JPH02151610A - Fluorinated copolymer and use thereof - Google Patents
Fluorinated copolymer and use thereofInfo
- Publication number
- JPH02151610A JPH02151610A JP63305443A JP30544388A JPH02151610A JP H02151610 A JPH02151610 A JP H02151610A JP 63305443 A JP63305443 A JP 63305443A JP 30544388 A JP30544388 A JP 30544388A JP H02151610 A JPH02151610 A JP H02151610A
- Authority
- JP
- Japan
- Prior art keywords
- fluorine
- containing copolymer
- vinyl ether
- chlorine
- copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001577 copolymer Polymers 0.000 title claims abstract description 78
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 30
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000460 chlorine Substances 0.000 claims abstract description 29
- 150000003961 organosilicon compounds Chemical class 0.000 claims abstract description 15
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052731 fluorine Inorganic materials 0.000 claims description 54
- 239000011737 fluorine Substances 0.000 claims description 53
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 47
- 150000001875 compounds Chemical class 0.000 claims description 22
- 239000002516 radical scavenger Substances 0.000 claims description 22
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- 238000000746 purification Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 5
- 150000007514 bases Chemical group 0.000 claims description 5
- 239000004593 Epoxy Substances 0.000 claims description 4
- 101100283604 Caenorhabditis elegans pigk-1 gene Proteins 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 abstract description 24
- 239000002904 solvent Substances 0.000 abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 12
- JMICBDHJGYAFMU-UHFFFAOYSA-N 3-ethenoxypropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCOC=C JMICBDHJGYAFMU-UHFFFAOYSA-N 0.000 abstract description 2
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 abstract 1
- 239000007870 radical polymerization initiator Substances 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 30
- -1 alkyl vinyl ethers Chemical class 0.000 description 22
- 239000003960 organic solvent Substances 0.000 description 22
- 239000003973 paint Substances 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 17
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 14
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 14
- 239000000178 monomer Substances 0.000 description 14
- 239000008096 xylene Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 239000003999 initiator Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000002835 absorbance Methods 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 150000002221 fluorine Chemical class 0.000 description 6
- 229920002313 fluoropolymer Polymers 0.000 description 6
- 239000004811 fluoropolymer Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000012456 homogeneous solution Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 239000008199 coating composition Substances 0.000 description 3
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 229960001545 hydrotalcite Drugs 0.000 description 3
- 229910001701 hydrotalcite Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 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
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 2
- VJGCZWVJDRIHNC-UHFFFAOYSA-N 1-fluoroprop-1-ene Chemical compound CC=CF VJGCZWVJDRIHNC-UHFFFAOYSA-N 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 229910019440 Mg(OH) Inorganic materials 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000005083 alkoxyalkoxy group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- NIDNOXCRFUCAKQ-UHFFFAOYSA-N bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2C(O)=O NIDNOXCRFUCAKQ-UHFFFAOYSA-N 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical group FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- BOOBDAVNHSOIDB-UHFFFAOYSA-N (2,3-dichlorobenzoyl) 2,3-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC=CC(C(=O)OOC(=O)C=2C(=C(Cl)C=CC=2)Cl)=C1Cl BOOBDAVNHSOIDB-UHFFFAOYSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- XMJQCVMNFPEJLN-UHFFFAOYSA-N 1-ethenoxy-4-methylpentane Chemical compound CC(C)CCCOC=C XMJQCVMNFPEJLN-UHFFFAOYSA-N 0.000 description 1
- YAOJJEJGPZRYJF-UHFFFAOYSA-N 1-ethenoxyhexane Chemical compound CCCCCCOC=C YAOJJEJGPZRYJF-UHFFFAOYSA-N 0.000 description 1
- XXCVIFJHBFNFBO-UHFFFAOYSA-N 1-ethenoxyoctane Chemical compound CCCCCCCCOC=C XXCVIFJHBFNFBO-UHFFFAOYSA-N 0.000 description 1
- IOSXLUZXMXORMX-UHFFFAOYSA-N 1-ethenoxypentane Chemical compound CCCCCOC=C IOSXLUZXMXORMX-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- YKTNISGZEGZHIS-UHFFFAOYSA-N 2-$l^{1}-oxidanyloxy-2-methylpropane Chemical group CC(C)(C)O[O] YKTNISGZEGZHIS-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- AXWJKQDGIVWVEW-UHFFFAOYSA-N 2-(dimethylamino)butanedioic acid Chemical compound CN(C)C(C(O)=O)CC(O)=O AXWJKQDGIVWVEW-UHFFFAOYSA-N 0.000 description 1
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 1
- XDRAKJQFCQVBMP-UHFFFAOYSA-N 2-but-2-enyl-3-methylbutanedioic acid Chemical compound CC=CCC(C(O)=O)C(C)C(O)=O XDRAKJQFCQVBMP-UHFFFAOYSA-N 0.000 description 1
- OUELSYYMNDBLHV-UHFFFAOYSA-N 2-ethenoxyethylbenzene Chemical compound C=COCCC1=CC=CC=C1 OUELSYYMNDBLHV-UHFFFAOYSA-N 0.000 description 1
- GNUGVECARVKIPH-UHFFFAOYSA-N 2-ethenoxypropane Chemical compound CC(C)OC=C GNUGVECARVKIPH-UHFFFAOYSA-N 0.000 description 1
- WBAMWFOXCUNUBX-UHFFFAOYSA-N 2-ethoxyethenylsilane Chemical compound O(CC)C=C[SiH3] WBAMWFOXCUNUBX-UHFFFAOYSA-N 0.000 description 1
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 1
- SMSVUYQRWYTTLI-UHFFFAOYSA-L 2-ethylhexanoate;iron(2+) Chemical compound [Fe+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O SMSVUYQRWYTTLI-UHFFFAOYSA-L 0.000 description 1
- ODGCZQFTJDEYNI-UHFFFAOYSA-N 2-methylcyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1(C)C=CCCC1C(O)=O ODGCZQFTJDEYNI-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 101100440271 Caenorhabditis elegans ccf-1 gene Proteins 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- CBWUNQZJGJFJLZ-UHFFFAOYSA-N [Cl].Cl Chemical compound [Cl].Cl CBWUNQZJGJFJLZ-UHFFFAOYSA-N 0.000 description 1
- NBJODVYWAQLZOC-UHFFFAOYSA-L [dibutyl(octanoyloxy)stannyl] octanoate Chemical compound CCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCC NBJODVYWAQLZOC-UHFFFAOYSA-L 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000003609 aryl vinyl group Chemical group 0.000 description 1
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 229950005499 carbon tetrachloride Drugs 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- NHOGGUYTANYCGQ-UHFFFAOYSA-N ethenoxybenzene Chemical compound C=COC1=CC=CC=C1 NHOGGUYTANYCGQ-UHFFFAOYSA-N 0.000 description 1
- VGIYPVFBQRUBDD-UHFFFAOYSA-N ethenoxycyclohexane Chemical class C=COC1CCCCC1 VGIYPVFBQRUBDD-UHFFFAOYSA-N 0.000 description 1
- HJVKTYVDOZVQPA-UHFFFAOYSA-N ethenoxycyclopentane Chemical compound C=COC1CCCC1 HJVKTYVDOZVQPA-UHFFFAOYSA-N 0.000 description 1
- AZDCYKCDXXPQIK-UHFFFAOYSA-N ethenoxymethylbenzene Chemical compound C=COCC1=CC=CC=C1 AZDCYKCDXXPQIK-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- IJNRGJJYCUCFHY-UHFFFAOYSA-N ethenyl-dimethoxy-phenylsilane Chemical compound CO[Si](OC)(C=C)C1=CC=CC=C1 IJNRGJJYCUCFHY-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 1
- 229940052308 general anesthetics halogenated hydrocarbons Drugs 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- GIWKOZXJDKMGQC-UHFFFAOYSA-L lead(2+);naphthalene-2-carboxylate Chemical compound [Pb+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 GIWKOZXJDKMGQC-UHFFFAOYSA-L 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 150000002923 oximes Chemical group 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical class ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
【発明の詳細な説明】
発明の技術分野
本発明は、着色がなく、しかも有機溶剤に溶解して常温
で速やかに硬化させることができるような含フッ素共重
合体の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to a method for producing a fluorine-containing copolymer that is free from coloration and can be dissolved in an organic solvent and rapidly cured at room temperature.
発明の技術的背景ならびにその問題点
建築物、車輌、船舶、航空機等の外装分野には耐候性、
耐久性の優れた塗料が要求され、ポリエステル系または
アクリル系の高級外装塗料が利用されている。しかし、
既存塗料の屋外耐用年数は短く、上述の高級塗料でさえ
数年で美観と基材保護作用を失ってしまう。Technical background of the invention and its problems Weather resistance,
Paints with excellent durability are required, and high-grade exterior paints based on polyester or acrylic are used. but,
Existing paints have a short outdoor service life, and even the above-mentioned high-quality paints lose their aesthetic appearance and substrate protection effect within a few years.
