JPH01319513A - Improved production of copolymer of ethylene vinyl acetate and reactive halogen-containing monomer - Google Patents
Improved production of copolymer of ethylene vinyl acetate and reactive halogen-containing monomerInfo
- Publication number
- JPH01319513A JPH01319513A JP15246788A JP15246788A JPH01319513A JP H01319513 A JPH01319513 A JP H01319513A JP 15246788 A JP15246788 A JP 15246788A JP 15246788 A JP15246788 A JP 15246788A JP H01319513 A JPH01319513 A JP H01319513A
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- vinyl
- monomer
- vinyl acetate
- ethylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000178 monomer Substances 0.000 title claims abstract description 78
- 229910052736 halogen Inorganic materials 0.000 title claims abstract description 26
- 150000002367 halogens Chemical class 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 229920001577 copolymer Polymers 0.000 title abstract description 7
- 239000005038 ethylene vinyl acetate Substances 0.000 title description 11
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 title description 11
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 title description 9
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 109
- 229920001971 elastomer Polymers 0.000 claims abstract description 62
- 239000000806 elastomer Substances 0.000 claims abstract description 58
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000005977 Ethylene Substances 0.000 claims abstract description 54
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 17
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 16
- 239000011593 sulfur Substances 0.000 claims abstract description 16
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000839 emulsion Substances 0.000 claims abstract description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 61
- XJELOQYISYPGDX-UHFFFAOYSA-N ethenyl 2-chloroacetate Chemical compound ClCC(=O)OC=C XJELOQYISYPGDX-UHFFFAOYSA-N 0.000 claims description 25
- 230000008569 process Effects 0.000 claims description 17
- 239000003638 chemical reducing agent Substances 0.000 claims description 15
- 229920002554 vinyl polymer Polymers 0.000 claims description 12
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 10
- 239000003945 anionic surfactant Substances 0.000 claims description 9
- 239000000460 chlorine Substances 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 claims description 5
- 238000010526 radical polymerization reaction Methods 0.000 claims description 3
- 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 claims description 2
- REEBWSYYNPPSKV-UHFFFAOYSA-N 3-[(4-formylphenoxy)methyl]thiophene-2-carbonitrile Chemical compound C1=CC(C=O)=CC=C1OCC1=C(C#N)SC=C1 REEBWSYYNPPSKV-UHFFFAOYSA-N 0.000 claims description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 2
- DFEHSFZILGOAJK-UHFFFAOYSA-N ethenyl 2-bromoacetate Chemical compound BrCC(=O)OC=C DFEHSFZILGOAJK-UHFFFAOYSA-N 0.000 claims description 2
- YCPJOTBZJGWFOT-UHFFFAOYSA-N ethenyl 2-chloro-2-methylpropanoate Chemical compound CC(C)(Cl)C(=O)OC=C YCPJOTBZJGWFOT-UHFFFAOYSA-N 0.000 claims description 2
- FHKXSTLIOCXCNC-UHFFFAOYSA-N ethenyl 2-chlorobutanoate Chemical compound CCC(Cl)C(=O)OC=C FHKXSTLIOCXCNC-UHFFFAOYSA-N 0.000 claims description 2
- BTOIAAYVFNXNPA-UHFFFAOYSA-N ethenyl 2-chloropropanoate Chemical compound CC(Cl)C(=O)OC=C BTOIAAYVFNXNPA-UHFFFAOYSA-N 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims description 2
- 239000002685 polymerization catalyst Substances 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 2
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims description 2
- 229940079827 sodium hydrogen sulfite Drugs 0.000 claims description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 2
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 2
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 2
- 229960001922 sodium perborate Drugs 0.000 claims description 2
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 2
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 claims description 2
- 239000011953 free-radical catalyst Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 14
- -1 (for example Chemical compound 0.000 abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 239000004094 surface-active agent Substances 0.000 abstract description 4
- 150000003254 radicals Chemical class 0.000 abstract description 3
- ZXFHYTWKGJWGFM-UHFFFAOYSA-N 1-chloroethenyl acetate Chemical compound CC(=O)OC(Cl)=C ZXFHYTWKGJWGFM-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002563 ionic surfactant Substances 0.000 abstract description 2
- 230000000379 polymerizing effect Effects 0.000 abstract 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
- 238000007792 addition Methods 0.000 description 18
- 239000006229 carbon black Substances 0.000 description 14
- 235000019241 carbon black Nutrition 0.000 description 14
- 239000000243 solution Substances 0.000 description 12
- 238000010059 sulfur vulcanization Methods 0.000 description 10
- 229920001897 terpolymer Polymers 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000007334 copolymerization reaction Methods 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 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 5
- 239000004816 latex Substances 0.000 description 5
- 229920000126 latex Polymers 0.000 description 5
- 230000002787 reinforcement Effects 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000000344 soap Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000004073 vulcanization Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 235000021355 Stearic acid Nutrition 0.000 description 4
- 229920002359 Tetronic® Polymers 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 239000008117 stearic acid Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000872 buffer Substances 0.000 description 3
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 3
- 229940106681 chloroacetic acid Drugs 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- 235000017281 sodium acetate Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229920001567 vinyl ester resin Polymers 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- JLIDVCMBCGBIEY-UHFFFAOYSA-N 1-penten-3-one Chemical compound CCC(=O)C=C JLIDVCMBCGBIEY-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000006238 High Abrasion Furnace Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- TVWTZAGVNBPXHU-FOCLMDBBSA-N dioctyl (e)-but-2-enedioate Chemical compound CCCCCCCCOC(=O)\C=C\C(=O)OCCCCCCCC TVWTZAGVNBPXHU-FOCLMDBBSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 239000006232 furnace black Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical class COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- VYPDUQYOLCLEGS-UHFFFAOYSA-M sodium;2-ethylhexanoate Chemical compound [Na+].CCCCC(CC)C([O-])=O VYPDUQYOLCLEGS-UHFFFAOYSA-M 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- SLBOQBILGNEPEB-UHFFFAOYSA-N 1-chloroprop-2-enylbenzene Chemical compound C=CC(Cl)C1=CC=CC=C1 SLBOQBILGNEPEB-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- OYLCUJRJCUXQBQ-UHFFFAOYSA-N 1-hepten-3-one Chemical compound CCCCC(=O)C=C OYLCUJRJCUXQBQ-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
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- GPOGMJLHWQHEGF-UHFFFAOYSA-N 2-chloroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCl GPOGMJLHWQHEGF-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 240000006108 Allium ampeloprasum Species 0.000 description 1
- 235000005254 Allium ampeloprasum Nutrition 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 241000416162 Astragalus gummifer Species 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- XEGJCFAFRZIZNG-UHFFFAOYSA-N ClCC(=O)OC=CC=C Chemical compound ClCC(=O)OC=CC=C XEGJCFAFRZIZNG-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 235000010643 Leucaena leucocephala Nutrition 0.000 description 1
- 240000007472 Leucaena leucocephala Species 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229920001615 Tragacanth Polymers 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- BGPLHMAJJNBWGQ-UHFFFAOYSA-L [Na+].[Na+].O=C.OO.[O-]S[O-] Chemical group [Na+].[Na+].O=C.OO.[O-]S[O-] BGPLHMAJJNBWGQ-UHFFFAOYSA-L 0.000 description 1
- XAQHXGSHRMHVMU-UHFFFAOYSA-N [S].[S] Chemical compound [S].[S] XAQHXGSHRMHVMU-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CGNRQCGWXXLTIA-UHFFFAOYSA-N bis(2-ethylhexyl) 2-methylidenebutanedioate Chemical compound CCCCC(CC)COC(=O)CC(=C)C(=O)OCC(CC)CCCC CGNRQCGWXXLTIA-UHFFFAOYSA-N 0.000 description 1
- 238000000861 blow drying Methods 0.000 description 1
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- QYMGIIIPAFAFRX-UHFFFAOYSA-N butyl prop-2-enoate;ethene Chemical compound C=C.CCCCOC(=O)C=C QYMGIIIPAFAFRX-UHFFFAOYSA-N 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- JBSLOWBPDRZSMB-BQYQJAHWSA-N dibutyl (e)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C\C(=O)OCCCC JBSLOWBPDRZSMB-BQYQJAHWSA-N 0.000 description 1
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 description 1
- OGVXYCDTRMDYOG-UHFFFAOYSA-N dibutyl 2-methylidenebutanedioate Chemical compound CCCCOC(=O)CC(=C)C(=O)OCCCC OGVXYCDTRMDYOG-UHFFFAOYSA-N 0.000 description 1
- ZFTFAPZRGNKQPU-UHFFFAOYSA-N dicarbonic acid Chemical class OC(=O)OC(O)=O ZFTFAPZRGNKQPU-UHFFFAOYSA-N 0.000 description 1
- HEJZJSIRBLOWPD-WCWDXBQESA-N didodecyl (e)-but-2-enedioate Chemical compound CCCCCCCCCCCCOC(=O)\C=C\C(=O)OCCCCCCCCCCCC HEJZJSIRBLOWPD-WCWDXBQESA-N 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- DSTWFRCNXMNXTR-AATRIKPKSA-N dipropyl (e)-but-2-enedioate Chemical compound CCCOC(=O)\C=C\C(=O)OCCC DSTWFRCNXMNXTR-AATRIKPKSA-N 0.000 description 1
- SMVRDGHCVNAOIN-UHFFFAOYSA-L disodium;1-dodecoxydodecane;sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O.CCCCCCCCCCCCOCCCCCCCCCCCC SMVRDGHCVNAOIN-UHFFFAOYSA-L 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229910001651 emery Inorganic materials 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- BEGBSFPALGFMJI-UHFFFAOYSA-N ethene;sodium Chemical group [Na].C=C BEGBSFPALGFMJI-UHFFFAOYSA-N 0.000 description 1
- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-UHFFFAOYSA-N 0.000 description 1
- YVELKSUQPQWUEW-UHFFFAOYSA-N ethenyl 3-chloropropanoate Chemical compound ClCCC(=O)OC=C YVELKSUQPQWUEW-UHFFFAOYSA-N 0.000 description 1
- XUPMJJRMJSWCAS-UHFFFAOYSA-N ethenyl 4-chlorobutanoate Chemical compound ClCCCC(=O)OC=C XUPMJJRMJSWCAS-UHFFFAOYSA-N 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229920006245 ethylene-butyl acrylate Polymers 0.000 description 1
- 229920006225 ethylene-methyl acrylate Polymers 0.000 description 1
- 239000005043 ethylene-methyl acrylate Substances 0.000 description 1
- ISXSFOPKZQZDAO-UHFFFAOYSA-N formaldehyde;sodium Chemical compound [Na].O=C ISXSFOPKZQZDAO-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910001869 inorganic persulfate Inorganic materials 0.000 description 1
- 150000004668 long chain fatty acids Chemical class 0.000 description 1
- 150000005679 long-chain carbonates Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- UTSYWKJYFPPRAP-UHFFFAOYSA-N n-(butoxymethyl)prop-2-enamide Chemical compound CCCCOCNC(=O)C=C UTSYWKJYFPPRAP-UHFFFAOYSA-N 0.000 description 1
- ULYOZOPEFCQZHH-UHFFFAOYSA-N n-(methoxymethyl)prop-2-enamide Chemical compound COCNC(=O)C=C ULYOZOPEFCQZHH-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical class C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920000962 poly(amidoamine) Polymers 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000005373 porous glass Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- VMBJJCDVORDOCF-UHFFFAOYSA-N prop-2-enyl 2-chloroacetate Chemical compound ClCC(=O)OCC=C VMBJJCDVORDOCF-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000010057 rubber processing Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- FCZYGJBVLGLYQU-UHFFFAOYSA-M sodium;2-[2-[2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethoxy]ethoxy]ethanesulfonate Chemical compound [Na+].CC(C)(C)CC(C)(C)C1=CC=C(OCCOCCOCCS([O-])(=O)=O)C=C1 FCZYGJBVLGLYQU-UHFFFAOYSA-M 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 239000000196 tragacanth Substances 0.000 description 1
- 235000010487 tragacanth Nutrition 0.000 description 1
- 229940116362 tragacanth Drugs 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
本発明はエチレン、酢やビニルおよびクロロ酢酸ビニル
（ＶＣＡ）の様な反応性ハロゲン含有モノマーの高ムー
ニー （Ｍｏｏｎｅｙ ）粘度共重合体（インターポリ
マー）ニジストマーの改良製造方法に関する。導入した
ー・ロゲン含有単位は加硫のキュアサイトとして働へ特
にこの方法は加硫の際引張強度が増加するインターポリ
マーエラストマー製品がえられる様に重合反応中クロロ
酢酸ビニルキュアサイトモノマーを加える新規の方法に
関する。DETAILED DESCRIPTION OF THE INVENTION This invention relates to an improved process for producing high Mooney viscosity interpolymer distomers of reactive halogen-containing monomers such as ethylene, vinegar and vinyl and chlorovinyl acetate (VCA). . In particular, this method introduces a novel method in which a vinyl chloroacetate cure site monomer is added during the polymerization reaction to yield an interpolymer elastomer product with increased tensile strength during vulcanization. Regarding the method.
