium persulfate aqueous solution added after resuming the polymerization reaction was 6.0 g, and the polymerization time was 4 hours 30 minutes.
Freezing, thawing, washing and drying were carried out in the same manner as in Polymerization Example 1 to obtain 21.0 g of a white fluorine-containing block copolymer B2.
The mass ratio of the TFE / P segment and the TFE / E segment is calculated from the amount of TFE / P copolymer B obtained in Polymerization Example 2 and the amount of fluorine-containing block copolymer B2 obtained in Example 3. The value was 46:54. The ratio of the units based on TFE to the units based on ethylene in the TFE / E segment was 54:46 (molar ratio). The melting point of the fluorine-containing block copolymer B2 was 250 ° C., and the 5% weight loss temperature was 430 ° C. The Q value at 300 ° C. was 15.7 mm 3 / s. The tensile modulus at 25 ° C. and the frequency of 10 Hz was 115 MPa, the tensile strength at break was 12.5 MPa, the tensile elongation at break was 450%, and the light transmittance at a wavelength of 800 nm was 91.0%. These results are shown in Table 1.
［比較例２］ブロックコポリマーの製造：重合温度は第１の工程８０℃、第２の工程２５℃
重合例４と同様の操作を行って、ＴＦＥ／Ｐ共重合体Ｄのラテックスを得た（第１の工程）。反応器の内温を１０℃まで冷却し、重合反応を停止した後、アンカー翼の回転を止め、反応器内の未反応モノマーを大気圧まで空放した。
その後、イオン交換水１８．４ｇに過硫酸アンモニウムの０．６ｇ、エチレンジアミン四酢酸二ナトリウム塩二水和物の０．０２２ｇと、硫酸第一鉄７水和物の０．０１７ｇとを溶解させた水溶液を仕込み、実施例２と同様の操作により含フッ素ブロックコポリマーＤ１のラテックスを得た。得られたラテックスのｐＨは８．０であった。重合反応を再開させた後のロンガリット１．２質量％の水溶液の添加量は、１６．０ｇであり、重合時間は４時間であった。
重合例１と同様に凍結、解凍、洗浄、乾燥を行い、白色の含フッ素ブロックコポリマーＤ１の２０．６ｇを得た。
ＴＦＥ／Ｐ系セグメントと、ＴＦＥ／Ｅ系セグメントとの質量比は、重合例４で得られたＴＦＥ／Ｐ共重合体Ｄ量及び比較例２で得られた含フッ素ブロックコポリマーＤ１量よりの計算値４６：５４であった。またＴＦＥ／Ｅ系セグメント中のＴＦＥに基づく単位とエチレンに基づく単位との比率は、５４：４６（モル比）であった。含フッ素ブロックコポリマーＤ１の融点は２５２℃であり、５％重量減少温度は４３１℃であった。３００℃でのＱ値は１５．４ｍｍ３／ｓであった。２５℃周波数１０Ｈｚでの引張弾性率は１２０ＭＰａ、引張破断強度は１０．８ＭＰａ、引張破断伸度は３２０％、波長８００ｎｍの光透過率は８８．８％であった。これらの結果を表１に示す。
[Comparative Example 2] Production of block copolymer: polymerization temperature was 80 ° C in the first step and 25 ° C in the second step.
The same operation as in Polymerization Example 4 was performed to obtain a latex of TFE / P copolymer D (first step). After the internal temperature of the reactor was cooled to 10 ° C. and the polymerization reaction was stopped, the rotation of the anchor blade was stopped and the unreacted monomer in the reactor was released to atmospheric pressure.
Thereafter, 0.6 g of ammonium persulfate, 0.022 g of ethylenediaminetetraacetic acid disodium salt dihydrate and 0.017 g of ferrous sulfate heptahydrate were dissolved in 18.4 g of ion-exchanged water. And a latex of a fluorine-containing block copolymer D1 was obtained by the same operation as in Example 2. The obtained latex had a pH of 8.0. The amount of Rongalite 1.2 mass% aqueous solution after resuming the polymerization reaction was 16.0 g, and the polymerization time was 4 hours.
Freezing, thawing, washing, and drying were performed in the same manner as in Polymerization Example 1 to obtain 20.6 g of a white fluorine-containing block copolymer D1.
The mass ratio of the TFE / P segment and the TFE / E segment was calculated from the amount of TFE / P copolymer D obtained in Polymerization Example 4 and the amount of fluorine-containing block copolymer D1 obtained in Comparative Example 2. The value was 46:54. The ratio of the units based on TFE to the units based on ethylene in the TFE / E segment was 54:46 (molar ratio). The melting point of the fluorinated block copolymer D1 was 252 ° C., and the 5% weight loss temperature was 431 ° C. The Q value at 300 ° C. was 15.4 mm 3 / s. The tensile modulus at 25 ° C. and 10 Hz was 120 MPa, the tensile strength at break was 10.8 MPa, the tensile elongation at break was 320%, and the light transmittance at a wavelength of 800 nm was 88.8%. These results are shown in Table 1.