一方、フッ素系重合体は熱的にも化学的にも極めて安定
であり、耐候性、耐水性、耐薬品性、耐溶剤性あるいは
離型性、低摩擦性、撥水性に優れているので、各種基材
の表面処理剤として好適である。しかし、従来知られて
いるフッ素系重合体は、前述のような性質が災いして、
有機溶媒に溶けに<<、塗膜の形成が困難であって、塗
料として非常に使用しにくかった。たとえば、現在知ら
れているフッ素系重合体の塗料は粉体塗料が多く、僅か
にpVdF (ポリビニリデンフルオライド)が高温下
に特定の溶媒に溶解する性質を利用して有機溶媒分散型
塗料として用いられているに過ぎない。しかもこれらの
フッ素系重合体の塗料は、皮膜形成の際に高温の焼付が
必要であるので、その利用分野が加熱設備のできる場所
に制限されていた。また加熱設備の存在および焼付工程
を行なわなければならないことは、作業に従事する人の
安全面や作業場の環境面からも好ましいものではない。On the other hand, fluoropolymers are extremely stable both thermally and chemically, and have excellent weather resistance, water resistance, chemical resistance, solvent resistance, mold releasability, low friction, and water repellency. Suitable as a surface treatment agent for various substrates. However, conventionally known fluoropolymers suffer from the above-mentioned properties,
It was difficult to form a coating film because it was soluble in organic solvents, making it extremely difficult to use it as a paint. For example, most of the currently known fluoropolymer paints are powder paints, and a small amount of pVdF (polyvinylidene fluoride) is used as an organic solvent-dispersed paint by taking advantage of its ability to dissolve in specific solvents at high temperatures. It's just being used. Moreover, these fluoropolymer paints require baking at a high temperature when forming a film, so their field of use has been limited to areas where heating equipment is available. Furthermore, the presence of heating equipment and the necessity of performing a baking process are not desirable from the viewpoint of the safety of the workers and the environment of the workplace.
そこで、近年になり溶剤可溶性あるいは高温での焼付工
程の必要のないフッ素系重合体の開発が試みられている
。Therefore, in recent years, attempts have been made to develop fluoropolymers that are solvent-soluble or do not require a baking process at high temperatures.
たとえば特開昭57−34107号公報には、フルオロ
オレフィン、シクロヘキシルビニルエーテル、アルキル
ビニルエーテルおよびヒドロキシアルキルビニルエーテ
ルからなる4元共重合体が開示されており、この共重合
体は有機溶剤に可溶であって、常温で硬化させることが
可能であることも記載されている。しかし、この共重合
体を常温硬化させるには、他にメラミン系硬化剤や尿素
樹脂系硬化剤が必要であり、その分だけ耐候性が低下す
る欠点がある。また、この共重合体のガラス転移温度は
常温以上すなわち25℃以上と比較的高い。また特公昭
4B−89412号公報には、実際の例は記載されてい
ないが、PTFE (ポリテトラフルオロエチレン)に
オレフィン性不飽和結合および加水分解可能な基をもつ
有機珪素化合物を、有機ヒドロペルオキシド等のラジカ
ル開始剤の存在下で機械的に処理したものは、常温で水
によって架橋し硬化することが示唆されている。しかし
、この方法で製造されるフッ素系重合体は、有機珪素化
合物がPTFEにグラフトした重合体であり、有機溶剤
には実質的に不溶である。For example, JP-A-57-34107 discloses a quaternary copolymer consisting of fluoroolefins, cyclohexyl vinyl ethers, alkyl vinyl ethers, and hydroxyalkyl vinyl ethers, and this copolymer is soluble in organic solvents. It is also described that it can be cured at room temperature. However, in order to cure this copolymer at room temperature, a melamine-based curing agent or a urea resin-based curing agent is also required, which has the disadvantage that weather resistance is reduced accordingly. Further, the glass transition temperature of this copolymer is relatively high, at or above room temperature, that is, at or above 25°C. Furthermore, although no actual example is described in Japanese Patent Publication No. 4B-89412, an organosilicon compound having an olefinic unsaturated bond and a hydrolyzable group is added to PTFE (polytetrafluoroethylene) using an organic hydroperoxide. It has been suggested that those mechanically treated in the presence of a radical initiator such as the above are crosslinked and cured by water at room temperature. However, the fluoropolymer produced by this method is a polymer in which an organosilicon compound is grafted onto PTFE, and is substantially insoluble in organic solvents.
本発明者らは、こ2のような現状に鑑みて、■ 有機溶
剤に低温で溶解し、
■ 硬化に際して特殊な硬化剤を必要とせず、■ 常温
で硬化し、
■ 硬化後は耐候性、耐水性、耐薬品性、耐溶剤性、低
摩擦性に優れ、
■ モノマー成分から直接重合できるような含フッ素共
重合体として、
[Aコ(a)フルオロオレフィン、
(b)ビニルエーテル、
(c)オレフィン性不飽和結合及び加水分解可能な基を
もつ有機珪素化合物、
とから実質的に構成される共重合体であって、[B]共
重合体中の(a)〜(e)の合計モル数に対して、(a
):30〜70モル%、(b):20〜60モル%、(
c)=1〜25モル%であって、
[C] ’7’ル・パーミェーションクロマトグラフ法
によって測定した数平均分子量(Mn)が3000〜2
00000、
で定義づけられる溶剤可溶性含フッ素共重合体およびこ
の含フッ素共重合体を有機溶剤に溶解してなる塗料を、
特願昭59〜283017号に提案した。In view of these two current circumstances, the present inventors have developed a material that: 1) dissolves in an organic solvent at low temperatures, 2) does not require a special curing agent during curing, 2) cures at room temperature, and 2) has weather resistance after curing. As a fluorine-containing copolymer that has excellent water resistance, chemical resistance, solvent resistance, and low friction properties, and can be directly polymerized from monomer components, [A co(a) fluoroolefin, (b) vinyl ether, (c) [B] A copolymer consisting essentially of an organosilicon compound having an olefinic unsaturated bond and a hydrolyzable group, wherein the total mole of (a) to (e) in the copolymer [B] For a number, (a
): 30-70 mol%, (b): 20-60 mol%, (
c) = 1 to 25 mol%, and the number average molecular weight (Mn) measured by [C] '7' le permeation chromatography is 3000 to 2
A solvent-soluble fluorine-containing copolymer defined by 00000 and a paint obtained by dissolving this fluorine-containing copolymer in an organic solvent,
This was proposed in Japanese Patent Application No. 59-283017.
この含フッ素共重合体は極めて優れた特性を有している
が、(a)フルオロオレフィンとして塩素を含むフルオ
ロオレフィンを用いると、得られる含フッ素共重合体は
黄色などに着色してしまうという問題点があった。した
がってこの含フッ素共重合体を有機溶剤に溶解させてな
る塗料を基材上に塗布して得られる塗膜は、黄色に着色
してしまうという問題点があった。This fluorine-containing copolymer has extremely excellent properties, but (a) when a fluoroolefin containing chlorine is used as the fluoroolefin, the resulting fluorine-containing copolymer is colored yellow or the like. There was a point. Therefore, there is a problem in that a coating film obtained by coating a substrate with a coating material prepared by dissolving this fluorine-containing copolymer in an organic solvent is colored yellow.
発明の目的
本発明は、上記のような問題点を解決しようとするもの
であって、着色がなく、しがち有機溶剤に溶解して常温
で速やかに硬化させることができるような含フッ素共重
合体の製造方法を提供することを目的としている。Purpose of the Invention The present invention aims to solve the above-mentioned problems, and it is an object of the present invention to provide a fluorine-containing copolymer that is free from coloration, easily dissolves in organic solvents, and can be rapidly cured at room temperature. The purpose is to provide a manufacturing method for coalescence.
発明の概要
本発明に係る含フッ素共重合体の製造方法は、(a)塩
素を含むフルオロオレフィン
(b)ビニルエーテル および
(c)オレフィン性不飽和結合および加水分解可能な基
を有する有機珪素化合物
を共重合させることによって含フッ素共重合体を製造す
るに際して、
重合反応時および/または得られた共重合体の精製時に
、系内に塩素捕捉剤を存在させることを特徴としている
。Summary of the Invention The method for producing a fluorine-containing copolymer according to the present invention comprises (a) a fluoroolefin containing chlorine, (b) a vinyl ether, and (c) an organosilicon compound having an olefinic unsaturated bond and a hydrolyzable group. When producing a fluorine-containing copolymer by copolymerization, a chlorine scavenger is present in the system during the polymerization reaction and/or during purification of the obtained copolymer.
本発明では、上記のような含フッ素共重合体を製造する
に際して、重合反応時および/または得られた共重合体
の精製時に、系内に塩素捕捉剤を存在させているため、
着色のない含フッ素共重合体を得ることができる。In the present invention, when producing the above-mentioned fluorine-containing copolymer, a chlorine scavenger is present in the system during the polymerization reaction and/or during the purification of the obtained copolymer.
A colorless fluorine-containing copolymer can be obtained.
発明の詳細な説明
以下本発明に係る含フッ素共重合体の製造方法について
具体的に説明する。DETAILED DESCRIPTION OF THE INVENTION The method for producing a fluorine-containing copolymer according to the present invention will be specifically described below.
まず本発明に係る含フッ素共重合体について説明すると
、この含フッ素共重合体は、(a)塩素を含有するフル
オロオレフィンと、(b) ビニルエーテルと、(c)
オレフィン性不飽和結合および加水分解可能な基を有す
る有機珪素化合物との3種類のモノマー成分単位からな
る共重合体である。しかし本発明の目的を損わない範囲
で、少量の他の共重合可能なモノマー成分、たとえばα
−オレフィン類、シクロオレフィン類、カルボン酸ビニ
ルエステル類、カルボン酸アリルエステル類などが共重
合されていてもかまわない。First, the fluorine-containing copolymer according to the present invention will be explained. This fluorine-containing copolymer consists of (a) fluoroolefin containing chlorine, (b) vinyl ether, and (c)
It is a copolymer consisting of three types of monomer component units with an organosilicon compound having an olefinic unsaturated bond and a hydrolyzable group. However, small amounts of other copolymerizable monomer components, such as α
-Olefins, cycloolefins, carboxylic acid vinyl esters, carboxylic acid allyl esters, etc. may be copolymerized.