エチレン−酢酸ビニル−クロロ酢酸ビニル（’Ｅ／ＶＡ
／ＣＶＡ）インターポリマーエラストマー〇製造法はこ
の技術分野において知られている。例えばカイザーマン
らは米国特許第３．９７２，８５７号において触媒とし
てｐ−）ルエンスルホンｌ！２を用いキシレン溶液中で
エチレン−酢酸ビニル（ＥＶＡ）コポリマーエラストマ
ーをクロロ酢酸と化学的に反応させてＥ／ＶＡ／ＶＣＡ
インターポリマーを製造している。クロロ酢酸によるＥ
ＶＡコポリマーの酸分解によって生成された酢酸は蒸留
によって除去され、今や化学的に加えられたＶＣＡ単位
をもつＥＶＡコポリマーはイソプロピルアルコールとの
沈澱によってえられる。石鹸−いおうキュア系によって
加硫されつる０、２乃至４．５重量％塩素を含むエラス
トマーがえられる。Ethylene-vinyl acetate-vinyl chloroacetate ('E/VA
/CVA) Interpolymer elastomer manufacturing methods are known in the art. For example, Kaiserman et al. in U.S. Pat. No. 3,972,857 used p-)luenesulfone l! as a catalyst. E/VA/VCA was obtained by chemically reacting an ethylene-vinyl acetate (EVA) copolymer elastomer with chloroacetic acid in a xylene solution using
Manufactures interpolymers. E with chloroacetic acid
The acetic acid produced by acid decomposition of the VA copolymer is removed by distillation, and the EVA copolymer with chemically added VCA units is now obtained by precipitation with isopropyl alcohol. Vulcanization with a soap-sulfur cure system yields elastomers containing 0.2 to 4.5% by weight chlorine.
石鹸−いおう加硫性エチレン−酢酸ビニルエラストマー
組成物の他の製法はチャンクらの米国特許第４，２０２
，８４５号がある。チャンクらはアクリレート エステ
ルモノマーをクロロ酢酸ビニル、キユアサイトモノマー
と共にニジストマー性ＥＶＡコポリマー骨格上に結合し
ている。Another method for making soap-sulfur vulcanizable ethylene-vinyl acetate elastomer compositions is disclosed in Chank et al., U.S. Pat. No. 4,202.
, No. 845. Chunk et al. coupled an acrylate ester monomer with vinyl chloroacetate, a cure site monomer, onto a di-stomeric EVA copolymer backbone.
前記のとおり上記反応性ノ・ロゲンキュアサイト金もつ
両組酸物は石鹸−いおう加硫をうけて有用なエラ２トマ
一性製品となる。一般に石鹸−いおう加硫にはエラスト
マーとカーボンブラック強化剤の他にステアリン酸ナト
リウム又は２−エチルカプロン酸ナトリウムの様な石鹸
、いおう、ステアリン酸および酸化防止剤が含まれる。As mentioned above, the reactive non-rogen cure site gold complex acids are subjected to soap-sulfur vulcanization to form useful elastomeric products. Generally, a soap-sulfur vulcanization includes, in addition to the elastomer and carbon black reinforcement, a soap, sulfur, stearic acid, and an antioxidant, such as sodium stearate or sodium 2-ethylcaproate.
石鹸−いおう加愼用エラストマーには不飽和物は必要な
い。実際の機構は確実でないが、−８Ｘ−架橋が導入さ
れる徴候がある。No unsaturations are required in soap-smoking elastomers. Although the actual mechanism is not certain, there are indications that an -8X-bridge is introduced.
〔ケンドラ−らのＤｉｅ Ａｎｇｅｗａｎｄｔｅ Ｍａ
ｋｒｏｍｏｌｅｌｃｕ−１ａｒｅ Ｃｈｅｍｉｅ、２９
／３０，２４１ （１９７３）Ｅとも角石鹸いおう加硫
は炭素−炭素不飽和２重結合がエラストマー中になくて
はならない普通のいおう加硫とは根本的にちがう。[Die Angewandte Ma by Kendra et al.
kromolecu-1are Chemie, 29
/30, 241 (1973) E. Sulfur sulfur vulcanization is fundamentally different from ordinary sulfur vulcanization in which carbon-carbon unsaturated double bonds must be present in the elastomer.
上記カイザーマンらとチャンクらのキュアサイトをエチ
レン−酢酸ビニルコポリマーエラストマー中に入れる化
学的方法に伴なって多くの利点がある。中でもカイザー
マンらの多工程方法は経費がかかる。先づＥＶＡを合疲
した後キシレンにとかし次いで比較的おそい複鈴な溶媒
方法でクロロ酢酸と反応させる必要がある。化学的改良
製品はイソプロピルアルコールの様な非溶媒を使って沈
澱回収乾燥する心安がある。溶媒と非溶媒の回収、分離
および精製には工業操作を要する。There are many advantages associated with the Kaiserman et al. and Chank et al. chemical method of incorporating curesite into ethylene-vinyl acetate copolymer elastomers. Among them, the multi-step method of Kaiserman et al. is expensive. The EVA must first be combined and then dissolved in xylene and then reacted with chloroacetic acid in a relatively slow and complex solvent process. Chemically modified products can be safely precipitated and dried using a non-solvent such as isopropyl alcohol. Recovery, separation, and purification of solvents and nonsolvents requires industrial operations.
チャンクらのグラフト重合法も多工程法であり、随拌物
から紗費増をうける。先づＥＶＡエラストマーを合成し
た後、スラリ操作において比較的高価外アクリレートエ
ステルモノマーどクラフトきせる必要がある。上記グラ
フト操作もＶＣＡキュアサイトを仕上りグラフト組成物
中に加える。The graft polymerization method of Chunk et al. is also a multi-step method and suffers from increased gauze costs due to the agitation. After first synthesizing the EVA elastomer, it is necessary to craft the relatively expensive acrylate ester monomer in a slurry operation. The above grafting operation also incorporates VCA cure site into the finished grafting composition.
エチレンおよび酢酸ビニルを比較的少量のＶＣＡ又は他
の同様なハロゲン含有キュアサイトモノマーと共重合さ
せる簡単な低コスト方法が使用できれば非常に好１しく
便利であろう。しかしポリマー化学者間ではＶＣＡはむ
しろ有力な鎖移動剤であるとされている。鎖移動剤に対
するこの傾向は、キユアサイトモノマーとしてＶＣＡを
用いて生成できるインターポリマーの分子量を制限し易
い。上記キュアサイトモノマーの調整動特性は普通の高
圧重合法に使われる様な高温においてより問題となる。It would be highly desirable and convenient to have a simple, low cost method for copolymerizing ethylene and vinyl acetate with relatively small amounts of VCA or other similar halogen-containing cure site monomers. However, among polymer chemists, VCA is considered to be a rather powerful chain transfer agent. This propensity for chain transfer agents tends to limit the molecular weight of interpolymers that can be produced using VCA as the cure site monomer. The tunable kinetics of the cure site monomers become more problematic at high temperatures such as those used in conventional high pressure polymerization processes.
故に十分高分子量Ｅ／ＶＡ／ＶＣＡインターポリマーエ
ラストマーを生成するために一般に比較的低温において
水性エマルジョン又は溶液におけるレドックスにより開
始された重合反応によって重合反応が行なわれている。Therefore, to produce sufficiently high molecular weight E/VA/VCA interpolymer elastomers, polymerization reactions are generally carried out by redox-initiated polymerization reactions in aqueous emulsions or solutions at relatively low temperatures.
こノ様ナエチレン、酢酸ビニルおよびクロロ酢酸ビニル
のエマルジョン重合反応の１方法はベラカーらの米国特
許第４，０９８，７４６号に発表されている。ベラカー
らは重合反応はバッチ方式で又はモノマーを反応媒質に
供給して、行なうことができると発表している。また重
合反応はエチレンの定圧、増加又は減少圧においてもで
きるとして因る。One method for the emulsion polymerization reaction of sodium ethylene, vinyl acetate, and vinyl chloroacetate is described in Belaker et al., US Pat. No. 4,098,746. Belaker et al. state that the polymerization reaction can be carried out batchwise or by feeding the monomers into the reaction medium. The polymerization reaction can also be carried out under constant, increasing or decreasing pressure of ethylene.
しかし共重合操作中エチレン圧変化又はモノマー添加の
方法又は速度がインターポリマー性質にどんな影響をも
つがベラカーらは伺も発表していない。更に重合反応中
ベラカーがＶＣＡモノマーを加えるときそれを酢酸ビニ
ルモノマーそのまま又は水性エマルジョンとしての中に
稀溶液（約１０重量％までの）として加えている。ＶＣ
Ａモノマー単独又は酢酸ビニルモノマー中比較的高濃度
でのＶＣＡモノマーの添加についてはベラカーらはふれ
ていない。However, Beraker et al. have not published any information on the effect that ethylene pressure changes or the method or rate of monomer addition during the copolymerization operation have on interpolymer properties. Additionally, when Veracar adds VCA monomer during the polymerization reaction, it is adding it as a dilute solution (up to about 10% by weight) in the vinyl acetate monomer neat or as an aqueous emulsion. VC
Beraker et al. do not mention the addition of VCA monomer alone or at a relatively high concentration in vinyl acetate monomer.
更にベラカーらは石鹸−いおうキュア系を使用しないで
むしろアミノプラスト樹脂、ポリアミン、ポリアミドア
ミン、又はホルムアルデヒドとアンモニア又はアミンの
混合物の様な架橋剤を架橋のために使用している。Additionally, Belaker et al. do not use soap-sulfur cure systems, but rather use crosslinking agents such as aminoplast resins, polyamines, polyamidoamines, or mixtures of formaldehyde and ammonia or amines for crosslinking.
米国特許第４，２８７，３２９号においてハイムベルグ
は酢酸ビニル約４０乃至約７０重ｉ＃、％を含みムーニ
ー粘度約３０乃至８０をもつ但ゲル含量のＥＶＡエラス
トマー合成用エマルジョン重合法を発表している。比較
的高温でなされる高圧重合法によって製造され約２０よ
りずっと大きいムーニー粘度をもちその結果やわらかく
粘くゴム加工装置で処理し混合することが極めて困姉な
ＥＶＡエラストマーと反対ニハイムベルグの高ムーニー
粘度エマルジョンエラストマーはあまシべたつかずゴム
装置で処理混合がずっと容易である。In U.S. Pat. No. 4,287,329, Heimberg disclosed an emulsion polymerization process for the synthesis of EVA elastomers containing about 40 to about 70% vinyl acetate and having a Mooney viscosity of about 30 to 80 gel content. There is. Nyheimberg's high Mooney viscosity emulsions, as opposed to EVA elastomers, which are produced by high pressure polymerization processes at relatively high temperatures and have Mooney viscosities much greater than about 20, and are therefore soft and viscous and extremely difficult to process and mix in rubber processing equipment. Elastomers are not sticky and are much easier to process and mix in rubber equipment.
出願人らは今や酢酸ビニル、エチレンおよび反応性ハロ
ゲン含有キュアサイトモノマーの高ムーニー粘度インタ
ーポリマーが容易に製造できることを全く意外にも発見
したのである。詳述すれば本発明はエチレン、酢酸ビニ
ルおよびハロゲン含有モノマー、例えばクロロ酢酸ビニ
ルを重合させ石鹸−いおう加硫の際引張強度を増加する
改良された高ムーニー粘度インターポリマーエラストマ
ー製法に関する。本発明の１態様でのキュアサイトモノ
マーは重合反応開始時の代シに重合操作中少しづつ又は
連続して加えられる。他の態様において、ハロゲン含有
キュアサイトモノマーはそのまま又は少なくも２０重量
−の濃度に酢酸ビニルモノマーでうすめて加えられる。Applicants have now quite surprisingly discovered that high Mooney viscosity interpolymers of vinyl acetate, ethylene, and reactive halogen-containing cure site monomers can be readily prepared. More particularly, this invention relates to an improved process for making high Mooney viscosity interpolymer elastomers that polymerize ethylene, vinyl acetate, and halogen-containing monomers, such as vinyl chloroacetate, to increase tensile strength during soap-sulfur vulcanization. In one embodiment of the present invention, the cure site monomer is added at the beginning of the polymerization reaction, either portionwise or continuously during the polymerization operation. In other embodiments, the halogen-containing cure site monomer is added neat or diluted with vinyl acetate monomer to a concentration of at least 20 wt.
更に他の態様においては重合反応中をとおしエチレン圧
も増加される。In yet other embodiments, ethylene pressure is also increased throughout the polymerization reaction.