［比較例３］含フッ素ブロックコポリマーの製造：重合温度は、第１の工程、第２の工程ともに８０℃。
重合例４と同様の操作を行って、ＴＦＥ／Ｐ共重合体Ｄのラテックスを得た（第１の工程）。反応器の内温を１０℃まで冷却し、重合反応を停止した後、アンカー翼の回転を止め、反応器内の未反応モノマーを大気圧まで空放した。
その後、反応器の内温を８０℃としてＴＦＥ／Ｅ＝８３／１７（モル比）のモノマー混合ガス（第２のモノマー成分）を、反応器の内圧が１．６０ＭＰａＧになるように圧入した。そして、過硫酸アンモニウムの２．０質量％水溶液を断続的に圧入して、重合反応を再開させた（第２の工程）。重合の進行に伴い、反応器内の圧力が低下するので、反応器の内圧が１．６０ＭＰａＧを維持するようにＴＦＥ／Ｅ＝５４／４６（モル比）のモノマー混合ガス（第２のモノマー成分）を連続的に圧入して、重合反応を続けた。ＴＦＥとエチレンからなるモノマー混合ガスの圧入量の総量が１１．５ｇとなった時点で、過硫酸アンモニウムの２質量％水溶液の添加を停止し、反応器の内温を１０℃まで冷却し、重合反応を停止し、含フッ素ブロックコポリマーＤ２のラテックスを得た。得られたラテックスのｐＨは８．３であった。重合反応を再開させ後の過硫酸アンモニウム２質量％の水溶液の添加量は、１６．０ｇであり、重合時間は４時間３０分であった。
重合例１と同様に凍結、解凍、洗浄、乾燥を行い、白色の含フッ素ブロックコポリマーＤ２の２１．０ｇを得た。
ＴＦＥ／Ｐ系セグメントと、ＴＦＥ／Ｅ系セグメントとの質量比は、ＴＦＥ／Ｐ共重合体Ｄ量及び含フッ素ブロックコポリマーＤ２量よりの計算値４５：５５であった。またＴＦＥ／Ｅ系セグメント中のＴＦＥに基づく単位とエチレンに基づく単位との比率は、５４：４６（モル比）であった。含フッ素ブロックコポリマーＤ２の融点は２５４℃であり、５％重量減少温度は４３０℃であった。３００℃でのＱ値は２７．０ｍｍ３／ｓであった。２５℃周波数１０Ｈｚでの引張弾性率は１２０ＭＰａ、引張破断強度は１０．５ＭＰａ、引張破断伸度は２８０％、波長８００ｎｍの光透過率は８５．５％であった。これらの結果を表１に示す。
[Comparative Example 3] Production of fluorine-containing block copolymer: The polymerization temperature was 80 ° C in both the first step and the second step.
The same operation as in Polymerization Example 4 was performed to obtain a latex of TFE / P copolymer D (first step). After the internal temperature of the reactor was cooled to 10 ° C. and the polymerization reaction was stopped, the rotation of the anchor blade was stopped and the unreacted monomer in the reactor was released to atmospheric pressure.
Thereafter, the internal temperature of the reactor was set to 80 ° C., and a monomer mixed gas (second monomer component) of TFE / E = 83/17 (molar ratio) was injected so that the internal pressure of the reactor became 1.60 MPaG. And the 2.0 mass% aqueous solution of ammonium persulfate was intermittently injected, and the polymerization reaction was restarted (2nd process). As the polymerization proceeds, the pressure in the reactor decreases, so that a monomer mixed gas (second monomer component) of TFE / E = 54/46 (molar ratio) so that the internal pressure of the reactor is maintained at 1.60 MPaG. ) Was continuously injected to continue the polymerization reaction. When the total amount of the monomer mixture gas consisting of TFE and ethylene reached 11.5 g, the addition of the 2 mass% aqueous solution of ammonium persulfate was stopped, the internal temperature of the reactor was cooled to 10 ° C., and the polymerization reaction And a latex of fluorine-containing block copolymer D2 was obtained. The pH of the obtained latex was 8.3. The amount of the aqueous solution of ammonium persulfate 2% by mass after resuming the polymerization reaction was 16.0 g, and the polymerization time was 4 hours 30 minutes.
Freezing, thawing, washing and drying were performed in the same manner as in Polymerization Example 1 to obtain 21.0 g of a white fluorine-containing block copolymer D2.