本発明で用いられるフルオロオレフィン(a)は、分子
中に少なくとも1個以上のフッ素原子および塩素原子を
有しており、好ましくはオレフィンの水素原子が全てフ
ッ素原子、塩素原子および他のハロゲン原子で置換され
ているペルハロオレフィンが好適である。さらに重合性
および得られる重合体の性質の観点からは、炭素原子数
2または3のフルオロオレフィンが好ましい。The fluoroolefin (a) used in the present invention has at least one fluorine atom and one chlorine atom in the molecule, and preferably all hydrogen atoms of the olefin are fluorine atoms, chlorine atoms, and other halogen atoms. Substituted perhaloolefins are preferred. Furthermore, from the viewpoint of polymerizability and properties of the resulting polymer, fluoroolefins having 2 or 3 carbon atoms are preferred.
このようなフルオロオレフィンとしては、具体的には以
下のような化合物が用いられる。Specifically, the following compounds are used as such fluoroolefins.
C(l F−CF 5CI(cIJ−CF2、CCl
2 −CF 5C(l F−C(l F、CHF−C
(1、C(1? 2−CCJI)F等の炭素原子数2の
フルオロオレフィン(フルオロエチレン系)。C(l F-CF 5CI(cIJ-CF2, CCl
2-CF5C(l F-C(l F, CHF-C
(1, C(1?2-CCJI)F and other fluoroolefins having 2 carbon atoms (fluoroethylene type).
CF CB CF−CF 、CF3CCN−CF2
、CF3CF−CFCN 。CF CB CF-CF , CF3CCN-CF2
, CF3CF-CFCN.
CF (l C(1−CF 、CF21! CF−
CF(l 5CFi 2CF讃CF2、CCD CF
−CF 5CF3CF−CHCD、、CCgF C
F−CHCΩ、CCΩa CF −CHCl1 、CF
N CF−CF2、CHBr CF−C0g2等の
炭素原子数3の]ルオロオレフィン(フルオロプロペン
系)。CF (l C(1-CF, CF21! CF-
CF (l 5CFi 2CF San CF2, CCD CF
-CF 5CF3CF-CHCD, CCgF C
F-CHCΩ, CCΩa CF -CHCl1, CF
]fluoroolefin (fluoropropene type) having 3 carbon atoms, such as N CF-CF2 and CHBr CF-C0g2.
CF C(1−CFCF3、
CF −〇FCF2CCgF2、
CF −mCFCF20CI3、
CH■CFCCg2CC!13、
CF (cF ) CCf1 ■CF2.C
F (cF2)80C1−CF2等の炭素原子数4以上
のフルオロオレフィン系。CF C (1-CFCF3, CF -〇FCF2CCgF2, CF -mCFCF20CI3, CH■CFCCg2CC!13, CF (cF) CCf1 ■CF2.C
Fluoroolefins having 4 or more carbon atoms, such as F (cF2)80C1-CF2.
これらの中では、上記のようにフルオロエチレンおよび
フルオロプロペン系が好ましく、とくにクロロトリフル
オロエチレン(cCIF−CF2)が好適である。Among these, as mentioned above, fluoroethylene and fluoropropene are preferred, and chlorotrifluoroethylene (cCIF-CF2) is particularly preferred.
また本発明において、フルオロオレフィンは、単独で用
いてもよく、また2種以上を混合して用いてもよい。Further, in the present invention, the fluoroolefins may be used alone or in combination of two or more.
本発明で用いられるビニルエーテル(b)ハ、ヒニル基
と、アルキル基、シクロアルキル基、アリール基、アラ
ルキル基などとがエーテル結合した化合物である。The vinyl ether (b) used in the present invention is a compound in which a hinyl group and an alkyl group, cycloalkyl group, aryl group, aralkyl group, etc. are ether bonded.
このようなビニルエーテルとしては、具体的には、エチ
ルビニルエーテル、プロピルビニルエーテル、イソプロ
ピルビニルエーテル、ブチルビニルエーテル、tert
−ブチルビニルエーテル、ペンチルビニルエーテル、ヘ
キシルビニルエーテル、イソヘキシルビニルエーテル、
オクチルビニルエーテル、4−メチル−】−ペンチルビ
ニルエーテル等の鎖状アルキルビニルエーテル類、シク
ロペンチルビニルエーテル、シクロヘキシルビニルエー
テル等のシクロアルキルビニルエーテル類、フェニルビ
ニルエーテル等のアリールビニルエーテル類、ベンジル
ビニルエーテル、フエネチルビニルエーテル等のアラル
キルビニルエーテル類を用いることができる。Specifically, such vinyl ethers include ethyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether, and tert vinyl ether.
-butyl vinyl ether, pentyl vinyl ether, hexyl vinyl ether, isohexyl vinyl ether,
Chain alkyl vinyl ethers such as octyl vinyl ether, 4-methyl-]-pentyl vinyl ether, cycloalkyl vinyl ethers such as cyclopentyl vinyl ether and cyclohexyl vinyl ether, aryl vinyl ethers such as phenyl vinyl ether, and aralkyl vinyl ethers such as benzyl vinyl ether and phenethyl vinyl ether. can be used.
これらの中ではとくに炭素数が8以下好ましくは2〜4
である鎖状アルキルビニルエーテルおよび炭素数が5〜
6であるシクロアルキルビニルエーテルが好ましく、さ
らにはエチルビニルエーテル、プロピルビニルエーテル
、ブチルビニルエーテル、シクロヘキシルビニルエーテ
ルが好適である。Among these, the number of carbon atoms is preferably 8 or less, preferably 2 to 4.
and a chain alkyl vinyl ether having 5 to 5 carbon atoms.
6 is preferred, and ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, and cyclohexyl vinyl ether are more preferred.
また本発明においては、上記のようなビニルエーテルは
、単独で用いてもよく、また複数混合して用いてもよい
。Further, in the present invention, the above-mentioned vinyl ethers may be used alone or in combination.
本発明で用いられる有機珪素化合物(e)は、分子中に
オレフィン性不飽和結合および加水分解可能な基を有す
る化合物であって、具体的には下記−数式(1)〜(3
)に示される化合物を例示することができる。The organosilicon compound (e) used in the present invention is a compound having an olefinic unsaturated bond and a hydrolyzable group in the molecule, and specifically has the following formulas (1) to (3).
) can be exemplified.
R’ R2Si Y1Y2 (1)R’ XSI
Y’ Y2 (2)R1SIY1Y2Y3
(3)
(式中、RR2は、オレフィン性不飽和結合を有し、炭
素、水素および場合によって酸素からなり、それぞれ同
一または相異なる基である。Xは、オレフィン性不飽和
結合を有しない有機基であり、Yl Y2、Y3はそれ
ぞれ同一または相異なる加水分解可能な基である。)
R1またはR2は、具体的には、ビニル、アリル(al
lyl) 、ブテニル、シクロへキセニル、シクロペン
タジェニルなどであり、とくに末端オレフィン性不飽和
基であることが好ましい。またR またはR2は、末端
不飽和酸のエステル結合を有する、
CH−〇H−0(cH2) 3
CH−C(cH)Coo (cH2) 3CH2−C(
cH3)Coo (cH2’) 2−0(cH2)3
CB −C(cH)COOCH2CH2H
などの基であることもできる。これらの中では、Rおよ
びRが酸素を含まず炭素と水素とから構成されているこ
とが好ましく、特にビニル基が最適である。R' R2Si Y1Y2 (1) R' XSI
Y' Y2 (2) R1SIY1Y2Y3
(3) (wherein, RR2 has an olefinically unsaturated bond and is composed of carbon, hydrogen, and optionally oxygen, and is the same or different group; X is an organic group having no olefinically unsaturated bond) (Y2, Y3 are the same or different hydrolyzable groups, respectively.) R1 or R2 is specifically, vinyl, allyl (al
lyl), butenyl, cyclohexenyl, cyclopentagenyl, etc., and terminal olefinically unsaturated groups are particularly preferred. Moreover, R or R2 has an ester bond of a terminal unsaturated acid, CH-〇H-0(cH2) 3 CH-C(cH)Coo (cH2) 3CH2-C(
It can also be a group such as cH3)Coo(cH2')2-0(cH2)3CB-C(cH)COOCH2CH2H. Among these, it is preferable that R and R do not contain oxygen and are composed of carbon and hydrogen, and a vinyl group is particularly suitable.
Xは、具体的には、1価の炭化水素基であるメチル、エ
チル、プロピル、テトラデシル、オクタデシル、フェニ
ル、ベンジル、トリルなどであり、またこれらの基は、
ハロゲン置換炭化水素基でもよい。Specifically, X is a monovalent hydrocarbon group such as methyl, ethyl, propyl, tetradecyl, octadecyl, phenyl, benzyl, tolyl, etc., and these groups are
It may also be a halogen-substituted hydrocarbon group.
YI Y 、Y3は、具体的には、メトキシ、エトキシ
、ブトキシ、メトキシエトキシなどのアルコキシ基、ア
ルコキシアルコキシ基、ホルミロキシ、アセトキシ、ブ
ロピオノキシなどのアシロキシ基、オキシムたとえば
0N−C(cHa )2、
一〇N請CHCH2C2H5および
一0N−C(cOR5)2などであり、その他任意の加
水分解し得る有機基である。Specifically, YI Y and Y3 are alkoxy groups such as methoxy, ethoxy, butoxy, and methoxyethoxy, alkoxyalkoxy groups, acyloxy groups such as formyloxy, acetoxy, and propionoxy, and oximes, such as 0N-C(cHa)2, 10 These include CHCH2C2H5 and 10N-C(cOR5)2, and any other hydrolyzable organic group.