更に詳述すれば本発明の方法はエチレン、酢酸ビニルお
よびハロゲン含有キュアサイトモノマーを非イオン性表
面活性剤、防イオン性表面活性剤およびフリーラジカル
重合反応触媒を含む水性エマルジョン中で５乃至８０℃
、好捷しくは２０乃至５５℃の温度と４００−４０００
ｐｓｉｇのエチレン圧のもとて共重合させ、かつ重合反
応開始後全重合時間の少なくとも１／２０の時間にわた
りハロゲン含有モノマーを間欠的又は連続して添加して
酢酸ビニル４０乃至７０重量％と塩素０．２乃至２重量
％を含む石鹸−いおう加硫性ニジストマーをえる共重合
方法に関する。本発明の他の１態様では重合反応を５乃
至８０℃、好１しくけ２０乃至５５℃の温度で行なわせ
、かつ重合反応開始後ハロゲン含有モノマーを全重合時
間の少なくとも１／２ｏにわたり間欠的又は連続して加
え捷だ重合反応中エチレン圧を重合開始時の４００−９
００ｐｓｉｇから終了時の２０００乃至４０００ ｐｓ
ｌｇまで増加する改良法である。ハロゲン含有キュアサ
イトモノマーはクロロ酢酸ビニルが好ましく、それは重
合反応にそのま１又は酢酸ビニルモノマーによる稀釈液
の形で添加できる。クロロ酢酸ビニルと酢酸ビニルの溶
液を用いる場合酢酸ビニル中のハロゲン含有キュアサイ
トモノマー濃度は少ｉくとも２０重量％である。この目
的には全酢酸ビニルモノマー添加量の約半分を超えない
量を用い酢酸ビニルモノマー残量は重合反応開始前に反
応器に加えられる。クロロ酢酸ビニルが重合反応にその
ま１加えられるときは重合反応開始時に酢酸ビニルモノ
マー全部が反応器にあるとよいが、重合反応開始時ビニ
ルの約半量以上を別派として加えることができる。More specifically, the method of the present invention involves heating ethylene, vinyl acetate, and halogen-containing cure site monomers in an aqueous emulsion containing a nonionic surfactant, an antiionic surfactant, and a free radical polymerization reaction catalyst at 5 to 80°C.
, preferably at a temperature of 20-55°C and a temperature of 400-4000°C.
psig of ethylene pressure, and after the start of the polymerization reaction, a halogen-containing monomer is added intermittently or continuously for at least 1/20 of the total polymerization time to form 40 to 70% by weight of vinyl acetate and chlorine. The present invention relates to a copolymerization process to obtain a soap-sulfur vulcanizable nidistomer containing 0.2 to 2% by weight. In another embodiment of the invention, the polymerization reaction is carried out at a temperature of 5 to 80°C, preferably 20 to 55°C, and after the start of the polymerization reaction, the halogen-containing monomer is intermittently added for at least 1/2 o of the total polymerization time. Or during the polymerization reaction by continuously adding ethylene pressure to 400-9 at the start of polymerization.
00 psig to 2000 to 4000 ps at end
This is an improved method that increases up to 1g. The halogen-containing cure site monomer is preferably vinyl chloroacetate, which can be added to the polymerization reaction neat or in the form of a dilution with vinyl acetate monomer. When a solution of vinyl chloroacetate and vinyl acetate is used, the concentration of halogen-containing cure site monomer in the vinyl acetate is at least 20% by weight. For this purpose, an amount not exceeding about half of the total amount of vinyl acetate monomer added is used, and the remaining amount of vinyl acetate monomer is added to the reactor before the start of the polymerization reaction. When vinyl chloroacetate is directly added to the polymerization reaction, it is preferable that all of the vinyl acetate monomer be in the reactor at the start of the polymerization reaction, but approximately half or more of the vinyl can be added separately at the start of the polymerization reaction.
発明の詳細な説
明
ビニルのいづれでもよい。クロロ酢酸ビニルをハロゲン
含有キュアサイトモノマーとして使用するときは組成物
はエチレンー酢醒ビニルークロロ酢酸ビニル（Ｅ／ＶＡ
／ＶＣＡ）インターポリマーと称する。酢酸が生モノマ
ーである場合ハ酢醪ビニルーエチレンークロロ酢酸ビニ
ル（ＶＡ／Ｅ／ＶＣＡ）インターポリマーと称すること
もある。DETAILED DESCRIPTION OF THE INVENTION Any vinyl material may be used. When vinyl chloroacetate is used as the halogen-containing cure site monomer, the composition is an ethylene-acetated vinyl-vinyl chloroacetate (E/VA
/VCA) interpolymer. When acetic acid is the raw monomer, it is sometimes referred to as vinegar-vinyl-ethylene-vinyl chloroacetate (VA/E/VCA) interpolymer.
一般にこのインターポリマーは約４０乃至約７０重量チ
、好１しくに約５５乃至約６５重ｆｔ％の酢酸ビニルが
混合されている。これらは一般に塩素約０．２乃至約２
重量敷普通０．５乃至１重量チを含む。ハロゲン含有キ
ュアサイトモノマーがＶＣＡであればこの塩素含量範囲
はそれぞれ添加ＶＣＡの６．８重量チに対し０６８、寸
た３４重量％に対し１、７重量チに相当するこのインタ
ーポリマー組成物の平衡は添加エチレンユニットと重合
反応に含すれている他のエチレン性不飽和モノマーユニ
ットより成る。一般にエチレンはニジストマーの約２５
乃至６０重量％、奸才しくけ約３０乃至４５重量％を構
成する。Generally, the interpolymer is mixed with about 40 to about 70 weight percent vinyl acetate, preferably about 55 to about 65 weight percent vinyl acetate. These generally contain chlorine from about 0.2 to about 2
Weight usually includes 0.5 to 1 weight. If the halogen-containing cure site monomer is VCA, this chlorine content range corresponds to 0.68% by weight for 6.8% by weight of added VCA, and 1.7% by weight for 34% by weight, respectively, of the equilibrium of this interpolymer composition. consists of added ethylene units and other ethylenically unsaturated monomer units included in the polymerization reaction. Generally, ethylene is about 25% of the nidistomer.
It makes up about 30 to 45% by weight, and about 30 to 45% by weight.
、キユアサイトモノマーとして使用できる反応性ハロゲ
ン含有モノマーは好才しくはクロロ酢酸ビニル、ブロモ
酢酸ビニル、２−クロロプロピオン酸ビニル、２−クロ
ロ酪酸ビニル、２−クロロイソ酪酸ビニルおよび２−ク
ロロエチルビニルエーテルより成る群からえらばれる。, reactive halogen-containing monomers that can be used as cure site monomers are preferably vinyl chloroacetate, vinyl bromoacetate, vinyl 2-chloropropionate, vinyl 2-chlorobutyrate, vinyl 2-chloroisobutyrate and 2-chloroethyl vinyl ether. selected from a group consisting of
グリシジルアクリレートおよびグリシジルメタクリレー
トも反応性モノマーとして使用でき他のハロゲン含有モ
ノマー、クロロ酢酸アリル、３−クロロプロピオン酸ビ
ニル、４−クロロ酪酸ビニル、２−クロロエチルメタク
リレートの様なハロアクリレートエステル、塩化ビニル
ベンジル等も同様である。クロロ酢酸ビニルは本発明の
方法特に便利なキュアサイトモノマーである。Glycidyl acrylate and glycidyl methacrylate can also be used as reactive monomers, as well as other halogen-containing monomers, such as allyl chloroacetate, vinyl 3-chloropropionate, vinyl 4-chlorobutyrate, haloacrylate esters such as 2-chloroethyl methacrylate, and vinylbenzyl chloride. The same applies to Vinyl chloroacetate is a particularly useful cure site monomer in the method of the invention.
他のエチレン性不飽和モノマーもエチレン、酢酸ビニル
およびハロゲン含有キュアサイトモノマーと共に加えら
れる。使うときはとのモノマーは全インターポリマーエ
ラストマーの約１０重量％を超えない量で使用される。Other ethylenically unsaturated monomers are also added along with ethylene, vinyl acetate and halogen-containing cure site monomers. When used, the monomers are used in amounts not exceeding about 10% by weight of the total interpolymer elastomer.
この追加コモノマーにはモノエチレン性不飽和脂肪族炭
化水素、例えばプロピレンとインブチレン；ハロゲン含
有オレフィン性モノマー、例えばぶつ化ビニル、塩化ビ
ニル、臭化ビニル、２ふつ化ビニリデン、１−クロロ−
１−フルオロエチレン、クロロトリフルオロエチレンお
よびテトラフルオロエチレン；不飽和モノカルボン酸モ
ノマー、例えばアクリル酸、メタクリル酸およびクロト
ン酸並びにそれらの重合性誘導体、例えばアルキルアク
リレートとメタクリレート、即ちメチルアクリレート、
エチルアクリレート、ｎ−プロピルアクリレート、ｎ−
ブチルアクリレート、インブチルアクリレート、２−エ
チルへキシルアクリレート、メチルメタクリレート、エ
チルメタクリレート、ｎ−プロピルメタクリレート、イ
ソブチルメタクリレート、１．６−ヘキサンジオールジ
アクリレート、アクリロニトリル、メタクリレートリル
、アクリルアミド、メタクリルアミド、Ｎ−メチロール
アクリルアミド、Ｎ−メトキシメチルアクリルアミドお
よびＮ−ブトキシメチルアクリルアミド、およびアクロ
レイン；モノエチレン性不飽和ジカルボン醒のアルキル
エステル、例えばジエチルマレエート、ジブチルマレエ
ート、ジオクチルマレエート、ジプロピルフマレート、
ジブチルフマレート、ジオクチルフマレート、ジドデシ
ルフマレート、ジブチルイタコネート、およびジオクチ
ルイタコネート；脂肪族ビニルエステル、例えばぎ酸ビ
ニル、プロピオン酸ビニル、トリメチル酢酸ビニルおよ
び酪酸ビニル；脂肪族ビニルエステル、例えばメチルビ
ニルエーテル、エチルビニルエーテルおよびｎ−ブチル
ビニルエーテル；ビニルケトン、例えばメチルビニルケ
トン、エチルビニルケトン、およびブチルビニルケトン
がある。These additional comonomers include monoethylenically unsaturated aliphatic hydrocarbons, such as propylene and imbutylene; halogen-containing olefinic monomers, such as vinyl butonide, vinyl chloride, vinyl bromide, vinylidene difluoride, 1-chloro-
1-fluoroethylene, chlorotrifluoroethylene and tetrafluoroethylene; unsaturated monocarboxylic acid monomers such as acrylic acid, methacrylic acid and crotonic acid and their polymerizable derivatives such as alkyl acrylates and methacrylates, i.e. methyl acrylate;
Ethyl acrylate, n-propyl acrylate, n-
Butyl acrylate, inbutyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isobutyl methacrylate, 1,6-hexanediol diacrylate, acrylonitrile, methacrylatrile, acrylamide, methacrylamide, N-methylol acrylamide, N-methoxymethylacrylamide and N-butoxymethylacrylamide, and acrolein; alkyl esters of monoethylenically unsaturated dicarbonates, such as diethyl maleate, dibutyl maleate, dioctyl maleate, dipropyl fumarate,
Dibutyl fumarate, dioctyl fumarate, didodecyl fumarate, dibutyl itaconate, and dioctyl itaconate; aliphatic vinyl esters such as vinyl formate, vinyl propionate, vinyl trimethyl acetate and vinyl butyrate; aliphatic vinyl esters such as methyl Vinyl ethers, ethyl vinyl ether and n-butyl vinyl ether; vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, and butyl vinyl ketone.
重合反応はバッチ方式又は連続方式で行なわせることが
できる。反応は溶媒なしでモノマーと重合反応を促進す
るための開始剤の様な補助剤のみを使用しバルク状で反
応させてもよく又は適当溶媒、例えばメタノール、ｔ−
ブチルアルコール、トルエン等中での溶液の形で反応さ
せてもよい。水性媒質中でエマルジョン重合法として行
なわせることがより好ましい。The polymerization reaction can be carried out batchwise or continuously. The reaction may be carried out in bulk without a solvent, using only the monomers and an auxiliary agent such as an initiator to accelerate the polymerization reaction, or in the presence of a suitable solvent such as methanol, t-
The reaction may be carried out in the form of a solution in butyl alcohol, toluene, or the like. It is more preferable to carry out the emulsion polymerization method in an aqueous medium.
この方法は一般にバッチエマルジョン重合方式として行
なわれるが、重合反応進行につれて重合系が１反応器か
ら次へポンプ輸送される連続バッチ反応器のシリーズ又
は”カスケードで方法を行なうことは本発明の範囲内で
あり、この様にして連続方法に近づく。Although this process is generally carried out as a batch emulsion polymerization system, it is within the scope of this invention to run the process in a series or "cascade" of successive batch reactors in which the polymerization system is pumped from one reactor to the next as the polymerization reaction progresses. , and in this way we approach a continuous method.