The mass ratio of the TFE / P segment to the TFE / E segment was 45:55 calculated from the amount of TFE / P copolymer D and the amount of fluorine-containing block copolymer D2. The ratio of the units based on TFE to the units based on ethylene in the TFE / E segment was 54:46 (molar ratio). The melting point of the fluorinated block copolymer D2 was 254 ° C., and the 5% weight loss temperature was 430 ° C. The Q value at 300 ° C. was 27.0 mm 3 / s. The tensile elastic modulus at 25 ° C. and the frequency of 10 Hz was 120 MPa, the tensile strength at break was 10.5 MPa, the tensile elongation at break was 280%, and the light transmittance at a wavelength of 800 nm was 85.5%. These results are shown in Table 1.
［比較例４］ＴＦＥ／Ｅ共重合体とＴＦＥ／Ｐ共重合体とのブレンド
ＴＦＥ／Ｅ共重合体（フルオンＬＭ７３０、旭硝子（株）製）とＴＦＥ／Ｐ共重合体（アフラス１５０ＣＳ、旭硝子（株）製）とを（株）東洋精機製作所製ラボプラストミルにて、３００℃で溶融混合した。ＴＦＥ／Ｅ共重合体とＴＦＥ／Ｐ共重合体との質量比は、５５：４５とした。
得られた混合物の融点、５％重量減少温度、３００℃でのＱ値は表１に示すとおりであった。また、表１に示すとおり、２５℃周波数１０Ｈｚでの引張弾性率は２３０ＭＰａ、引張破断強度は１７．３ＭＰａ、引張破断伸度は２７４％、波長８００ｎｍの光透過率は８６．０％であった。
[Comparative Example 4] Blend of TFE / E copolymer and TFE / P copolymer TFE / E copolymer (Fullon LM730, manufactured by Asahi Glass Co., Ltd.) and TFE / P copolymer (Aphras 150CS, Asahi Glass ( Manufactured by Toyo Seiki Seisakusho Co., Ltd. at 300 ° C. The mass ratio of the TFE / E copolymer and the TFE / P copolymer was 55:45.
Table 1 shows the melting point, the 5% weight loss temperature, and the Q value at 300 ° C. of the obtained mixture. As shown in Table 1, the tensile modulus at 25 ° C. and the frequency of 10 Hz was 230 MPa, the tensile strength at break was 17.3 MPa, the tensile elongation at break was 274%, and the light transmittance at a wavelength of 800 nm was 86.0%. .
以上の結果から、本発明の方法で得られたＴＦＥ／ＥセグメントとＴＦＥ／Ｐセグメントを有するブロックコポリマーは、引張弾性率が低く、引張破断強度、引張破断伸度が高く、光透過性が高い。よって、軟質電線の被覆材として、また、展張性に優れるビニールハウス等の農業用フィルムとして、適している。 From the above results, the block copolymer having the TFE / E segment and the TFE / P segment obtained by the method of the present invention has a low tensile elastic modulus, a high tensile breaking strength, a high tensile breaking elongation, and a high light transmittance. . Therefore, it is suitable as a covering material for a soft electric wire and as an agricultural film for a greenhouse or the like having excellent stretchability.
Claims (3)
前記テトラフルオロエチレン／プロピレン系セグメントの存在下に、テトラフルオロエチレンとエチレンとを主成分とする第２のモノマー成分を共重合し、前記テトラフルオロエチレン／プロピレン系セグメントに、テトラフルオロエチレン／エチレン系セグメントを結合する第２の工程とを有し、
前記第２の工程において、前記テトラフルオロエチレン／プロピレン系セグメントと、前記テトラフルオロエチレン／エチレン系セグメントとの質量比が、３０：７０〜７０：３０となるように、前記テトラフルオロエチレン／プロピレン系セグメントおよび前記第２のモノマー成分を供給することを特徴とする含フッ素ブロックコポリマーの製造方法。 Mainly tetrafluoroethylene and propylene in the presence of a radical polymerization initiator and an iodine compound represented by the general formula RI 2 (wherein R is an alkylene group or fluoroalkylene group having 3 or more carbon atoms). A first step of copolymerizing a first monomer component as a component at a polymerization temperature of 0 to 50 ° C. to produce a tetrafluoroethylene / propylene-based segment;
In the presence of the tetrafluoroethylene / propylene segment, a second monomer component mainly composed of tetrafluoroethylene and ethylene is copolymerized, and the tetrafluoroethylene / propylene segment is tetrafluoroethylene / ethylene-based. It has a second step of coupling the segments,
In the second step, the tetrafluoroethylene / propylene-based segment so that the mass ratio of the tetrafluoroethylene / propylene-based segment and the tetrafluoroethylene / ethylene-based segment is 30:70 to 70:30. A method for producing a fluorine-containing block copolymer, comprising supplying a segment and the second monomer component .
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| WO2017188397A1 (en) * | 2016-04-28 | 2017-11-02 | 旭硝子株式会社 | Coated cable |
| CN110191919B (en) | 2017-01-18 | 2022-01-18 | 3M创新有限公司 | Fluorinated block copolymers |
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