本発明では有機珪素化合物は、上記のような一般式(3
)で表わされる化合物であることが好ましく、とくに基
YI Y2 Y3が同一である有機珪素化合物が好まし
い。これらの中でもR1がビニル基であり、Y1〜Y3
がアルコキシ基またはアルコキシアルコキシ基である有
機珪素化合物が特に好ましく、たとえばビニロキシプロ
ピルトリメトキシシラン、ビニルトリメトキシシラン、
ビニルトリエトキシシラン、ビニルトリス(メトキシエ
トキシ)シランなどが好ましい。またビニルメチルジェ
トキシシラン、ビニルフエニルジメトキシシランなども
同様に用いることができる。In the present invention, the organosilicon compound has the general formula (3
) is preferable, and organosilicon compounds in which the groups YI, Y2, and Y3 are the same are particularly preferable. Among these, R1 is a vinyl group, Y1 to Y3
Particularly preferred are organosilicon compounds in which is an alkoxy group or an alkoxyalkoxy group, such as vinyloxypropyltrimethoxysilane, vinyltrimethoxysilane,
Vinyltriethoxysilane, vinyltris(methoxyethoxy)silane, etc. are preferred. Furthermore, vinylmethyljethoxysilane, vinylphenyldimethoxysilane, etc. can be used similarly.
本発明に係る含フッ素共重合体では、(a)〜(e)の
七ツマー成分の含有割合は、(a)〜(e)の合計モル
数を基準として、(a)は30〜70モル%好ましくは
40〜60モル%の量であり、(b)は20〜60モル
%好ましくは20〜50モル%の量であり、(c)は1
〜25モル%好ましくは3〜20モル%の量であること
が望ましい。In the fluorine-containing copolymer according to the present invention, the content ratio of the heptamer components (a) to (e) is 30 to 70 moles based on the total number of moles of (a) to (e). % preferably in an amount of 40 to 60 mol %, (b) in an amount of 20 to 60 mol %, preferably 20 to 50 mol %, and (c) in an amount of 1
Desirably, the amount is from 3 to 25 mol%, preferably from 3 to 20 mol%.
このような本発明に係る含フッ素共重合体は、常温にお
いて、たとえばベンゼン、トルエン、キシレンなどの芳
香族炭化水素類、アセトン、メチルエチルケトンなどの
ケトン類、ジエチルエーテル、ジプロピルエーテル、メ
チルセロソルブ、エチルセロソルブなどのエーテル類、
酢酸エチル、酢酸ブチルなどのエステル類、エタノール
などのアルコール類、トリクロロメタン、ジクロロエタ
ン、クロロベンゼンなどのハロゲン化炭化水素類などに
溶解する。Such a fluorine-containing copolymer according to the present invention can be used, at room temperature, for example, aromatic hydrocarbons such as benzene, toluene, and xylene, ketones such as acetone and methyl ethyl ketone, diethyl ether, dipropyl ether, methyl cellosolve, and ethyl ether. Ethers such as cellosolve,
It dissolves in esters such as ethyl acetate and butyl acetate, alcohols such as ethanol, and halogenated hydrocarbons such as trichloromethane, dichloroethane, and chlorobenzene.
したがって上記のような含フッ素共重合体を上記のよう
な有機溶剤に溶解させて塗料組成物を調製することがで
きる。Therefore, a coating composition can be prepared by dissolving the above-mentioned fluorine-containing copolymer in the above-mentioned organic solvent.
上記のような含フッ素共重合体から塗料組成物を調製す
る場合には、有機溶剤として、トルエン、キシレン、酢
酸ブチル、イソブチルメチルケトン、メチルセロソルブ
、エチルセロソルブあるいはこれらの混合物などを用い
ることが好ましい。When preparing a coating composition from the above-mentioned fluorine-containing copolymer, it is preferable to use toluene, xylene, butyl acetate, isobutyl methyl ketone, methyl cellosolve, ethyl cellosolve, or a mixture thereof as the organic solvent. .
このような含フッ素共重合体は、有機珪素化合物(c)
に由来する加水分解可能な有機基を有しているので、水
分と接触することにより重合体の分子鎖間に橋かけ反応
が起こり、硬化する。したがって、大気中の湿気によっ
ても当然のことながら架橋が起こり得る。この含フッ素
共重合体は・単独でも架橋が進むことは明白であるが、
塗料として用いる場合には、基材に塗布された含フッ素
共重合体の皮膜が迅速に硬化するように、シラノール縮
合触媒を塗料組成物中に予め添加しておくこともでき、
また塗装置前に添加しておくこともできる。この場合、
含フッ素共重合体とシラノール縮合触媒を含んだ有機溶
剤液を基材に塗布すると、有機溶剤が蒸散して空気中の
湿分と接触しだすと同時に硬化反応が起こり、皮膜硬化
が起こる。Such a fluorine-containing copolymer is an organosilicon compound (c)
Since it has a hydrolyzable organic group derived from , a cross-linking reaction occurs between the molecular chains of the polymer when it comes into contact with moisture, resulting in curing. Therefore, as a matter of course, moisture in the atmosphere can also cause crosslinking. It is clear that crosslinking of this fluorine-containing copolymer progresses even when used alone;
When used as a paint, a silanol condensation catalyst can be added in advance to the paint composition so that the fluorine-containing copolymer film applied to the base material is rapidly cured.
It can also be added before painting. in this case,
When an organic solvent solution containing a fluorine-containing copolymer and a silanol condensation catalyst is applied to a substrate, a curing reaction occurs as the organic solvent evaporates and comes into contact with moisture in the air, resulting in film hardening.
シラノール触媒としては、公知のものを用いることがで
き、具体的には、ジブチル錫ジラウレート、ジオクチル
錫ジラウレート、酢酸第1錫、オクタン酸第1錫、ナフ
テン酸鉛、2−エチルヘキサン酸鉄、ナフテン酸コバル
トなどのカルボン酸金属塩1、エチルアミン、ヘキシル
アミン、ジブチルアミン、ピペリジンなどの有機塩基、
無機酸および有機脂肪酸などの酸などが用いられる。こ
のうちアルキル錫カルボン塩、たとえばジブチル錫ジラ
ウレート、ジオクチル錫ジラウレート、ジブチル錫ジオ
クトエート、ジブチル錫ジアセテートが好ましい。As the silanol catalyst, known ones can be used, and specifically, dibutyltin dilaurate, dioctyltin dilaurate, stannous acetate, stannous octoate, lead naphthenate, iron 2-ethylhexanoate, and naphthene. Carboxylic acid metal salts such as cobalt acid 1, organic bases such as ethylamine, hexylamine, dibutylamine, piperidine,
Acids such as inorganic acids and organic fatty acids are used. Among these, alkyltin carbon salts such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, and dibutyltin diacetate are preferred.
本発明に係る含フッ素共重合体の橋かけ反応は、常温す
なわち室温付近(0〜40’C)で十分進行するが、必
要に応じて加熱下で反応を行わしめてもよい。The crosslinking reaction of the fluorine-containing copolymer according to the present invention proceeds sufficiently at room temperature, that is, around room temperature (0 to 40'C), but the reaction may be carried out under heating if necessary.
本発明に係る含フッ素共重合体を塗料として使用する場
合には、通常の液体塗料と同じように刷毛、スプレー
ローラコータ等で金属、木、プラスチック、セラミック
、紙、ガラスなどの基材表面に塗布することができる。When using the fluorine-containing copolymer according to the present invention as a paint, it can be applied with a brush or spray in the same way as ordinary liquid paints.
It can be applied to the surface of base materials such as metal, wood, plastic, ceramic, paper, and glass using a roller coater or the like.
硬化後の被膜は、耐候性、耐薬品性、耐溶剤性、耐水性
、耐熱性、低摩擦性に優れ、さらに透明性、光沢、伸び
性にも優れている。The cured film has excellent weather resistance, chemical resistance, solvent resistance, water resistance, heat resistance, and low friction, as well as excellent transparency, gloss, and elongation.
本発明では、上記のような含フッ素共重合体を製造する
に際して、重合反応時または得られた共重合体の精製時
あるいはこの両方に、系内に塩素捕捉剤を存在させる。In the present invention, when producing the above-mentioned fluorine-containing copolymer, a chlorine scavenger is present in the system during the polymerization reaction, during purification of the obtained copolymer, or both.
具体的には、上記のような(a)塩Xを含むフルオロオ
レフィン、(b)ビニルエーテルおよび(c)有機珪素
化合物を共重合させる際に、反応系に塩素捕捉剤を存在
させ、しかも得られた含フッ素共重合体をアルコールな
どの有機溶媒で精製処理する際に系内に塩素捕捉剤を存
在させておくことが好ましい。Specifically, when copolymerizing (a) a fluoroolefin containing salt X, (b) vinyl ether, and (c) an organosilicon compound as described above, a chlorine scavenger is present in the reaction system, and When the fluorine-containing copolymer is purified using an organic solvent such as alcohol, it is preferable to have a chlorine scavenger present in the system.
塩素捕捉剤としては、以下のような化合物を用いること
ができる。As the chlorine scavenger, the following compounds can be used.
(伺M AN (OH) 2x+3y−2z (A)
ax y
zH20(式中、MはMg、C
aまたはZnであり、AはCO3またはHPO4であり
、X% )’ SZは正数であり、aは0または正数で
ある。)で示される複合化合物。(KiM AN (OH) 2x+3y-2z (A)
ax y
zH20 (where M is Mg, C
a or Zn, A is CO3 or HPO4, X%)' SZ is a positive number, and a is 0 or a positive number. ) complex compound.