本発明の共重合方法を水性エマルジョン中で行なうとき
非イオン性と陰イオン性表面活性剤、触媒、緩衝液、硫
酸第１鉄７水化物および還元剤が水とモノマーと共に含
１れる。一般に表面活性剤、触媒、緩衝液、硫散第１鉄
７水化物は脱イオン水にとかし重合反応開始前に直接反
応器に加える。酢酸とニルモノマーを次に加えるが、必
要ならば重合反応中小しづつ加える。最も一般には大部
分（半分以上）の酢酸ビニルを重合開始前に加える。重
合反応中の水対酢酸ビニルモノマーの初めの比率はモノ
マー１００部当り水約４０乃至約１７００部であり、モ
ノマー１００部当り水約７５乃至約１２０部が好ましい
。酢醗ビニルモノマー添加後反応器を閉ぢ攪拌機を運転
し窒素を交互に加圧放出して反応器とそれに通じるパイ
プ内から空気を置換した。次いで反応器にエチレン圧を
加え内容物を攪拌して望む重合温度に加熱した。エチレ
ン圧を重合圧に調節し反応器に少量の還元剤溶液を入れ
て重合を開始させた。−旦重合反応が開始すれば還元剤
流を一定量に調節し重合反応の間保持する。When the copolymerization process of the present invention is carried out in an aqueous emulsion, nonionic and anionic surfactants, catalysts, buffers, ferrous sulfate heptahydrate, and reducing agents are included along with water and monomers. Generally, the surfactant, catalyst, buffer, and sulfurized ferrous heptahydrate are dissolved in deionized water and added directly to the reactor before the polymerization reaction begins. The acetic acid and nyl monomer are then added, if necessary in small increments throughout the polymerization reaction. Most commonly, the majority (more than half) of the vinyl acetate is added before polymerization begins. The initial ratio of water to vinyl acetate monomer during the polymerization reaction is from about 40 to about 1700 parts water per 100 parts of monomer, preferably from about 75 to about 120 parts water per 100 parts of monomer. After the addition of the vinegar-vinyl monomer, the reactor was closed, the stirrer was operated, and nitrogen was alternately released under pressure to replace air from the reactor and the pipes leading thereto. Ethylene pressure was then applied to the reactor and the contents were stirred and heated to the desired polymerization temperature. The ethylene pressure was adjusted to the polymerization pressure, and a small amount of reducing agent solution was added to the reactor to initiate polymerization. - Once the polymerization reaction has started, the reducing agent flow is adjusted to a constant level and maintained during the polymerization reaction.
上記のとおり非イオン性と陰イオン性表面活性剤を使用
する。非イオン活性剤は使用酢酸とニルモノマー１００
部当り約２．５乃至約１０部の範囲で変えてもよい。酢
酸ビニル１００部当り非イオン性界面活性剤約２．７５
乃至約４部を使用するとよい。一般に非イオン性表面活
性剤量の減少につれてエラストマーのムーニー粘度は最
大となり易い。Use nonionic and anionic surfactants as described above. The nonionic activator used was acetic acid and nil monomer 100
It may vary from about 2.5 parts per part to about 10 parts per part. Approximately 2.75 nonionic surfactants per 100 parts of vinyl acetate
From about 4 parts to about 4 parts may be used. Generally, as the amount of nonionic surfactant decreases, the Mooney viscosity of the elastomer tends to reach its maximum.
しかし非イオン性表面活性剤の最適量は実験によってえ
られる。酢酸ビニル１００部当シ約０．１乃至約１部の
陰イオン性表面活性剤が使われるが、酢酸ビニルモノマ
ー１００部当り０．２５乃至０．７５部の使用が好まし
い。非イオン性および陰イオン性表面活性剤は上記のと
おり全部最初から重合媒質中にあってよいが、必要なら
ば］方又は両方の全部又は１部を少しづつ加えてもよい
。However, the optimum amount of nonionic surfactant can be determined by experimentation. From about 0.1 to about 1 part of anionic surfactant per 100 parts of vinyl acetate is used, preferably from 0.25 to 0.75 parts per 100 parts of vinyl acetate monomer. The nonionic and anionic surfactants may all be initially in the polymerization medium as described above, but if desired, all or part of one or both may be added in portions.
本発明の改良重合法に使用できる非イオン性表面活性剤
ＨＥＶＡおよびＶＡＥコポリマーおよびターポリマー格
子の製造に知れているどんな普通の非イオン性表面活性
剤でもよい。この製品は一般にポリエチレン又はポリオ
キシ（エチレン／プロピレン）基の様な水溶性オキシア
ルキレン１又は２以上をもつ。この型の便第１」な非イ
オン性表面活性剤は米国特許第２，６７４，６１．９号
、２，６７７．７００号および４，２８７，３２９号に
記載されておｐ、これらの特許は参考に本明細省に加え
ておく。非イオン性表面活性剤１又は２以上の混合物も
共重合反応に便利に使用できる。テトロニック９０８は
特に有用な非イオン性表面活性剤である。Nonionic surfactants that can be used in the improved polymerization process of this invention can be any conventional nonionic surfactants known for the production of HEVA and VAE copolymer and terpolymer lattices. This product generally has one or more water-soluble oxyalkylenes such as polyethylene or polyoxy (ethylene/propylene) groups. This type of nonionic surfactant is described in U.S. Pat. are included in this specification for reference. Mixtures of one or more nonionic surfactants can also be conveniently used in the copolymerization reaction. Tetronic 908 is a particularly useful nonionic surfactant.
非イオン性表面活性剤と同様従来エチレンと酢酸ビニル
のエマルジョン重合用に知られている普通の陰イオン表
面活性剤も本発明方法に便利である。使用できる多くの
陰イオン性表面活性剤のなかにはトリトンＸ−２００（
ロームアンドハース社）、アルキルアリールポリエーテ
ルスルホン酸ナトリウム；トリトンＱＳ−９（ロームア
ンドハース社）、リン醸塩エステル；アリパルＣｏ ４
３３（ＧＡＦ）、ノニルフェノール（エチレンオキシ）
エタノール硫酸ナトリウム；デュパノールＭＥドライ（
デュポン社）、ラウリル硫酸ナトリウム；およびエマ−
サル６４５３ （エメリーケミカルズ）、ラウリルエー
テル硫酸ナトリウム２５％活性水溶液がある。エマ−サ
ル６４５３は特に便利な陰イオン性表面活性剤である。Common anionic surfactants conventionally known for emulsion polymerization of ethylene and vinyl acetate as well as nonionic surfactants are useful in the process of the invention. Among the many anionic surfactants that can be used is Triton X-200 (
Rohm and Haas), sodium alkylaryl polyether sulfonate; Triton QS-9 (Rohm and Haas), phosphorus salt ester; Alipal Co 4
33 (GAF), nonylphenol (ethyleneoxy)
Sodium ethanol sulfate; Dupanol ME Dry (
DuPont), sodium lauryl sulfate; and em-
Sal 6453 (Emery Chemicals), a 25% active aqueous solution of sodium lauryl ether sulfate. Emersal 6453 is a particularly useful anionic surfactant.
共重合反応に使われる触媒は従来ＥＶＡコポリマー格子
製造に知られた普通のフリーラジカル重合触媒であり、
過酸化水素、過塩素酸ナトリウム、および過ほう酸ナト
リウムの様な無機過酸素化合物；過硫酸ナトリウム、過
硫酸カリウム、および過硫酸アンモニウムの様な無機過
硫酸塩がある。触媒は一般に使用酢酸ビニルモノマー基
準で約０．０５乃至約３重量％の量で使われる。普通触
媒使用量は約０．２乃至１％である。過硫酸アンモニウ
ムが特に便利な触媒である。The catalyst used in the copolymerization reaction is a common free radical polymerization catalyst conventionally known for producing EVA copolymer lattices.
There are inorganic peroxygen compounds such as hydrogen peroxide, sodium perchlorate, and sodium perborate; inorganic persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate. Catalysts are generally used in amounts of about 0.05 to about 3 weight percent, based on the vinyl acetate monomer used. The amount of catalyst used is usually about 0.2 to 1%. Ammonium persulfate is a particularly convenient catalyst.
本発明の方法において反応器に少量の還元剤（時には共
触媒という）をしづかに加えて重合反応を開始し保つこ
とが好ましい。触媒と還元剤の反応によって反応開始剤
が生成される。（レドックス活性化）還元剤は水素亜硫
酸ナトリウム、メタ重亜硫酸ナトリウム、ヒドロ亜硫酸
ナトリウムおよびホルムアルデヒドスルホキシル酸ナト
リウムでもよい。ホルムアルデヒドスルホキシル醗ナト
リウムが好ましい。還元剤は普通水溶液として加えられ
る。還元剤濃度は広範囲にわたシ０．１乃至２重量％、
普通０．２５乃至０．７５重量％の水溶液である。In the process of the present invention, it is preferred to slowly add a small amount of reducing agent (sometimes referred to as a cocatalyst) to the reactor to initiate and maintain the polymerization reaction. A reaction initiator is produced by the reaction between the catalyst and the reducing agent. (Redox Activation) The reducing agent may be sodium hydrogen sulfite, sodium metabisulfite, sodium hydrosulfite, and sodium formaldehyde sulfoxylate. Sodium formaldehyde sulfoxyl is preferred. The reducing agent is usually added as an aqueous solution. The reducing agent concentration ranges over a wide range from 0.1 to 2% by weight;
It is usually a 0.25 to 0.75% by weight aqueous solution.
変動性原子価遷移金属塩からえられた低イオン濃度がこ
の重合のレドックス開始時に促進剤として便利に使われ
る。Low ionic concentrations obtained from variable valence transition metal salts are conveniently used as promoters during the redox initiation of this polymerization.
硫酸第１鉄７水化物がこの目的の好ましい塩である。酢
酸ビニルモノマー１００部当セ約０．０００５乃至約０
．０５部、好ましくは０．００１乃至０．０１部の塩が
使われる。またアルカリ性緩衝剤、例えば重炭酸ナトリ
ウム、重炭酸アンモニウム、酢酸ナトリウム等もｐＨを
望む値に保つため添加できる。一般に緩衝剤量は酢酸ビ
ニルモノマー基準で約０．１０乃至１．０重量％である
。Ferrous sulfate heptahydrate is a preferred salt for this purpose. From about 0.0005 to about 0 per 100 parts of vinyl acetate monomer
．． 0.05 parts, preferably 0.001 to 0.01 parts of salt are used. Alkaline buffers such as sodium bicarbonate, ammonium bicarbonate, sodium acetate, etc. can also be added to maintain the pH at the desired value. Generally, the amount of buffering agent is about 0.10 to 1.0% by weight based on vinyl acetate monomer.
本発明の共重合方法に重要ではないが、一般にこの技術
分野で知られた型の保護コロイドを重合中に加えてもよ
い。Although not critical to the copolymerization process of the present invention, protective colloids of types generally known in the art may be added during the polymerization.
部分的および完全加水分解されたポリビニルアルコール
；セルローズエーテル、例えばヒドロキシメチルセルロ
ーズ、ヒドロキシエチルセルローズ、エチルヒドロキン
エチルセルローズおよびエトキシル化澱粉誘導体：天然
および合成ゴム、例えばトラガカントゴムとアラビアゴ
ム；ポリアクリル酸、およびポリ（メチルビニルエーテ
ル／無水マレイン醪）、の様な知られた普通の保護コロ
イドが使用に適している。partially and fully hydrolyzed polyvinyl alcohol; cellulose ethers, such as hydroxymethylcellulose, hydroxyethylcellulose, ethylhydroquine ethylcellulose and ethoxylated starch derivatives; natural and synthetic rubbers, such as tragacanth and acacia; polyacrylic acid, and Known common protective colloids such as poly(methyl vinyl ether/anhydrous maleic mash) are suitable for use.
酢酸ビニル、エチレンおよび反応性ノ・ロゲン含有モノ
マーの高ムーニー粘度インターポリマーが生成され石鹸
−いおうキュア系を用い加硫するとよい物理的性質かえ
られる本発明の改良方法において、エチレンと酢酸ビニ
ルの重合開始後また重合反応進行中に７・ロゲン含有キ
ュアサイトモノマーが加えられる。ＶＣＡ又は他のノ１
０ゲン含有モノマーは連続して又は間欠的に（準連続し
て）加えられる。キュアサイトモノマーは全重合時間に
わたυ連続して又は不連続で加えうるが、一般にキュア
サイトモノマー添加全時間は全重合時間の少なくとも約
１／２０から約シ４の時間である。全重合時間は重合反
応開始からエチレン圧を開放し重合終了までの時間、普
通８乃至１０時間である。In an improved process of the present invention, a high Mooney viscosity interpolymer of vinyl acetate, ethylene, and a reactive nitrogen-containing monomer is produced which changes its physical properties when vulcanized using a soap-sulfur cure system. After initiation and during the progress of the polymerization reaction, a 7.logen-containing cure site monomer is added. VCA or other No.1
The zero-gen containing monomer is added continuously or intermittently (quasi-continuously). The cure site monomer may be added continuously or discontinuously over the total polymerization time, but generally the total cure site monomer addition time is at least about 1/20 to about 4 hours of the total polymerization time. The total polymerization time is the time from the start of the polymerization reaction until the end of the polymerization after releasing the ethylene pressure, and is usually 8 to 10 hours.