(イ)で示される複合化合物としては、具体的には、下
記のような化合物が用いられる。Specifically, the following compounds are used as the composite compound represented by (a).
M g A II (OH) C0・4 H2
0Mg AN (OH) C0・5H2082
20B
Mg Aj) (OB) Co ・4H2
0Mg A、11 (OH) C0・4H2
0M g A D (OH) HP 0
・4 H20Ca Al (OH) CO−
4H20Z n A g(OH) C0・4
H20この(イ)で示される複合化合物は、上記のよう
な式で正確に示されない化合物であってもよく、たとえ
ばMg l (OH) ・3H20のOHの一部
がCO3で置換された化合物であってもよい。またこれ
らの化合物は、結晶水が除去されていてもよい。M g A II (OH) C0・4 H2
0Mg AN (OH) C0・5H2082
20B Mg Aj) (OB) Co ・4H2
0Mg A, 11 (OH) C0・4H2
0M g A D (OH) HP 0
・4 H20Ca Al (OH) CO-
4H20Z n A g(OH) C0・4
H20 The complex compound represented by (a) may be a compound that is not exactly represented by the above formula, for example, a compound in which part of the OH of Mg l (OH) 3H20 is replaced with CO3. There may be. Further, water of crystallization may be removed from these compounds.
このような複合化合物のうちでは、MがMgであり、A
がCO3である化合物が好ましい。In such a complex compound, M is Mg and A
Compounds in which is CO3 are preferred.
(ロ)アルカリ土類金属の塩基性化合物アルカリ土類金
属の塩基性化合物としては、具体的には、Mg 01C
a Oなどのアルカリ土類金属酸化物、Mg(OH)
、Ca(OH) 2などの7ルカリ土類金属水酸化物
、MgCO3、CaCO3などのアルカリ土類金属炭酸
塩などが用いられる。(b) Basic compound of alkaline earth metal As the basic compound of alkaline earth metal, specifically, Mg 01C
a Alkaline earth metal oxides such as O, Mg(OH)
, heptalkaline earth metal hydroxides such as Ca(OH) 2 , alkaline earth metal carbonates such as MgCO 3 and CaCO 3 , and the like are used.
上記のようなアルカリ土類金属の塩基性化合物は、
(MgCO) ・ Mg(OH) 拳
5 H20などの複塩であってもよく、またこれらの
化合物は結晶水が除去されていもよい。Basic compounds of alkaline earth metals such as those mentioned above are
(MgCO) Mg(OH) Fist 5 H20 or other double salts may be used, and these compounds may have water of crystallization removed.
これらのアルカリ土類金属の塩基性化合物のうちでは、
Mg含有化合物が好ましい。Among these basic compounds of alkaline earth metals,
Mg-containing compounds are preferred.
(ハ)エポキシ基含有化合物
エポキシ基含有化合物としては、γ−グリシドキシプロ
ピルトリメトキシシラン、β−(3,4−エポキシシク
ロヘキシル)エチルトリメトキシシランなどのケイ素含
有エポキシ化合物、トリメチロールプロパンポリグリシ
ジルエーテル、ネオペンチルグリコールジグリシジルエ
ーテルなどの脂肪族エポキシ化合物などが用いられる。(c) Epoxy group-containing compounds Examples of epoxy group-containing compounds include silicon-containing epoxy compounds such as γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and trimethylolpropane polyglycidyl. Aliphatic epoxy compounds such as ether and neopentyl glycol diglycidyl ether are used.
このうちγ−グリシドキシプロピルトリメトキシシラン
などのケイ素含有エポキシ化合物が好ましい。Among these, silicon-containing epoxy compounds such as γ-glycidoxypropyltrimethoxysilane are preferred.
上記のような塩素捕捉剤のうち、無機化合物である塩素
捕捉剤は、有機化合物である塩素捕捉剤と比較して、塩
素(塩酸)との反応が速く、かつ重合系あるいは精製系
に溶解していないため、系外に除去しやすいため好まし
く用いられる。特に(イ)で示した複合化合物が好まし
い。Among the chlorine scavengers mentioned above, chlorine scavengers that are inorganic compounds react faster with chlorine (hydrochloric acid) than chlorine scavengers that are organic compounds, and they do not dissolve in polymerization or purification systems. It is preferably used because it is easy to remove from the system. Particularly preferred are the composite compounds shown in (a).
上記のような塩素捕捉剤を、゛重合反応時または得られ
た共重合体の精製時あるいはこの両方に存在させること
によって、得られる含フッ素共重合体の着色を効果的に
防止することができる。特に塩素捕捉剤を重合反応時に
系内に存在させることによって、得られる含フッ素共重
合体の着色を効果的に防止することができる。Coloring of the obtained fluorine-containing copolymer can be effectively prevented by making the above-mentioned chlorine scavenger present during the polymerization reaction, during the purification of the obtained copolymer, or both. . In particular, by allowing a chlorine scavenger to be present in the system during the polymerization reaction, coloring of the resulting fluorine-containing copolymer can be effectively prevented.
また得られた含フッ素共重合体をアルコール類などで精
製処理する際に系内に塩素捕捉剤を存在させることによ
って、この含フッ素共重合体をトルエンなどの有機溶剤
に溶解させて塗料とし、この塗料を金属などの基材に塗
布して塗膜を形成した際に、基材に錆が発生するのを効
果的に防止することができる。In addition, when the obtained fluorine-containing copolymer is purified with alcohol or the like, a chlorine scavenger is present in the system, and this fluorine-containing copolymer is dissolved in an organic solvent such as toluene to form a paint. When this paint is applied to a base material such as metal to form a coating film, it is possible to effectively prevent rust from forming on the base material.
このような塩素捕捉剤を、重合反応時に用いる場合には
、(a)フルオロオレフィンに含まれる塩素原子1モル
に対して065〜100g好ましくは1〜70gの量で
用いることが好ましい。When such a chlorine scavenger is used during the polymerization reaction, it is preferably used in an amount of 065 to 100 g, preferably 1 to 70 g, per mole of chlorine atoms contained in (a) fluoroolefin.
また塩素捕捉剤を、精製時に用いる場合には、得られた
含フッ素共重合体100gに対して0.5〜100g好
ましくは1〜70gの量で用いることが好ましい。When a chlorine scavenger is used during purification, it is preferably used in an amount of 0.5 to 100 g, preferably 1 to 70 g, per 100 g of the obtained fluorine-containing copolymer.
なお得られた含フッ素共重合体を有機溶媒で精製処理す
る際には、有機溶媒としてアルコール類を用いることが
好ましいが、アルコール類としては0、メタノール、エ
タノール、プロパツール、イソプロパツール、n−ブタ
ノール、1so−ブタノール、tert−ブタノールな
どが用いられる。Note that when the obtained fluorine-containing copolymer is purified with an organic solvent, it is preferable to use alcohols as the organic solvent. -butanol, 1so-butanol, tert-butanol, etc. are used.
本発明では、重合反応系および/または精製系に上記の
ような塩素捕捉剤を存在させる以外は、従来既知の方法
に従って含フッ素共重合体を製造することができる。す
なわち本発明に係る含フッ素共重合体は、上記のような
各モノマー(a)〜(c)を周知のラジカル開始剤の存
在下共重合することによって製造することができる。こ
こで(a)〜(c)の各成分はいずれも存在することが
必要であり、たとえば(a)成分と(c)成分とのみで
は共重合が生じないが、(b)成分を加えることによっ
て(a) 、(b) 、 (c)の各成分が共重合する
。In the present invention, the fluorine-containing copolymer can be produced according to a conventionally known method, except that the above-mentioned chlorine scavenger is present in the polymerization reaction system and/or purification system. That is, the fluorine-containing copolymer according to the present invention can be produced by copolymerizing each of the above monomers (a) to (c) in the presence of a known radical initiator. Here, each component (a) to (c) must be present; for example, copolymerization will not occur with only components (a) and (c), but adding component (b) Components (a), (b), and (c) are copolymerized by this.
このような含フッ素共重合体を製造する際にはラジカル
開始剤として、公知の種々のものが使用できる。具体的
には有機ペルオキシド、有機ベルエステルたとえばベン
ゾイルペルオキシド、ジクロルベンゾイルペルオキシド
、ジクミルペルオキシド、ジーtert−ブチルペルオ
キシド、2,5−ジメチル−2,5−ジ(ペルオキシベ
ンゾエート)ヘキシン−3、■、4−ビス(tert−
ブチルペルオキシイソプロピル)ベンゼン、ラウロイル
ペルオキシド、tert−ブチルベルアセテート、2.
5−ジメチル−2,5−ジ(tert−ブチルペルオキ
シ)ヘキシン−3,2,5−ジメチル−2,5−ジ(t
ert−ブチルペルオキシ)ヘキサン、tert−ブチ
ルベルベンゾエート、tert−ブチルベルフェニルア
セテ−)、tert−ブチルベルイソブチレート、te
rt−ブチルベルー5C1e−オクトエート、tert
−ブチルベルピバレート、クミルベルピバレート、1e
rt−ブチルベルジエチルアセテートなど、その他アゾ
化合物たとえばアゾビス−イソブチルニトリル、ジメチ
ルアゾイソブチレートなどが用いられる。このうちジク
ミルペルオキシド、ジーtert−ブチルペルオキシド
、2,5−ジメチル−2,5−ジ(tert−ブチルペ
ルオキシ)ヘキシン−3,2,5−ジメチル−2,5−
ジ(tert−ブチルペルオキシ)ヘキサン、1.4−
ビス(tert−ブチルペルオキシイソプロピル)ベン
ゼンなどのジアルキルペルオキシドが好ましい。When producing such a fluorine-containing copolymer, various known radical initiators can be used. Specifically, organic peroxides, organic bersesters such as benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(peroxybenzoate) hexyne-3, 4-bis(tert-
butylperoxyisopropyl)benzene, lauroylperoxide, tert-butylberacetate, 2.
5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3,2,5-dimethyl-2,5-di(t
tert-butylperoxy)hexane, tert-butylberbenzoate, tert-butylberphenylacetate), tert-butylberisobutyrate, te
rt-butylberu 5C1e-octoate, tert
-Butylbelpivalate, cumylbelpivalate, 1e
Other azo compounds such as azobis-isobutylnitrile, dimethylazoisobutyrate, etc. are used, such as rt-butylbergiethyl acetate. Among these, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3,2,5-dimethyl-2,5-
Di(tert-butylperoxy)hexane, 1.4-
Dialkyl peroxides such as bis(tert-butylperoxyisopropyl)benzene are preferred.
上記のような共重合反応は、有機溶媒からなる反応媒体
中で行われることが好ましい。このような有機溶媒とし
ては、ベンゼン、トルエン、キシレンなどの芳香族炭化
水素、n−ヘキサン、シクロヘキサン、n−ヘプタンな
どの脂肪族炭化水素、クロロベンゼン、ブロモベンゼン
、ヨードベンゼン、0−ブロモトルエンなどのハロゲン
化芳香族炭化水素、テトラクロロメタン、t、t、t−
トリクロロエタン、テトラクロロエチレン、■−クロロ
ブタンなどのハロゲン化脂肪族炭化水素等を用いること
ができる。The copolymerization reaction as described above is preferably carried out in a reaction medium consisting of an organic solvent. Examples of such organic solvents include aromatic hydrocarbons such as benzene, toluene, and xylene, aliphatic hydrocarbons such as n-hexane, cyclohexane, and n-heptane, and chlorobenzene, bromobenzene, iodobenzene, and 0-bromotoluene. Halogenated aromatic hydrocarbon, tetrachloromethane, t, t, t-
Halogenated aliphatic hydrocarbons such as trichloroethane, tetrachloroethylene, and -chlorobutane can be used.
上記のような共重合反応は、上記のような溶媒中でラジ
カル開始剤をモノマーの合計モル数に対してモル比でl
O〜2X10−3の範囲で添加して行うことが好ましい
。また重合温度は一30〜200℃、好ましくは20〜
100℃である。The copolymerization reaction as described above is carried out in a solvent as described above using a radical initiator in a molar ratio of 1 to the total number of moles of monomers.
It is preferable to add in a range of 0 to 2×10 −3 . The polymerization temperature is -30 to 200°C, preferably 20 to 200°C.
The temperature is 100°C.
本発明に係る含フッ素共重合体と、有機顔料などとの親
和性をより向上させるため、含フッ素共重合体の分子鎖
中にカルボキシル基を導入することもできる。具体的に
は、不飽和カルボン酸またはその誘導体を含フッ素共重
合体にグラフト重合すればよい。このような目的で用い
られる不飽和カルボン酸類としては、アクリル酸、メタ
クリル酸、α−エチルアクリル酸、マレイン酸、フマー
ル酸、イタコン酸、シトラコン酸、テトラヒドロフタル
酸、メチルテトラヒドロフタル酸、エンドシス−ビシク
ロ[2,2,11ヘプト−5−エン−2,3−ジカルボ
ン酸(ナジック酸■)、メチル−エンドシス−ビシクロ
[2,2,1]ヘプト−5−エン−2,3−ジカルボン
酸(メチルナジック酸■)などの不飽和カルボン酸、該
不飽和カルボン酸のハライド、アミド、イミド、酸無水
物、エステルすなわち塩化マレニル、マレイミド、無水
マレイン酸、無水シトラコン酸、マレイン酸モノメチル
、マレイン酸ジメチルなどがある。In order to further improve the affinity between the fluorine-containing copolymer according to the present invention and organic pigments, a carboxyl group can also be introduced into the molecular chain of the fluorine-containing copolymer. Specifically, an unsaturated carboxylic acid or a derivative thereof may be graft-polymerized onto a fluorine-containing copolymer. Unsaturated carboxylic acids used for this purpose include acrylic acid, methacrylic acid, α-ethyl acrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, endocys-bicyclo [2,2,11hept-5-ene-2,3-dicarboxylic acid (nadic acid), methyl-endocys-bicyclo[2,2,1]hept-5-ene-2,3-dicarboxylic acid (methyl Unsaturated carboxylic acids such as nadic acid (■), halides, amides, imides, acid anhydrides, and esters of unsaturated carboxylic acids, including maleyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, etc. There is.
このようにして得られた含フッ素共重合体は、上記のよ
うに塩素捕捉剤を共存させたアルコール類などの有機溶
剤で処理して精製し、次いて該溶剤と残留モノマーを除
去すると含フッ素共重合体が得られる。その後、得られ
た含フッ素共重合体をキシレンなどの有機溶剤に溶解さ
せ、固形物を濾過した後、有機溶剤の濃度を調整すると
、含フッ素共重合体塗料が得られる。The fluorine-containing copolymer thus obtained is purified by treatment with an organic solvent such as alcohol in which a chlorine scavenger coexists as described above, and then the solvent and residual monomer are removed. A copolymer is obtained. Thereafter, the obtained fluorine-containing copolymer is dissolved in an organic solvent such as xylene, solid matter is filtered, and the concentration of the organic solvent is adjusted to obtain a fluorine-containing copolymer paint.
本発明に係る含フッ素共重合体の利用分野としては、上
記してきたように各種の有機溶剤に溶解した形で塗料組
成物として用いるのが最適である。As described above, the fluorine-containing copolymer according to the present invention is most suitable for use as a coating composition in the form of a solution in various organic solvents.
この場合、顔料あるいは染料などを塗料組成物に配合し
て着色塗料としてもよく、さらに必要に応じて通常合成
樹脂に配合される各種添加剤を配合してもよい。また上
記のような含フッ素共重合体を、シリル化アクリル樹脂
、シリコン系塗料、シリル化ポリオレフィンなどのアル
コキシシリル基あるいはシラノール基を有する樹脂の改
質剤として使用してもよい。In this case, pigments or dyes may be added to the paint composition to form a colored paint, and if necessary, various additives commonly added to synthetic resins may also be added. Further, the above-described fluorine-containing copolymer may be used as a modifier for resins having alkoxysilyl groups or silanol groups, such as silylated acrylic resins, silicone paints, and silylated polyolefins.
発明の効果
本発明では、上記のような含フッ素共重合体を製造する
に際して、重合反応時および/または得られた共重合体
の精製時に、系内に塩素捕捉剤を存在させているため、
着色のない含フッ素共重合体を得ることができる。Effects of the Invention In the present invention, when producing the above-mentioned fluorine-containing copolymer, a chlorine scavenger is present in the system during the polymerization reaction and/or during the purification of the obtained copolymer.
A colorless fluorine-containing copolymer can be obtained.
以下本発明の内容を好適な例でもって説明するが、とく
に断わりのない限り本発明はこれらの例に制限されるも
のではなく、本発明の目的を損わない範囲でいかなる態
様も可能である。The content of the present invention will be explained below using preferred examples, but unless otherwise specified, the present invention is not limited to these examples, and any embodiments are possible without impairing the purpose of the present invention. .
実施例1
内容積1.5gのステンレス製撹拌機付きオートクレー
ブ内を窒素置換し、窒素気流下にベンゼン180m1.
エチルビニルエーテル(EVE)106g、n−ブチル
ビニルエーテル(BYE)21.0g、)リメトキシビ
ニルシラン(TMVS)62.2g、合成ハイドロタル
サイト(Mg4.5A[2(OH) 13Co3・3.
5H20)粉末の焼成品(!IHT)13.Ogを仕込
んだ。その後、クロロトリフルオロエチレン(cTPE
) 257 gをオートクレーブ中に導入し、65℃ま
で昇温した。Example 1 The interior of a stainless steel autoclave with an internal volume of 1.5 g and equipped with a stirrer was purged with nitrogen, and 180 ml of benzene was added under a nitrogen stream.
Ethyl vinyl ether (EVE) 106g, n-butyl vinyl ether (BYE) 21.0g, )rimethoxyvinylsilane (TMVS) 62.2g, synthetic hydrotalcite (Mg4.5A[2(OH)13Co3.3.
5H20) Powder fired products (!IHT) 13. I prepared Og. Then, chlorotrifluoroethylene (cTPE)
) 257 g was introduced into an autoclave, and the temperature was raised to 65°C.
上記のようにして得られた混合液に、過酸化ジラウロイ
ル7.6gをベンゼン120ccに溶解させてなる開始
剤溶液を4時間かけてフィードした。An initiator solution prepared by dissolving 7.6 g of dilauroyl peroxide in 120 cc of benzene was fed to the mixture obtained as described above over 4 hours.
さらに65℃で6時間反応を行なった後、オートクレー
ブを水冷し、反応を停止させた。After further reacting at 65° C. for 6 hours, the autoclave was cooled with water to stop the reaction.
冷却後、未反応モノマーを追い出し、オートクレーブを
開放し、1.”lのナス形フラスコに反応液を取り出し
た。After cooling, unreacted monomers are expelled, the autoclave is opened, and 1. The reaction solution was taken out into a 1" eggplant-shaped flask.