添加を間欠的に行なえばキュアサイトモノマー添加時は
モノマー抑制時と交互である。そこでキュアサイトモノ
マー添加時は２乃至１００回又はそれ以上となりまた七
ツマー抑制時も同数回となる。一般にＶＣＡが間欠的に
加えられるときＶＣＡキュアサイトモノマー添加と抑制
時５乃至約１０回が使われる。添加時間長さは広く変っ
てもよくまたモノマー添加時間は停止時間と同じでもち
がってもよい。If the addition is carried out intermittently, the time when the cure site monomer is added is alternated with the time when the monomer is suppressed. Therefore, when the cure site monomer is added, the number of times is 2 to 100 or more, and when the 7-mer is suppressed, the number of times is the same. Generally, when VCA is added intermittently, 5 to about 10 times of VCA cure site monomer addition and suppression are used. The length of addition time may vary widely and the monomer addition time may be the same as or different from the stop time.
各添加時におけるモノマー添加速度は一定でも変えても
よく各回置えてもよい。この速度はキュアサイトモノマ
ー供給ポンプ速度を変えて変更できる。必要ならばキュ
アサイトモノマー添加速度を増し例えば適当高圧注入機
を使う様＝２５−
な追加添加を殆んど瞬間的にすることもできる。The monomer addition rate at each addition time may be constant or variable, and may be set at each time. This rate can be varied by changing the cure site monomer feed pump speed. If desired, the rate of cure site monomer addition can be increased to make additional addition almost instantaneous, for example using a suitable high pressure injection machine.
クロロ酢酸ビニル又は他のハロゲン含有モノマーはその
まま又は酢酸ビニルモノマーとの混合物としてのいづれ
でも添加できる。酢酸ビニルで稀釈するとき（弓：ハロ
ゲン含有モノマーは混合物の２０重量−以上とする。こ
の様に重合中ＶＣＡ添加によって物理的性質の改良され
たエラストマーがえられることがはからずもわかったの
である。重合反応に酢酸ビニルモノマー中のＶＣＡ’ｚ
上記のとおシの間欠方法であるが酢酸ビニルモノマー中
ＶＣＡ２０重童チ又はそれ以」二の濃度で加えることも
本発明の範囲内である。Vinyl chloroacetate or other halogen-containing monomers can be added either neat or as a mixture with vinyl acetate monomer. When diluted with vinyl acetate (bow: the halogen-containing monomer is at least 20% by weight of the mixture), it was unexpectedly found that the addition of VCA during polymerization yields an elastomer with improved physical properties.Polymerization VCA'z in vinyl acetate monomer for reaction
It is within the scope of the present invention to use the intermittent method described above, but to add VCA in vinyl acetate monomer at a concentration of 20% or more.
Ｅ／Ｖ Ａ／Ｖ ＣＡエマルジョン共重合反応圧力は４
００ｐｓｉｇの低圧から約４０００ ｐｓｉｇの高圧ま
で広範に変えられる。重合圧力はエチレン圧縮機によっ
て反応器にエチレンを供給して保持する。使用圧力はタ
ーポリマーエラストマー中の望むエチレン濃度によりえ
らばれる。E/V A/V CA emulsion copolymerization reaction pressure is 4
Pressures can vary widely from as low as 00 psig to as high as about 4000 psig. Polymerization pressure is maintained by supplying ethylene to the reactor by an ethylene compressor. The working pressure is selected depending on the desired ethylene concentration in the terpolymer elastomer.
＝２６−
エチレン圧力は重合反応中比較的一定に保たれるが、本
発明の特に便利な実施態様においてエチレン圧は重合反
応温度記のとおりキュアサイトモノマーの添加につれて
増加される。エチレン圧増加は一般に重合開始特約４０
０−９００ ｐｓｉｇから重合終了時の約２０００−４
０００ｐｓｉｇまでの範囲である。エチレン圧は重合最
初の１乃至２時間内で約１２００ｐｓｉｇに増した後重
合終了時最大せで次第に上昇させる。この様にエチレン
圧を調整して添加酢酸ビニル約５５乃至約６５重量％を
含み１だ普通の石鹸−いおうキュア方式を用いて加硫し
たとき高引張強度をもつＥ／ＶＡ／ＶＣＡインターポリ
マーニラストマーが製造できる。=26- Although the ethylene pressure is kept relatively constant during the polymerization reaction, in a particularly convenient embodiment of the invention the ethylene pressure is increased as the cure site monomer is added as per the polymerization reaction temperature. Ethylene pressure increase is generally 40%
0-900 psig to about 2000-4 at the end of polymerization
000 psig. Ethylene pressure is increased to about 1200 psig within the first 1 to 2 hours of polymerization and then gradually increased to a maximum pressure at the end of polymerization. The E/VA/VCA interpolymer leek containing about 55 to about 65% by weight of added vinyl acetate and having high tensile strength when vulcanized using the conventional soap-sulfur cure method by adjusting the ethylene pressure in this way Stomers can be manufactured.
本発明の重合方法を２又は３以上の反応器で次々に連続
に近い方法で行なうときはキュアサイトモノマーを定期
的に加えながら次々に高いが一定エチレン圧で各反応器
を運転することがしばしば便利である。When the polymerization process of the present invention is carried out in a nearly continuous manner in two or more reactors, each reactor is often operated one after the other at a high but constant ethylene pressure while periodically adding cure site monomer. It's convenient.
重合反応温度は約５乃至約８０℃でよいが、２０乃至５
５℃の温度が′ｔｆｆｉシい。もちろん上記触媒と反応
させて重合反応開始に要するフリーラジカルを生成する
ため低温においては還元剤使用の必要なことはこの分野
の経験者は認めるであろう。重合全時間は１時間から２
０時間の長時間におよぶ。しかし約８乃至約１０時間が
最も普通である。The polymerization reaction temperature may be from about 5 to about 80°C, but from 20 to 50°C.
The temperature of 5℃ is too low. Of course, those skilled in the art will recognize the necessity of using a reducing agent at low temperatures to react with the catalyst to generate the free radicals necessary to initiate the polymerization reaction. Total polymerization time is 1 to 2 hours.
It lasts for a long time of 0 hours. However, about 8 to about 10 hours is most common.
インターポリマーエラストマーは重合反応からラテック
スの形で回収される。インターポリマー自体はラテック
スを硫酸ナトリウム、塩化ナトリウムの様な塩の高温飽
和水溶液に加えて分離できる。まにインターポリマーは
凍結、噴脩乾燥の様な知られた他の方法によってもラテ
ックスから回収できる。回収したインターポリマーは次
に洗って残留表面活性剤、触媒残漬、凝固に使用した塩
その仙の物質を除去して乾燥するとよい。The interpolymer elastomer is recovered from the polymerization reaction in latex form. The interpolymer itself can be separated by adding the latex to a hot saturated aqueous solution of a salt such as sodium sulfate or sodium chloride. The interpolymer may also be recovered from the latex by other known methods such as freezing and blow drying. The recovered interpolymer may then be washed to remove residual surfactant, catalyst residue, salts and other substances used in coagulation, and dried.
本発明の方法によｐえられたインターポリマーエラスト
マーは普通の石鹸−いおうキュア系および混合成分と適
合する。石鹸、いおうその他の成分は既知の方法でエラ
ストマー中に混合できる。２ゴムローラー、バンパーリ
ー混合機、双スクリュー混合機の様な適当混合機が使用
できるが、２ゴムローラーが最もよい。The interpolymer elastomers prepared by the process of the invention are compatible with conventional soap-sulfur cure systems and blending components. Soaps, sulfur and other ingredients can be incorporated into the elastomer in a known manner. Any suitable mixer can be used, such as a two-rubber roller, a bumperley mixer, a twin screw mixer, but a two-rubber roller is best.
石鹸−いおう加硫系には一般に長鎖カルボン醗塩又は石
鹸、いおう、長鎖脂肪酸および酸化防止剤が含まれる。Soap-sulfur vulcanization systems generally include a long chain carbonate or soap, sulfur, long chain fatty acids, and an antioxidant.
この型のいおう加硫方式はキュアサイトとして炭素−炭
素２重結合をもつ普通のいおう加硫法と異なり、米国特
許第３゜４５８．４６１号、３，９３９，１２８号およ
び３，９７２．８５７号に十分に開示されている。上記
特許記述は参考として本明細書に加えておく。This type of sulfur vulcanization method is different from the ordinary sulfur vulcanization method which has a carbon-carbon double bond as the cure site, and is described in U.S. Pat. fully disclosed in the issue. The above patent description is incorporated herein by reference.
種々の充填剤や強化剤も使用できるが、非充填組成物を
加硫することも本発明の範囲内である。充填強化剤の例
には種々の型のカーボンブラック、例えばファーネスブ
ラツり、チャンネルブラック、サーマルブラック等があ
る。It is within the scope of this invention to vulcanize unfilled compositions, although various fillers and reinforcing agents may also be used. Examples of fill reinforcement agents include various types of carbon blacks, such as furnace blacks, channel blacks, thermal blacks, and the like.
特定型カーボンブラックは急速押Ｗ、シファーネスブラ
ック（工業名称、ＦＥＦ：ＡＳＴＭ扁Ｎ５５０）、単弦
化ファーネスブラック（工業名称、ＳＲＦ；ＡＳＴＭ屋
Ｎ７７４）および高摩耗ファーネスブラック（工業名称
、ＨＡＦ ； ＡＳＴＭ Ａ Ｎ３３０ ）がある。こ
れらのうちＮ５５０カーボンブラツクが特に便利である
。使用できる他の普通充填強化剤には種々の型のシリカ
、アルミナおよび粘土、けい藻土、硫化バリウム、ガラ
ス繊維等がある。Specific types of carbon blacks include rapid press W, deep steel furnace black (industrial name, FEF; ASTM N550), single chord furnace black (industrial name, SRF; ASTM Ya N774), and high abrasion furnace black (industrial name, HAF; ASTM). AN330). Of these, N550 carbon black is particularly useful. Other common fill reinforcements that can be used include various types of silica, alumina and clay, diatomaceous earth, barium sulfide, glass fibers, and the like.
一般にエラストマー１００部当り約３０−６０部の充填
強化剤を使用したとき最高強度かえられる。しかしこの
値はガイドラインでありある用途には約２５乃至１００
部の充填強化剤が使われる。Generally, maximum strength is achieved when about 30-60 parts of filler reinforcement are used per 100 parts of elastomer. However, this value is a guideline and for some applications it is approximately 25 to 100.
filler reinforcement is used.
必要ならば他の変性用樹脂又はエラストマーが本発明の
ターポリマーエラストマーと混合できる。これらには種
々のポリエチレン、ポリプロピレン、ＥＶＡ、およびＶ
ＡＥコポリマー、塩化ポリビニル、ポリクロロプレン、
ポリアクリレートゴム、ポリウレタン、塩素化ポリエチ
レン、ポリエステル、エチレン−プロピレン−ジエン
モノマ・−（ＥＰＤＭ）ターポリマー、エチレン−メチ
ルアクリレートエラストマー、エチレン−ブチルアクリ
レートエラストマー、ブタジェン−アクリロニトリルエ
ラストマーおよび他の知られたエラストマーと樹脂があ
る。一般に変性用樹脂又はニジストマーは混合物の約１
０乃至約４０重量％含まれる。Other modifying resins or elastomers can be mixed with the terpolymer elastomers of this invention if desired. These include various polyethylene, polypropylene, EVA, and V
AE copolymer, polyvinyl chloride, polychloroprene,
Polyacrylate rubber, polyurethane, chlorinated polyethylene, polyester, ethylene-propylene-diene
These include monomer-(EPDM) terpolymers, ethylene-methyl acrylate elastomers, ethylene-butyl acrylate elastomers, butadiene-acrylonitrile elastomers and other known elastomers and resins. Generally the modifying resin or nidistomer is about 1% of the mixture.
0 to about 40% by weight.
次の実施例は本発明を更によく例証するであろう。特に
断らない限り部とパーセントはすべて重量基準である。The following examples will better illustrate the invention. All parts and percentages are by weight unless otherwise noted.