この反応液にキシレン210g、メタノール120g、
5H713,Ogを加え、50℃で1.5時間さらに6
0℃で1.5時間撹拌下に加熱処理した。In this reaction solution, 210 g of xylene, 120 g of methanol,
5H713,Og was added and further heated at 50°C for 1.5 hours.
Heat treatment was performed at 0° C. for 1.5 hours with stirring.
処理後、エバポレーターにて減圧下に残留モノマーおよ
び溶媒を留去し、次いでキシレン550gを加え、撹拌
により均一溶液とした。After the treatment, residual monomers and solvent were distilled off under reduced pressure using an evaporator, and then 550 g of xylene was added and stirred to form a homogeneous solution.
この溶液を濾過してSHTを除去し、減圧濃縮して無色
透明な重合体366gを得た。This solution was filtered to remove SHT and concentrated under reduced pressure to obtain 366 g of a colorless and transparent polymer.
得られたポリマーのGPCによる数平均分子量は10.
000であった。The number average molecular weight of the obtained polymer by GPC was 10.
It was 000.
また、この共重合体の組成分析を元素分析およびNMR
を用いて行なったところ、CTFE/EVE/BVE/
TMVS−50/37/6/7(モル比)であった。In addition, the composition analysis of this copolymer was carried out by elemental analysis and NMR.
CTFE/EVE/BVE/
TMVS-50/37/6/7 (molar ratio).
このようにして得られた含、フッ素共重合体の着色度を
、黄色の補色である波長420nmの光の吸光度を下記
のようにして測定したところ、6.4であった。The degree of coloring of the fluorine-containing copolymer thus obtained was 6.4 when the absorbance of light at a wavelength of 420 nm, which is a complementary color to yellow, was measured as follows.
く波長420nm光の吸収測定法〉
含フッ素共重合体100重量部をキシレン100重量部
に溶解させ、樹脂溶液を調製する。Absorption measurement method for light with a wavelength of 420 nm> 100 parts by weight of a fluorine-containing copolymer is dissolved in 100 parts by weight of xylene to prepare a resin solution.
一方Multlpurpose Recordlng
5pectrophotos+eter MPS−20
00(島原製作所製)を用いて、予めキシレンの波長4
20 rv光の吸光度を測定しておく。On the other hand, Multlpurpose Recordlng
5pectrophotos+eter MPS-20
00 (manufactured by Shimabara Seisakusho),
20 Measure the absorbance of RV light.
次いで、上記樹脂溶液の吸収を調べ、これよりキシレン
の吸収分を差引いた値を樹脂の吸光度とした。Next, the absorption of the resin solution was examined, and the value obtained by subtracting the absorption of xylene from this was taken as the absorbance of the resin.
なおこの測定における吸光度と目視による着色度判定(
ガードナーNo)との概略の関係を以下に示す。In addition, in this measurement, the absorbance and visual coloring degree judgment (
The approximate relationship with Gardner No.) is shown below.
ガードナー No、1 吸光度 50X10−3ガ
ードナー N092 吸光度 100X10−3実施
例2
実施例1と同様にして塩酸捕捉剤の量を変えて共重合体
を得た。塩酸捕捉剤の量および重合体の着色度を表1に
示す。Gardner No. 1 Absorbance 50X10-3 Gardner N092 Absorbance 100X10-3 Example 2 A copolymer was obtained in the same manner as in Example 1 by changing the amount of the hydrochloric acid scavenger. The amount of hydrochloric acid scavenger and the degree of coloration of the polymer are shown in Table 1.
実施例3
実施例1における重合反応後、オートクレーブ開放以後
の操作を以下のように行なったらキシレン210gを加
え、エバポレータにて減圧下に残留モノマーおよび溶媒
を留去し、次いでキシレンを550gを加え、撹拌によ
り均一溶液とした。この溶液を濾過してSHTを除去し
、減圧濃縮して共重合体を得た。Example 3 After the polymerization reaction in Example 1, the following operations were performed after opening the autoclave: 210 g of xylene was added, the residual monomer and solvent were distilled off under reduced pressure using an evaporator, and then 550 g of xylene was added. A homogeneous solution was obtained by stirring. This solution was filtered to remove SHT and concentrated under reduced pressure to obtain a copolymer.
得られた重合体の着色度を表1に示す。Table 1 shows the degree of coloration of the obtained polymer.
実施例4〜8
実施例1における塩酸捕捉剤の種類、量および精製時に
加えるアルコール量を変えて共重合体を得た。塩酸捕捉
剤の種類、量および加えたアルコール量、得られた共重
合体の着色度を表1に示す。Examples 4 to 8 Copolymers were obtained by changing the type and amount of the hydrochloric acid scavenger and the amount of alcohol added during purification in Example 1. Table 1 shows the type and amount of the hydrochloric acid scavenger, the amount of alcohol added, and the degree of coloration of the obtained copolymer.
実施例9
実施例1と同様の重合装置を用い、装置内を窒素置換し
、窒素気流下にベンゼン180m1、エチルビニルエー
テル(EVE) 106 g、 n−ブチルビニルエ−
テル(BYE)21.0g、)リエトキシビニルシラン
(TEVS) 79. 9 g、合成ハイドロタルサイ
ト(Mg AIJ (OH) 13CO34,5
2
3,5H20)粉末の焼成品(SIIT) 13.
Ogを仕込んだ。その後、クロロトリフルオロエチレン
(cTFE) 257 gをオートクレーブ中に導入し
、65℃まで昇温した。Example 9 Using the same polymerization apparatus as in Example 1, the inside of the apparatus was replaced with nitrogen, and 180 ml of benzene, 106 g of ethyl vinyl ether (EVE), and n-butyl vinyl ether were added under a nitrogen stream.
BYE 21.0g,) ethoxyvinylsilane (TEVS) 79. 9 g, synthetic hydrotalcite (Mg AIJ (OH) 13CO34,5
2 3,5H20) Powder fired products (SIIT) 13.
I prepared Og. Thereafter, 257 g of chlorotrifluoroethylene (cTFE) was introduced into the autoclave, and the temperature was raised to 65°C.
上記のようにして得られた混合液に、過酸化ジラウロイ
ル7.6gをベンゼン120ccに溶解させてなる開始
剤溶液を4時間かけてフィードした。An initiator solution prepared by dissolving 7.6 g of dilauroyl peroxide in 120 cc of benzene was fed to the mixture obtained as described above over 4 hours.
さらに65℃で6時間反応を行なった後、オートクレー
ブを水冷し、反応を停止させた。After further reacting at 65° C. for 6 hours, the autoclave was cooled with water to stop the reaction.
冷却後、未反応モノマーを追い出し、オートクレーブを
開放し、1.5Nのナス形フラスコに反応液を取り出し
た。After cooling, unreacted monomers were expelled, the autoclave was opened, and the reaction solution was taken out into a 1.5N eggplant flask.
この反応液に、キシレン210g、エタノール1.73
g、5HTi3.Ogを加え、50℃で1.5時間さら
に60℃で1.5時間撹拌下に加熱処理した。To this reaction solution, 210 g of xylene and 1.73 g of ethanol were added.
g, 5HTi3. After adding Og, the mixture was heated at 50°C for 1.5 hours and then at 60°C for 1.5 hours with stirring.
処理後、エバポレーターにて減圧下に残留モノマ、−お
よび溶媒を留去し、次いでキシレン550gを加え、撹
拌により均一溶液とした。After the treatment, residual monomers and solvents were distilled off under reduced pressure using an evaporator, and then 550 g of xylene was added and stirred to form a homogeneous solution.
この溶液を濾過してSHTを除去し、減圧濃縮して重合
体406gを得た。This solution was filtered to remove SHT and concentrated under reduced pressure to obtain 406 g of a polymer.
共重合体の着色度を表1に示す。Table 1 shows the degree of coloration of the copolymer.
実施例10
実施例1と同様の重合装置を用い、装置内を窒素置換し
、窒素気流下にベンゼン180m1.エチルビニルエー
テル(EVE) 106 g、 n−ブチルビニルエー
テル(BVE) 21. 0 g、 3−ヒ=o−t−
ジプロピルトリメトキシシラン(VoPTMS) 86
.6g1合成ハイドロタルサイト(Mg AlF2
.52
(OH) C0・3.5H20)粉末の焼成品(SI
IT) 13. 0 gを仕込んだ。その後、クロロト
リフルオロエチレン(cTFE) 257 gをオート
クレーブ中に導入し、65℃まで昇温した。Example 10 Using the same polymerization apparatus as in Example 1, the inside of the apparatus was replaced with nitrogen, and 180 ml of benzene was added under a nitrogen stream. Ethyl vinyl ether (EVE) 106 g, n-butyl vinyl ether (BVE) 21. 0 g, 3-hi=o-t-
Dipropyltrimethoxysilane (VoPTMS) 86
.. 6g1 synthetic hydrotalcite (Mg AlF2
.. 52 (OH) C0・3.5H20) Powder fired product (SI
IT) 13. 0 g was charged. Thereafter, 257 g of chlorotrifluoroethylene (cTFE) was introduced into the autoclave, and the temperature was raised to 65°C.
このようにして得られた混合液に、過酸化ジラウロイル
7.6gをベンゼン120ccに溶解させてなる開始剤
溶液を4時間かけてフィードした。An initiator solution prepared by dissolving 7.6 g of dilauroyl peroxide in 120 cc of benzene was fed to the mixture thus obtained over 4 hours.
さらに65℃で6時間反応を9行なった後、オートクレ
ーブを水冷し、反応を停止させた。After further 9 reactions at 65° C. for 6 hours, the autoclave was cooled with water to stop the reaction.
冷却後、未反応上ツマ−を追い出し、オートクレーブを
開放し、1.’lのナス形フラスコに反応液を取り出し
た。After cooling, remove the unreacted upper part, open the autoclave, and proceed as follows: 1. The reaction solution was taken out into a 1.5-liter eggplant-shaped flask.
この反応液に、キシレン210f、メタノール120g
、5HT13.ogを加え、50℃で1.5時間さらに
60℃で1.5時間撹拌下に加熱処理した。To this reaction solution, add 210 g of xylene and 120 g of methanol.
, 5HT13. The mixture was heated at 50° C. for 1.5 hours and then at 60° C. for 1.5 hours with stirring.
処理後、エバポレーターにて減圧下に残留モノマーおよ
び溶媒を留去し、次いでキシレン550gを加え、撹拌
により均一溶液とした。After the treatment, residual monomers and solvent were distilled off under reduced pressure using an evaporator, and then 550 g of xylene was added and stirred to form a homogeneous solution.
この溶液を濾過して5I(Tを除去し、減圧濃縮して重
合体448gを得た。This solution was filtered to remove 5I(T) and concentrated under reduced pressure to obtain 448 g of a polymer.
共重合体の着色度を表1に示す。Table 1 shows the degree of coloration of the copolymer.
比較例1
実施例1と同様の重合装置を用い、装置内を窒素置換し
、窒素気流下にベンゼン180m1.エチルビニルエー
テル(EVE) 106 g、 n−ブチルビニルエー
テル(BYE)21゜Ogl トリメトキシビニルシラ
ン(TMVS) 62. 2 gを仕込んだ。その後、
クロロトリフルオロエチレン(cTPE)257gをオ
ートクレーブ中に導入し、65℃まで昇温した。Comparative Example 1 Using the same polymerization apparatus as in Example 1, the inside of the apparatus was replaced with nitrogen, and 180 ml of benzene was added under a nitrogen stream. Ethyl vinyl ether (EVE) 106 g, n-butyl vinyl ether (BYE) 21° Ogl Trimethoxyvinyl silane (TMVS) 62. 2 g was added. after that,
257 g of chlorotrifluoroethylene (cTPE) was introduced into the autoclave, and the temperature was raised to 65°C.
このようにして得られた混合液に、に過酸化ジー7つo
イル7.6gをベンゼン120ccに溶解させてなる開
始剤溶液を4時間かけてフィードした。Add 7 o peroxide to the mixture thus obtained.
An initiator solution prepared by dissolving 7.6 g of chlorine in 120 cc of benzene was fed over 4 hours.
さらに65℃で6時間反応を行なった後、オートクレー
ブを水冷し、反応を停止させた。After further reacting at 65° C. for 6 hours, the autoclave was cooled with water to stop the reaction.
冷却後、未反応モノマーを追い出し、オートクレーブを
開放し、1.5Nのナス形フラスコに反応液を取り出し
、エバポレーターにて減圧下に残留モノマーおよび溶媒
を留去して共重合体380gを得た。After cooling, unreacted monomers were expelled, the autoclave was opened, and the reaction solution was taken out into a 1.5N eggplant-shaped flask, and the residual monomers and solvent were distilled off under reduced pressure using an evaporator to obtain 380 g of a copolymer.
得られた共重合体の着色度を表1に示す。Table 1 shows the degree of coloration of the obtained copolymer.
Claims (1)
を有する有機珪素化合物 を共重合させることによって含フッ素共重合体を製造す
るに際して、 重合反応時および/または得られた共重合体の精製時に
、系内に塩素捕捉剤を存在させることを特徴とする含フ
ッ素共重合体の製造方法。 2、塩素捕捉剤が、M_xAl_y(OH)_2_x_
+_3_y_−_2_z(A)_z・aH_2O(式中
、MはMg、CaまたはZnであり、AはCO_3また
はHPO_4であり、x、y、zは正数であり、aは0
または正数である)で示される化合物である請求項第1
項に記載の含フッ素共重合体の製造方法。 3、塩素捕捉剤がアルカリ土類金属の塩基性化合物であ
る請求項第1項に記載の含フッ素共重合体の製造方法。 4、塩素捕捉剤がエポキシ含有化合物である請求項第1
項に記載の含フッ素共重合体の製造方法。[Claims] 1. A fluorine-containing copolymer by copolymerizing (a) a fluoroolefin containing chlorine, (b) a vinyl ether, and (c) an organosilicon compound having an olefinic unsaturated bond and a hydrolyzable group. 1. A method for producing a fluorine-containing copolymer, characterized in that a chlorine scavenger is present in the system during the polymerization reaction and/or during purification of the obtained copolymer. 2. The chlorine scavenger is M_xAl_y(OH)_2_x_
+_3_y_-_2_z(A)_z・aH_2O (where M is Mg, Ca or Zn, A is CO_3 or HPO_4, x, y, z are positive numbers, a is 0
or a positive number) Claim 1
A method for producing a fluorine-containing copolymer as described in 2. 3. The method for producing a fluorine-containing copolymer according to claim 1, wherein the chlorine scavenger is a basic compound of an alkaline earth metal. 4. Claim 1, wherein the chlorine scavenger is an epoxy-containing compound.
A method for producing a fluorine-containing copolymer as described in 2.
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63305443A JP2725726B2 (en) | 1988-12-02 | 1988-12-02 | Method for producing fluorinated copolymer |
EP19890312391 EP0372805A3 (en) | 1988-12-02 | 1989-11-29 | Process for producing fluorine-containing copolymer and fluorine-containing copolymer composition |
EP94119270A EP0646625A3 (en) | 1988-12-02 | 1989-11-29 | Fluorine-containing copolymer composition. |
CA002004271A CA2004271C (en) | 1988-12-02 | 1989-11-30 | Process for producing fluorine-containing copolymer and fluorine-containg copolymer composition |
US07/444,401 US5043393A (en) | 1988-12-02 | 1989-12-01 | Process for producing fluorine-containing copolymer and fluorine-containing copolymer composition |
KR1019890017798A KR920006447B1 (en) | 1988-12-02 | 1989-12-02 | Process for producing fluorine-containing copolymer and fluorine-containing copolymer composition |
US07/698,859 US5179181A (en) | 1988-12-02 | 1991-05-13 | Process for producing fluorine-containing copolymer and fluorine-containing copolymer composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63305443A JP2725726B2 (en) | 1988-12-02 | 1988-12-02 | Method for producing fluorinated copolymer |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH02151610A true JPH02151610A (en) | 1990-06-11 |
JP2725726B2 JP2725726B2 (en) | 1998-03-11 |
Family
ID=17945203
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP63305443A Expired - Lifetime JP2725726B2 (en) | 1988-12-02 | 1988-12-02 | Method for producing fluorinated copolymer |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2725726B2 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05271349A (en) * | 1992-03-30 | 1993-10-19 | Central Glass Co Ltd | Production of resin for coating |
WO1998049210A1 (en) * | 1997-04-25 | 1998-11-05 | Asahi Kasei Kogyo Kabushiki Kaisha | Polyvinylidene chloride latex and process for the preparation thereof |
WO2010095722A1 (en) * | 2009-02-23 | 2010-08-26 | 旭硝子株式会社 | Method for producing fluoroolefin copolymer solution and method for producing paint composition |
WO2013175962A1 (en) * | 2012-05-24 | 2013-11-28 | ダイキン工業株式会社 | Fluorine-containing polymer and method for producing same |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61141713A (en) * | 1984-12-14 | 1986-06-28 | Mitsui Petrochem Ind Ltd | Solvent-soluble fluorocarbon polymer and its use |
JPS62265605A (en) * | 1986-05-13 | 1987-11-18 | Mitsui Petrochem Ind Ltd | Optical fiber having clad part essentially consisting of fluorine polymer |
-
1988
- 1988-12-02 JP JP63305443A patent/JP2725726B2/en not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61141713A (en) * | 1984-12-14 | 1986-06-28 | Mitsui Petrochem Ind Ltd | Solvent-soluble fluorocarbon polymer and its use |
JPS62265605A (en) * | 1986-05-13 | 1987-11-18 | Mitsui Petrochem Ind Ltd | Optical fiber having clad part essentially consisting of fluorine polymer |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05271349A (en) * | 1992-03-30 | 1993-10-19 | Central Glass Co Ltd | Production of resin for coating |
WO1998049210A1 (en) * | 1997-04-25 | 1998-11-05 | Asahi Kasei Kogyo Kabushiki Kaisha | Polyvinylidene chloride latex and process for the preparation thereof |
US6172158B1 (en) | 1997-04-25 | 2001-01-09 | Asahi Kasei Kogyo Kabushiki Kaisha | Vinylidene chloride-based latex and process for producing the same |
WO2010095722A1 (en) * | 2009-02-23 | 2010-08-26 | 旭硝子株式会社 | Method for producing fluoroolefin copolymer solution and method for producing paint composition |
US8461251B2 (en) | 2009-02-23 | 2013-06-11 | Asahi Glass Company, Limited | Method for producing fluoroolefin copolymer solution and method for producing coating composition |
WO2013175962A1 (en) * | 2012-05-24 | 2013-11-28 | ダイキン工業株式会社 | Fluorine-containing polymer and method for producing same |
JP2014001369A (en) * | 2012-05-24 | 2014-01-09 | Daikin Ind Ltd | Fluorine-containing polymer and method for producing the same |
Also Published As
Publication number | Publication date |
---|---|
JP2725726B2 (en) | 1998-03-11 |
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