クロロ酢酸ビニル、過硫酸アンモニウム、酢酸ビニル、
エチレン、ステアリン酸、いおう等の様な使用薬品は業
者から購入した良好又は高純度級のもの又は内部で製造
したものであった。ナトリウムホルムアルデヒドスルホ
キレート２水化物は終始還元剤として使用した。Vinyl chloroacetate, ammonium persulfate, vinyl acetate,
The chemicals used, such as ethylene, stearic acid, sulfur, etc., were of good or high purity grade purchased from commercial suppliers or manufactured in-house. Sodium formaldehyde sulfochelate dihydrate was used as the reducing agent throughout.
インターポリマーの塩素含量は修正シュニガー法によっ
て測定した。ビニルエステル含量は鹸化法によって測定
した。記号ＶＡＭは酢酵ビニルモノマーを示す。ムーニ
ー粘度、ＭＬ （＋４−４） １１２１２″Ｃ，はＡＳ
ＴＭ Ｄ １６４６−６８によって測定しＭＶとあられ
した。エラストマーのゲル含量は蓋付きビーカー内のキ
シレン６００−中にポリマー３２を加え攪拌器で８０−
９０℃で２４時間攪拌して測定した。液を秤量した粗多
孔質ガラスフリットをとおして熱いうち幻過した。重量
増加分をゲルと考え原試料重量のパーセントであられし
た。The chlorine content of the interpolymers was determined by a modified Schniger method. Vinyl ester content was determined by saponification method. The symbol VAM indicates fermented vinyl monomer. Mooney viscosity, ML (+4-4) 11212″C, is AS
It was measured by TMD 1646-68 and was found to be MV. To determine the gel content of the elastomer, add polymer 32 to 600 mm of xylene in a beaker with a lid and stir to 80 mm.
The measurement was performed after stirring at 90°C for 24 hours. The liquid was passed through a weighed coarse porous glass frit while hot. The weight increase was considered a gel and expressed as a percentage of the original sample weight.
加硫したエラストマーの引張強度と伸度はＡＳＴＭＤ−
４１２により測定した。引張値と伸度は異なるキュア時
間において測定したが、最大引張強度とそれに相轟する
伸度（チ）を示した。The tensile strength and elongation of the vulcanized elastomer are as per ASTM D-
412. The tensile value and elongation were measured at different curing times, and showed the maximum tensile strength and the corresponding elongation (chi).
実施例１
本発明の方法によってＥ／ＶＡ／ＶＣＡターポリマーニ
ジストマーを製造した。強力攪拌器と冷却用ジャケット
をもつ１ガロン圧力反応機を重合用に使って次のものを
装入した：
脱イオン水 ８５０ ２非イオ
ン性表面活性剤（テトロニック９０８） ２６
ｙ隘イオン性表面活性剤（エマ−サル６４５３）
４ ｆ過硫酸アンモニウム
４ タ硫酸第１鉄７水化物 ０
．０２Ｆ酢酸ナトリウム
３．２９ＶＡＭ ８
００ ｆ反応機に窒素圧力を加え放出し数回繰返し
て空気を排除しエチレンを入れ１１０００−１２００ｐ
ｓｉとし攪拌しながら約５０℃に加熱した。次いで重合
反応開始のため０．２重量涜ホルムアルデヒドスルホキ
シル酸ナトリウム還元剤水溶液約２５−を加えた。５０
分後にクロロ酢酸ビニル４．２ｆを１０分間にわたり反
応機に加えた。次の各５時間の最後の１０分間に同量の
ＶＣＡを加え全部で２５７を加えた。次いで更に２時間
重合させた。重合反応中（添加時間を含む）の温度は５
０℃に保ち、エチレン圧は約１２８０乃至１．４００
ｐｓｉｇとし還元剤溶液を重合反応維持に十分な割合で
連続添加した。重合８時間後に水を加えてラテックス粘
度を低下し反応機から排出し少量のｐ−メトキシフェノ
ールを鎖停止剤としてラテックスに加えた。次に高温硫
酸ナトリウム濃水溶液を加えてＥ／ＶＡ／ＶＣＡエラス
トマーを凝固させた。水洗して塩類その他の物質を除い
たポリマーを真空オーブンで乾燥した。Ｅ／ＶＡ／ＶＣ
Ａインターポリマー（ＭＶ ３５．５ ）はゲルの証拠
を示さすＶＡ６０．３チとＣ１０，５１チを含んでいた
。Example 1 An E/VA/VCA terpolymer distomer was prepared by the method of the present invention. A 1 gallon pressure reactor with a strong stirrer and cooling jacket was used for the polymerization and charged with: 850 ml of deionized water 26 ml of nonionic surfactant (Tetronic 908)
Ionic surfactant (Emersal 6453)
4 f ammonium persulfate
4 Ferrous sulfate heptahydrate 0
．． 02F Sodium acetate
3.29 VAM 8
Apply nitrogen pressure to the 00 f reactor, release it, repeat several times to remove air, and add ethylene to 11000-1200p.
The mixture was heated to about 50° C. with stirring. Then, 0.2 weight percent of an aqueous solution of sodium formaldehyde sulfoxylate reducing agent was added to initiate the polymerization reaction. 50
Minutes later, 4.2 f of vinyl chloroacetate was added to the reactor over 10 minutes. The same amount of VCA was added during the last 10 minutes of each of the next 5 hours for a total of 257 doses. Then, polymerization was continued for an additional 2 hours. The temperature during the polymerization reaction (including addition time) was 5.
Maintained at 0℃, ethylene pressure approximately 1280 to 1.400
psig and the reducing agent solution was continuously added at a rate sufficient to maintain the polymerization reaction. After 8 hours of polymerization, water was added to reduce the latex viscosity, the reactor was discharged, and a small amount of p-methoxyphenol was added to the latex as a chain stopper. A hot concentrated aqueous sodium sulfate solution was then added to solidify the E/VA/VCA elastomer. The polymer, which had been washed with water to remove salts and other substances, was dried in a vacuum oven. E/VA/VC
The A interpolymer (MV 35.5 ) contained VA 60.3 and C10,51 showing evidence of gel.
加硫物性質を検べるため石鹸いおうキュア系を用いて加
硫した。加硫のためＥ／ＶＡ／ＶＣＡインターポリマー
を次のとおり混合した：
Ｅ／ＶＡ／ＶＣＡ ターポリ−？−１００部アゲライト
樹脂Ｄ（商品名）１．０ 部いおう
０．８ 部ステアリン酸
２．０ 部Ｎ５５０カーボンブラ
ック ４１，０ 部Ｎ５５０カーボンブ
ラックとナトリウム−２−エチルヘキサノエートとの等
景況合物 ８．０ 部属径２．５インチロー
ラーをもつ標準ローラー実験混合器を用いて各成分を上
記順序でニジストマーに１５０−１７０下で混合した。In order to examine the properties of the vulcanizate, it was vulcanized using a soap sulfur cure system. E/VA/VCA interpolymers were mixed for vulcanization as follows: E/VA/VCA Terpoly? -100 parts Agelite Resin D (trade name) 1.0 parts
0.8 parts stearic acid
2.0 parts N550 carbon black 41.0 parts Equal compound of N550 carbon black and sodium-2-ethylhexanoate 8.0 parts each using a standard roller experimental mixer with 2.5 inch diameter rollers. The ingredients were mixed in the above order into the nidistomer under 150-170°C.
全混合時間２５分であった。Ｅ／ＶＡ／ＶＣＡエラスト
マーはその高ムーニー粘度の結果としてよい性質を示し
た。引張強度と破断伸度率は１７０℃のプレスで硬化し
たエラストマー加硫シートからえた試料を使って測定し
た。最適加伝性（３８０チ伸度における引張強度１８４
０ｐｓｉ ）は１５分キュア後にあられれた。特に断
らない限り以後の加硫すべてにいおう０．８２を使用し
た。Total mixing time was 25 minutes. The E/VA/VCA elastomer exhibited good properties as a result of its high Mooney viscosity. Tensile strength and elongation at break were measured using samples obtained from elastomer vulcanized sheets cured in a press at 170°C. Optimal loadability (tensile strength 184 at 380 inch elongation)
0 psi) appeared after 15 minutes of curing. Unless otherwise specified, 0.82 was used in all subsequent vulcanizations.
重合反応を反復し、但しエチレン圧を１２６０乃至１３
６０ｐｓｉｇに保ち、全重合時間を９時間としたときえ
られたＶ Ａ／Ｅ／Ｖ ＣＡクーポリマーはＶＡ５８．
６％とＣＩｏ、５０％を含んでいた。上記のとおリコン
パウンデイングしキュアしたインターポリマーエラスト
マー１ｄ１８４０ｐｓ＋ の引張値と３９０係の破断
伸Ｉｌｌもっていた。Repeat the polymerization reaction, but at an ethylene pressure of 1260 to 13
When maintained at 60 psig and with a total polymerization time of 9 hours, the resulting VA/E/V CA copolymer had a VA of 58.
6% and CIo, 50%. The interpolymer elastomer 1d, which was recompounded and cured as described above, had a tensile value of 1840 ps+ and an elongation at break of 390.
比１ｆｌ実験Ａ
本発明の方法によってえられた改良結果とクロロ酢酸ビ
ニルキュアザイトモノマ一連続的又は間欠的添加を比較
するため次の比較実験を行々つだ。重合用として次の成
分を反応機に加えた二 ′
脱イオン水 ８５０ ２非イオ
ン性表面活性剤
（商品テトロニック９０８） ２
６ ｙ陰イオン性表面活性剤
（商品エマ−ザル６４５３）
４ 濾過硫酸アンモニウム
４９硫酸第１鉄７水化物 ０．
０２９酢酸ナトリウム ３
．２ｆＶＡＭ ８０
０ ｆ実施例Ｉの方法のとおり反応機にエチレン圧
を加えた後ナトリウムホルムアルデヒドスルホキシレー
ト ０．５％水溶液添加によって重合を開始させた。重
合反応８．５時間にわたり還元剤溶液を加えまたエチレ
ン圧は１１５０乃至１３８０ｐ８ｉｇとした。普通の方
法でＥ／Ｖ Ａ／Ｖ ＣＡターポリマーを凝固回収した
。生成物１ｄＶＡ ６０．０％とＣ１０，７８チを含み
ムーニー粘度３４であった。Ratio 1fl Experiment A The following comparative experiment was conducted to compare the improved results obtained by the method of the present invention with continuous or intermittent addition of vinyl chloroacetate curezite monomer. The following ingredients were added to the reactor for polymerization: 2' Deionized water 850 2 Nonionic surfactant (Product Tetronic 908) 2
6y Anionic surfactant (product Emazal 6453)
4 Filtered ammonium sulfate
49 Ferrous sulfate heptahydrate 0.
029 Sodium acetate 3
．． 2fVAM 80
0 f Polymerization was initiated by adding 0.5% aqueous sodium formaldehyde sulfoxylate after applying ethylene pressure to the reactor as in the method of Example I. The reducing agent solution was added over the course of the polymerization reaction for 8.5 hours and the ethylene pressure was 1150 to 1380 p8ig. The E/V A/V CA terpolymer was coagulated and recovered in a conventional manner. The product had a Mooney viscosity of 34, containing 60.0% 1 dVA and 10.78% C.
上記のえたターポリマーを用いて次の調合により３混合
組成物を製造した。Using the terpolymer obtained above, three mixed compositions were prepared by the following formulation.
Ａ：１） Ａ （２） Ａ （３）Ｅ／ＶＡ／
ＶＣＡ ターポリ？−１００１００１００Ｎ７７４カー
ボンブラツク ４５ ４５ ４５エイジ
ライト樹脂Ｄ（商品名） １．０ １．０
１．０ステアリン酸 ２．０ ２
．、ｏ ２．０いおう ０
．３ ０．５ ０．９１ナトリウム２−エチＨヒナ
ノエー） ４．０ ４．０４６０組成物を
混合し普通の方法で１７０℃でキュアし引張値と伸度を
検べた。Ａ（１）、Ａ（２）およびＡ（３）ｔ；ｔ、そ
れぞれ１２６０ｐｓｉ（１６０％）、１４８０ｐｓｉ（
１３０％）、および１３００ｐｓｉ（１１０％）であっ
た。この引張値と伸度を実施例Ｉのそれと比較すれは本
発明の方法によ丈製造したＥ／ＶＡ／ＶＣＡエラストマ
ーは普通の石鹸−いおうキュア系を用いて加硫したとき
著しく高い引張値を示すことは明白である。A:1) A (2) A (3)E/VA/
VCA Tarpoli? -100100100N774 Carbon Black 45 45 45 Agelite Resin D (Product Name) 1.0 1.0
1.0 stearic acid 2.0 2
．． , o 2.0 Iou 0
．． 3 0.5 0.91 Sodium 2-EthyH Hinanoe) 4.0 4.0460 The compositions were mixed and cured at 170° C. in a conventional manner, and the tensile value and elongation were examined. A(1), A(2) and A(3)t;t, 1260 psi (160%), 1480 psi (
130%), and 1300psi (110%). A comparison of the tensile values and elongation with those of Example I shows that the E/VA/VCA elastomer made by the method of the present invention exhibits significantly higher tensile values when cured using a conventional soap-sulfur cure system. The indication is clear.
実施例■
石鹸−いおう加硫後のＥ／ＶＡ／ＶＣＡエラストマーの
引張値と伸度に対するカーボンブラックの影響を示すた
め実施例■と比較実験Ａを反復した。実施例Ｉと比較実
験Ａによって製造したＥ／ＶＡ／ＶＣＡエラストマーの
コンパウンディングにカーボンブラック、Ｎ５５０とＮ
７７４−１１を変えて使用した。反応器にＶＣＡモノマ
ーを最初から全部加えて比較実験Ａ方法により製造した
Ｅ／Ｖ Ａ／Ｖ ＣＡエラストマー（エラストマーＩＩ
Ａという）はＶＡ５７．７ｉ量チ、ＣＩｏ、７４重量％
を含み、ムーニー粘度３４であった。ＶＣＡモノマーを
定期的に少量づつ加えた実施例Ｉの方法により製造した
Ｅ／ＶＡ／ＶＣＡエラストマー（エラスト−ｑ −ＩＩ
Ｂという）けＶＡ６４．３重量チとＣＩｏ、７１重ｆ
Ｉ−％を含み、ムーニー粘度は３６５であった。Example ■ Example ■ and Comparative Experiment A were repeated to demonstrate the effect of carbon black on the tensile values and elongation of E/VA/VCA elastomers after soap-sulfur vulcanization. Carbon black, N550 and N
A modified version of 774-11 was used. E/V A/V CA elastomer (Elastomer II
A) is VA57.7i, CIo, 74% by weight
The Mooney viscosity was 34. E/VA/VCA elastomer (Elasto-q-II) prepared by the method of Example I with periodic small additions of VCA monomer.
(referred to as B), VA64.3 weight chi and CIo, 71 weight f
Mooney viscosity was 365.
カーボンブラック量を変えた以外は実施例■の方法のと
おり混合し加硫したエラストマー■ＡとＩＩＢの結果は
次のとおシであるっ
使用カーボンブラック Ｎ７７４ Ｎ７７４ Ｎ５５０
Ｎ７７４ Ｎ５０キユア オペレーター Ｉ１１
■ＩＩＩＩ引張値、ｐｓｉ ３分 １１３０１０２
０ ｘ１７ｏ １４３（１１７４０〃 ７分 １１
５０１０５０１２３０１４００１６００〃１５分 １１
１０１０１０１１９０１５６０１８８０〃３０分 １１
２０１１３０１２００１４８０１８３０伸度、チ ３分
１９０ １４０ １３０ ３５０ ３１０〃
７分 １５０ １４０ １４０ ３４０ ２５０〃１
５分 １５０ １４．０ １３０ ４００ ３１０〃
３０分 １６０ １６０ １４０ ３７０ ３３０上
記結果から本発明の重合反応中ＶＣＡキュアサイトモノ
マーを定期的添加する改良方法はＮ７７４とＮ５５０両
カーボンブラックを使用してより高い引張値を与えるこ
とは明らかである。しかしＮ５５０カーボンブラツクは
均一な高引張値を与えたので特に断らない限りあとの実
施例には全部Ｎ５５０を使用した。Elastomer mixed and vulcanized according to the method of Example ■ except that the amount of carbon black was changed. The results of A and IIB are as follows. Carbon black used: N774 N774 N550
N774 N50 Cure Operator I11
■III tensile value, psi 3 minutes 1130102
0 x17o 143 (11740〃 7 minutes 11
501050123014001600〃15 minutes 11
101010119015601880〃30 minutes 11
201130120014801830 Elongation, Chi 3 minutes 190 140 130 350 310〃
7 minutes 150 140 140 340 250〃1
5 minutes 150 14.0 130 400 310〃
30 minutes 160 160 140 370 330 From the above results it is clear that the improved method of periodically adding VCA cure site monomer during the polymerization reaction of the present invention provides higher tensile values using both N774 and N550 carbon blacks. However, since N550 carbon black gave uniformly high tensile values, N550 was used in all subsequent examples unless otherwise noted.
実施例■および■
Ｅ／ＶＡ／ＶＣＡインターポリマー組成物の変更能力を
示すため実施例Ｉの方法にクロロ酢酸ビニル添加量を増
して２実験を行なった。重合反応の初め６時間の毎時の
終り７−１０分間にＶＣＡモノマーの６等分の１づつ装
入した。Examples (1) and (2) To demonstrate the ability to modify E/VA/VCA interpolymer compositions, two experiments were conducted using the method of Example I with increased amounts of vinyl chloroacetate. One-sixth portion of the VCA monomer was charged 7-10 minutes after each hour during the first 6 hours of the polymerization reaction.
実施例Ｉに記載の方法とちがう実験詳細は表に示してい
る。Experimental details different from the method described in Example I are given in the table.
ニジストマーと加硫物の性質も表に示している。The properties of the nidistomers and vulcanizates are also shown in the table.
４１一
実施例■ 実施例■
エチレン圧力（ｐｓｉｇ） １２７０−１４３０
１１１０−１１６０クロロ酢酸ビニル（合計ｆ）
３０ ４０重合時間（合計時間）９８
エラストマー酢酸ビニル％ ６１，４
６７．３〃 塩素 ％ ０．６
５ ０．９１ム一ニー粘度
３３ ３９．５加硫生成物弓１張強度（ｐｓ
ｉ ） １８３０ １８００〃 伸度 （％
） ３４０ ２６０実施例■と■
過硫酸アンモニウム−ナトリウムスルホキシレート触媒
系を過酸化水素−ナトリウムホルムアルデヒドスルホキ
シレート触媒系に代えて２実験を行ない変更方法を示し
た。41 Example ■ Example ■ Ethylene pressure (psig) 1270-1430
1110-1160 vinyl chloroacetate (total f)
30 40 Polymerization time (total time) 98 Elastomer vinyl acetate% 61.4
67.3 Chlorine % 0.6
5 0.91 muuni viscosity
33 39.5 Vulcanized product bow 1 tensile strength (ps
i) 1830 1800〃 Elongation (%
) 340 260 Examples (1) and (2) Two experiments were conducted in which the ammonium persulfate-sodium sulfoxylate catalyst system was replaced with a hydrogen peroxide-sodium formaldehyde sulfoxylate catalyst system to demonstrate a modified method.
この実験に次のものを装入した。The following items were loaded into this experiment:
実施例■ 実施例■
脱イオン水 ８５０ ｆ ８５
０ Ｆテトロニック（商品）９０８ ２６
ｒ ２６ ｆエマ−サル（商品）６４５３
４９４９ナトリウムホルムアルデヒドラＪ、
＝キシレート １．５ｆ２ｆ硫酸第１鉄７水化物
０．０２ｆ Ｏ，０２ｆぎ酸
０．４９ ０．４ｆＶ
ＡＭ ８００ ｆ ８
００ ｆ反応機を加熱し普通の方法でエチレン加圧し
た。しかし過酸化水素０．５チ水溶液を反応機に連続秤
量添加し重合を開始し反応させた。重合の初め６時間の
毎時終り１０分間にクロロ酢酸ビニルの６分の１つつ加
えた。各反応にクロロ酢酸ビニル合計３２．５９を加え
た。回収し配合し普通のとおり加硫したＥ／ＶＡ／ＶＣ
Ａターポリマーエラストマーにおいて重合時間、エチレ
ン圧および生成物性質は次のとおりであった。Example■ Example■ Deionized water 850 f 85
0 F Tetronic (product) 908 26
r 26 f Emersal (product) 6453
4949 Sodium Formaldehydra J,
=Xylate 1.5f2f ferrous sulfate heptahydrate
0.02f O, 02f formic acid
0.49 0.4fV
AM 800 f8
The 00 f reactor was heated and pressurized with ethylene in the usual manner. However, 0.5% aqueous solution of hydrogen peroxide was continuously added to the reactor to initiate polymerization and reaction. One sixth of the vinyl chloroacetate was added every 10 minutes at the end of every hour for the first 6 hours of the polymerization. A total of 32.59 vinyl chloroacetate was added to each reaction. E/VA/VC recovered, blended and vulcanized as usual
Polymerization time, ethylene pressure and product properties were as follows for the A terpolymer elastomer.
実施例■ 実施例■
エチレン圧（ｐａｔ ） １２８０１４８０
１２９０−１．４１０重合時間（全時間）
９ ８．５エラストマー酢酸ビニル（％
） ６２．８ ６３〃 地素 （
％） ０．７ ０．７１〃
ムーニー粘度 ２４．５ ２６加硫
生成物引張強度（ｐｓｉ ） １８１０ １８
７０〃 伸度 （％） ３２０ ３
１０実施例■１
本実施例は改良エラストマーの性能を示すため行なった
。Example■ Example■ Ethylene pressure (pat) 12801480
1290-1.410 polymerization time (total time)
9 8.5 Elastomer vinyl acetate (%
) 62.8 63〃 Earth (
%) 0.7 0.71〃
Mooney viscosity 24.5 26 Vulcanized product tensile strength (psi) 1810 18
70〃 Elongation (%) 320 3
10 Example 1 This example was conducted to demonstrate the performance of the improved elastomer.
実施例■の一般法によって反応を行なわせたが、但し重
合中エチレン圧全増加した。酢酸とニルモノマーは全量
最初に装入し、クロロ酢酸ビニル３２２は重合反応の初
めの６時間中に間欠的に加えた。エチレン初圧７２０
ｐｓｉｇであったが、圧力は重合反応の初め１．５時間
に１２００ｐｓｉｇに上昇した。エチレン圧は更に増加
し残υ時間中（全重合時間８５時間）に最終２１００
ｐｓｉｇとした。標準方法でＥ／ＶＡ／ＶＣＡターポリ
マーを回収し、分析したととろＶＡ６５．１％およびＣ
Ｉｏ、８５％であった。またムーニー粘度は４４であっ
た。The reaction was carried out according to the general method of Example (1), except that the total ethylene pressure increased during the polymerization. Acetic acid and vinyl monomer were initially charged in their entirety, and vinyl chloroacetate 322 was added intermittently during the first 6 hours of the polymerization reaction. Ethylene initial pressure 720
psig, but the pressure rose to 1200 psig during the first 1.5 hours of the polymerization reaction. The ethylene pressure increased further and reached a final pressure of 2100 during the remaining υ hours (total polymerization time 85 hours).
psig. The E/VA/VCA terpolymer was recovered and analyzed using standard methods and was found to have 65.1% VA and C
Io was 85%. Further, the Mooney viscosity was 44.
Ｅ／Ｖ Ａ／Ｖ ＣＡエラストマーを実施例Ｉの調合で
混合し１７０℃で３０分加研した。３０分キュアした後
の加硫生成物の引張強度は１９２０ｐｓｉｇであシまた
伸度２４０チであった。上の結果から使用ＶＡＭ全量を
重合反応開始時に加えまた重合中ＶＣＡを間欠的に加え
かつエチレン圧を重合中にわたシ増加すればＥ／Ｖ Ａ
／Ｖ ＣＡエラストマーのムーニー粘度と引張値が更に
改良されるだろうことは明白である。E/V A/V CA elastomers were mixed in the formulation of Example I and polished at 170° C. for 30 minutes. After curing for 30 minutes, the vulcanized product had a tensile strength of 1920 psig and an elongation of 240 inches. From the above results, if the entire amount of VAM used is added at the start of the polymerization reaction, VCA is added intermittently during the polymerization, and the ethylene pressure is increased during the polymerization, E/V A can be reduced.
It is clear that the Mooney viscosity and tensile values of /VCA elastomers would be further improved.
実施例■
実施例■を反復した、但し全重合時間を９．７５時間に
増した。この重合のエチレン初圧を７２０ ｐｓｉｇと
し重合量始後１時間以内に１２００ ｐｓｉｇに上昇し
残り８．７５時間中除々に２４５０ｐｓｉｇまで増した
。えたＥ／ＶＡ／ＶＣＡエラストマーのムーニー粘度は
３６でありＶＡ６２．４％とＣＩｏ、９３チを含んでい
た。標準石鹸いおうキュア系を用い１７０℃で加硫した
ニジストマーの最大引張値は１９４０ｐｓｉ であり
伸度は２４０％であった。Example ■ Example ■ was repeated except that the total polymerization time was increased to 9.75 hours. The initial pressure of ethylene in this polymerization was set at 720 psig and rose to 1200 psig within 1 hour after the start of polymerization, and gradually increased to 2450 psig during the remaining 8.75 hours. The obtained E/VA/VCA elastomer had a Mooney viscosity of 36 and contained a VA of 62.4% and a CIo of 93 H. The maximum tensile value of the nystomer cured at 170° C. using a standard soap sulfur cure system was 1940 psi and the elongation was 240%.
実施例■
実施例Ｉの一般法と同じ反応体を使用して行なった実施
例によってクロロ酢酸ビニルキュアサイトモノマ一連続
添加性能を示している。反応器のエチレン圧を約１３２
０ｐｓｉｇとした後ナトリウムホルムアルデヒドスルホ
キシレート水溶液を添加し重合反応を開始させた。３時
間後クロロ酢酸ビニル４０ｆを１時間３０分にわたり連
続添加して重合反応を更に５時間１５分つづけた。還元
剤液は重合中終始連続添加し才だエチレン圧は１３２０
乃至１４１〇ｐｓｉｇに保った。普通の方法で回収した
Ｅ／ＶＡ／ＶＣＡターポリマーのムーニー粘度は３６で
ありＶＡ５８．３％とＣ１０，４７％を含んでいた。加
硫したエラストマーの引張値は１６８０ ｐｓｉ で
ありまた伸度は２８０チであった。EXAMPLE 1 An example conducted using the same reactants as in the general procedure of Example I demonstrates single continuous addition performance of the vinyl chloroacetate cure site monomer. The ethylene pressure in the reactor is approximately 132
After setting the pressure to 0 psig, an aqueous sodium formaldehyde sulfoxylate solution was added to initiate the polymerization reaction. After 3 hours, 40f of vinyl chloroacetate was continuously added over 1 hour and 30 minutes, and the polymerization reaction was continued for another 5 hours and 15 minutes. The reducing agent liquid is added continuously throughout the polymerization.The ethylene pressure is 1320.
The pressure was maintained between 1410 psig and 1410 psig. The E/VA/VCA terpolymer recovered by conventional methods had a Mooney viscosity of 36 and contained 58.3% VA and 10.47% C. The vulcanized elastomer had a tensile value of 1680 psi and an elongation of 280 inches.
実施例Ｘ
クロロ酢酸ビニルモノマーを酢酸とニルモノマーで稀釈
する実施例によって連続添加法の変法を示すものである
。Example X A modification of the continuous addition method is illustrated by an example in which vinyl chloroacetate monomer is diluted with acetic acid and vinyl monomer.
反応は実施例■と同様に行なったが、但しＶＡＭ ７０
０２のみを反応機に装入した。残り１００９のＶＡＭは
ＶＣＡ３２′ｉと混合しくＶＣＡ２４％濃度）エタ液を
重合開始６時間にわたシ反応機に連続均一に加えた。全
重合時間７．５時間中エチレン圧は１２４０乃至１．４
１０ ｐｓｉｇであった。えたＥ／Ｖ Ａ／Ｖ ＣＡエ
ラストマーのムーニー粘度は３３であシＶＡ５９．４チ
とＣ１０，６０％を含んでいた。The reaction was carried out in the same manner as in Example 2, except that VAM 70
Only 02 was charged into the reactor. The remaining 1009 VAM was mixed with VCA 32'i (VCA 24% concentration) and an ethyl solution was continuously and uniformly added to the reactor 6 hours after the start of polymerization. During the total polymerization time of 7.5 hours, the ethylene pressure was 1240 to 1.4.
It was 10 psig. The obtained E/V A/V CA elastomer had a Mooney viscosity of 33, a VA of 59.4 and a C content of 10.60%.
普通の１７０℃石鹸−いおう加硫法でえた生成物は７分
キュア後最大引張値１７３０ｐｓｉ と伸度２６０％
をもっていた。The product obtained by the ordinary 170°C soap-sulfur vulcanization method has a maximum tensile value of 1730 psi and an elongation of 260% after 7 minutes of curing.
had.
比較実験Ｂ
重合反応開始時に酢酸ビニルモノマーの全部又は少々く
も大部分があることの重要性を示すため実施例Ｘの方法
を反復したが、但しＶＡ、Ｍ ３００ ｆとＶＣＡ １
３．９ ｆを反応機に装入した。ＶＡＭ５００ｆ中クロ
ロ酢酸ビニル２３．１ｆ（ＶＣＡ濃度４．７％）の溶液
をつくり重合開始から６．３時間にわたり反応機に連続
均等に加えた。試験中エチレン圧は１１６０乃至１３８
０ｐｓｉｇ（全重合時間１０時間）であった。えたＥ／
Ｖ Ａ／Ｖ ＣＡエラストマーのＶＡは５５．７％で、
Ｃ１は０．８１％であった。エラストマーのムーニー粘
度は僅か１３であシ、Ｎ７７４カーボンブラツク使用加
硫後の最大引張強度が僅か１０１０ ｐｓｉ であり
伸度２５０％であった。低エチレン圧（９２０−９６０
ｐｓｉｇ）で重合を反復してエラストマーのＶＡ、！：
ＶＣＡ含景を増加しくＶＡ６２．４チとＣ１１，０２％
）捷た加硫生成物の引張値を僅かに改良する（伸度２０
０チにおいて１２４０ｐｓｉ）ことはできた。エラスト
マーのムーニー粘度１４は本質的に不変であった。配合
のＮ７７４の代９にＮ５５０を使っても実施例Ｘのエラ
ストマーにおいてえた引張値に匹敵する値はえられかか
ったであろう。Comparative Experiment B To demonstrate the importance of having all or a small portion of the vinyl acetate monomer present at the beginning of the polymerization reaction, the method of Example
3.9 f was charged to the reactor. A solution of 23.1f vinyl chloroacetate (VCA concentration 4.7%) in VAM500f was prepared and added continuously and evenly to the reactor over a period of 6.3 hours from the start of polymerization. Ethylene pressure during the test was 1160 to 138
It was 0 psig (total polymerization time 10 hours). EtaE/
VA of VA/V CA elastomer is 55.7%,
C1 was 0.81%. The elastomer had a Mooney viscosity of only 13, a maximum tensile strength of only 1010 psi and an elongation of 250% after vulcanization using N774 carbon black. Low ethylene pressure (920-960
VA of the elastomer by repeating polymerization at psig),! :
Increased VCA inclusion, VA62.4chi and C11.02%
) Slightly improves the tensile value of the shredded vulcanized product (elongation 20
1240 psi at zero position). The Mooney viscosity of the elastomer was essentially unchanged. Using N550 in place 9 of N774 in the formulation would have almost produced tensile values comparable to those obtained with the Example X elastomer.
特許出願人 クワンタムケミカルコーポレーション〃
〃 用薄良治２−．、
／１ ＼
、、゛
、′、、二・５′Patent applicant: Quantum Chemical Corporation
〃 Yosuka Ryoji 2-. , /1 \ ,,゛,',,2・5'
Claims (1)
びフリーラジカル重合触媒を含む水性エマルジョン中に
おいてエチレン、酢酸ビニルおよびハロゲン含有キユア
サイトモノマーを共重合して酢酸ビニル４０乃至７０重
量％と塩素０．２乃至２重量％を含む石鹸−いおう加硫
性エラストマーを生成する方法において、温度５乃至８
０℃、エチレン圧４００乃至４０００ｐｓｉｇにおいて
重合反応開始後全重合時間の少なくとも１／２０にわた
り該ハロゲン含有モノマーを連続的又は間欠的に添加し
て重合させることを特徴とする方法。 ２、キユアサイトモノマーがクロロ酢酸ビニル、ブロモ
酢酸ビニル、２−クロロプロピオン酸ビニル、２−クロ
ロ酪酸ビニル、２−クロロイソ酪酸ビニル又は２−クロ
ロエチルビニルエーテルからえらばれたハロゲン含有ビ
ニルモノマーである請求項１に記載の方法。３、酢酸ビ
ニルモノマー全量が重合開始時に含まれている請求項１
又は２に記載の方法。４、酢酸ビニルモノマーの大部分
が重合開始時に含まれており上記モノマーの少量がその
後加えられる請求項１又は２に記載の方法。 ５、酢酸ビニルモノマーの少量をハロゲン含有ビニルモ
ノマーと混合し重合中連続的又は間欠的に添加する請求
項４に記載の方法。 ６、重合温度を２０乃至５５℃としかつハロゲン含有ビ
ニルモノマーがクロロ酢酸ビニルである請求項１から５
までのいづれかに記載の方法。 ７、エラストマーが５５乃至６５重量％の酢酸ビニルと
０．５及至１重量％の塩素を含む請求項６に記載の方法
。 ８、フリーラジカル触媒が過酸化水素、過塩素酸ナトリ
ウム、過ほう酸ナトリウム、過硫酸ナトリウム、過硫酸
カリウム又は過硫酸アンモニウムでありかつ、酢酸ビニ
ルモノマー基準０．５乃至３重量％の量で含まれている
請求項７に記載の方法。 ９、水素亜硫酸ナトリウム、メタ重亜硫酸ナトリウム、
ヒドロ亜硫酸ナトリウム又はホルムアルデヒドスルホキ
シル酸ナトリウムからえらばれた還元剤を共触媒として
使用する請求項８に記載の方法。 １０、重合中エチレン圧を重合開始時の４００乃至９０
０ｐｓｉｇから重合終了時の２０００乃至４０００ｐｓ
ｉｇまで増加する請求項１から９までのいづれかに記載
の方法。 １１、重合開始１乃至２時間以内にエチレン圧を約１２
００ｐｓｉｇまで増加する請求項１０に記載の方法。[Claims] 1. Vinyl acetate is produced by copolymerizing ethylene, vinyl acetate, and a halogen-containing cure site monomer in an aqueous emulsion containing a nonionic surfactant, an anionic surfactant, and a free radical polymerization catalyst. In a method for producing a soap-sulfur vulcanizable elastomer containing 40 to 70% by weight of chlorine and 0.2 to 2% by weight of chlorine, the temperature is 5 to 8%.
A method characterized in that the halogen-containing monomer is continuously or intermittently added for at least 1/20 of the total polymerization time after the initiation of the polymerization reaction at 0° C. and an ethylene pressure of 400 to 4000 psig. 2. The cure site monomer is a halogen-containing vinyl monomer selected from vinyl chloroacetate, vinyl bromoacetate, vinyl 2-chloropropionate, vinyl 2-chlorobutyrate, vinyl 2-chloroisobutyrate, or 2-chloroethyl vinyl ether. The method described in Section 1. 3. Claim 1, wherein the entire amount of vinyl acetate monomer is contained at the start of polymerization.
Or the method described in 2. 4. A process according to claim 1 or 2, wherein the majority of the vinyl acetate monomer is included at the beginning of the polymerization and a small amount of said monomer is added afterwards. 5. The method according to claim 4, wherein a small amount of vinyl acetate monomer is mixed with the halogen-containing vinyl monomer and added continuously or intermittently during the polymerization. 6. Claims 1 to 5, wherein the polymerization temperature is 20 to 55°C and the halogen-containing vinyl monomer is vinyl chloroacetate.
The method described in any of the above. 7. The method of claim 6, wherein the elastomer contains 55 to 65% by weight vinyl acetate and 0.5 to 1% by weight chlorine. 8. The free radical catalyst is hydrogen peroxide, sodium perchlorate, sodium perborate, sodium persulfate, potassium persulfate or ammonium persulfate, and is contained in an amount of 0.5 to 3% by weight based on the vinyl acetate monomer. 8. The method according to claim 7. 9. Sodium hydrogen sulfite, sodium metabisulfite,
9. The process as claimed in claim 8, wherein a reducing agent selected from sodium hydrosulfite or sodium formaldehyde sulfoxylate is used as cocatalyst. 10. Ethylene pressure during polymerization is 400 to 90 at the start of polymerization.
From 0 psig to 2000 to 4000 ps at the end of polymerization
10. A method according to any of claims 1 to 9, wherein the ig is increased to ig. 11. Within 1 to 2 hours of starting polymerization, reduce the ethylene pressure to about 12
11. The method of claim 10, wherein the pressure is increased to 00 psig.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15246788A JPH01319513A (en) | 1988-06-22 | 1988-06-22 | Improved production of copolymer of ethylene vinyl acetate and reactive halogen-containing monomer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15246788A JPH01319513A (en) | 1988-06-22 | 1988-06-22 | Improved production of copolymer of ethylene vinyl acetate and reactive halogen-containing monomer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01319513A true JPH01319513A (en) | 1989-12-25 |
Family
ID=15541150
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15246788A Pending JPH01319513A (en) | 1988-06-22 | 1988-06-22 | Improved production of copolymer of ethylene vinyl acetate and reactive halogen-containing monomer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01319513A (en) |
-
1988
- 1988-06-22 JP JP15246788A patent/JPH01319513A/en active Pending
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