JPS63278910A - Manufacture of high-molecular weight polymer - Google Patents
Manufacture of high-molecular weight polymerInfo
- Publication number
- JPS63278910A JPS63278910A JP11418887A JP11418887A JPS63278910A JP S63278910 A JPS63278910 A JP S63278910A JP 11418887 A JP11418887 A JP 11418887A JP 11418887 A JP11418887 A JP 11418887A JP S63278910 A JPS63278910 A JP S63278910A
- Authority
- JP
- Japan
- Prior art keywords
- molecular weight
- polymerization
- polymer
- meth
- initiator
- 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
- 229920006158 high molecular weight polymer Polymers 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000000178 monomer Substances 0.000 claims abstract description 26
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 18
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 17
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 15
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 229920000642 polymer Polymers 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 150000004659 dithiocarbamates Chemical group 0.000 claims 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical group NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 abstract description 19
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 15
- 150000001875 compounds Chemical class 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 9
- 238000012662 bulk polymerization Methods 0.000 abstract description 8
- 239000002904 solvent Substances 0.000 abstract description 8
- 239000000853 adhesive Substances 0.000 abstract description 4
- 230000001070 adhesive effect Effects 0.000 abstract description 4
- 229920001169 thermoplastic Polymers 0.000 abstract description 3
- 239000002270 dispersing agent Substances 0.000 abstract description 2
- 239000008394 flocculating agent Substances 0.000 abstract description 2
- 239000012778 molding material Substances 0.000 abstract description 2
- 239000004416 thermosoftening plastic Substances 0.000 abstract description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
- 238000006116 polymerization reaction Methods 0.000 description 18
- 239000003999 initiator Substances 0.000 description 14
- -1 2-ethylhexyl Chemical group 0.000 description 8
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000001226 reprecipitation Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- 239000012990 dithiocarbamate Substances 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010557 suspension polymerization reaction Methods 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- IOEJYZSZYUROLN-UHFFFAOYSA-M Sodium diethyldithiocarbamate Chemical compound [Na+].CCN(CC)C([S-])=S IOEJYZSZYUROLN-UHFFFAOYSA-M 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 229940116901 diethyldithiocarbamate Drugs 0.000 description 2
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 2
- 229950004394 ditiocarb Drugs 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000012966 redox initiator Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-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
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical group OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- YAXXOCZAXKLLCV-UHFFFAOYSA-N 3-dodecyloxolane-2,5-dione Chemical compound CCCCCCCCCCCCC1CC(=O)OC1=O YAXXOCZAXKLLCV-UHFFFAOYSA-N 0.000 description 1
- LAIUFBWHERIJIH-UHFFFAOYSA-N 3MC7 Natural products CCCCC(C)CC LAIUFBWHERIJIH-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 235000003325 Ilex Nutrition 0.000 description 1
- 241000209035 Ilex Species 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 235000009827 Prunus armeniaca Nutrition 0.000 description 1
- 244000018633 Prunus armeniaca Species 0.000 description 1
- 241000219289 Silene Species 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- CKESHWQHGBKZBB-UHFFFAOYSA-N [4-(diethylcarbamothioylsulfanylmethyl)phenyl]methyl n,n-diethylcarbamodithioate Chemical compound CCN(CC)C(=S)SCC1=CC=C(CSC(=S)N(CC)CC)C=C1 CKESHWQHGBKZBB-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- BVBCEEGYULUZFK-UHFFFAOYSA-N benzyl n-methylcarbamodithioate Chemical compound CNC(=S)SCC1=CC=CC=C1 BVBCEEGYULUZFK-UHFFFAOYSA-N 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- CSNJTIWCTNEOSW-UHFFFAOYSA-N carbamothioylsulfanyl carbamodithioate Chemical compound NC(=S)SSC(N)=S CSNJTIWCTNEOSW-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- LMBWSYZSUOEYSN-UHFFFAOYSA-N diethyldithiocarbamic acid Chemical compound CCN(CC)C(S)=S LMBWSYZSUOEYSN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- LZWYWAIOTBEZFN-UHFFFAOYSA-N ethenyl hexanoate Chemical compound CCCCCC(=O)OC=C LZWYWAIOTBEZFN-UHFFFAOYSA-N 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- WHDGWKAJBYRJJL-UHFFFAOYSA-K ferbam Chemical compound [Fe+3].CN(C)C([S-])=S.CN(C)C([S-])=S.CN(C)C([S-])=S WHDGWKAJBYRJJL-UHFFFAOYSA-K 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- JPVRJMGCWMBVMY-UHFFFAOYSA-N methylcarbamothioylsulfanyl n-methylcarbamodithioate Chemical compound CNC(=S)SSC(=S)NC JPVRJMGCWMBVMY-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 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
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- GWQWBFBJCRDINE-UHFFFAOYSA-M sodium;carbamodithioate Chemical compound [Na+].NC([S-])=S GWQWBFBJCRDINE-UHFFFAOYSA-M 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- RKQOSDAEEGPRER-UHFFFAOYSA-L zinc diethyldithiocarbamate Chemical compound [Zn+2].CCN(CC)C([S-])=S.CCN(CC)C([S-])=S RKQOSDAEEGPRER-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
【発明の詳細な説明】
〔発明の背景〕
（産業上の利用分野）
本発明は、高分子量重合体の製造法に関するものである
。DETAILED DESCRIPTION OF THE INVENTION [Background of the Invention] (Industrial Field of Application) The present invention relates to a method for producing high molecular weight polymers.
更に詳しくは、本発明はジチオカーバメート基を有する
重合開始剤を用いてラジカル重合性ビニル単量体を光に
よシ塊状重合させ、重量平均分子量１００万以上の重合
体を得る製造法に関するものである。More specifically, the present invention relates to a method for producing a polymer having a weight average molecular weight of 1,000,000 or more by subjecting radically polymerizable vinyl monomers to bulk polymerization by light using a polymerization initiator having a dithiocarbamate group. be.
（従来の技術）
重合体の分子量と機械物性、化学物性等の諸物性には一
般的な相関があることは広く知られている。一般に、高
分子材料の分子量が増大すれば剛性凝集力、耐摩耗性、
耐薬品性が向上することも知られている。従って、近年
、粘着剤の粘着力、りＩＪ−ｆ％性の向上酸を材料の剛
性、弾力性、耐摩耗性、耐薬品性の向上、高分子凝集剤
の凝集力向上、或いは高分子相溶化剤における分散性の
向上等各分野における諸性能向上の為、高分子量重合体
の需要は高オシククある。(Prior Art) It is widely known that there is a general correlation between the molecular weight of a polymer and various physical properties such as mechanical properties and chemical properties. In general, as the molecular weight of a polymer material increases, its rigidity, cohesive force, wear resistance,
It is also known to improve chemical resistance. Therefore, in recent years, there have been efforts to use acids to improve the adhesive strength and IJ-f% properties of adhesives, to improve the rigidity, elasticity, abrasion resistance, and chemical resistance of materials, to improve the cohesive strength of polymer flocculants, or to improve the polymer phase. There is a strong demand for high molecular weight polymers to improve performance in various fields such as improved dispersibility in solubilizers.
高分子量重合体を製造するための重合方法としては一般
にラジカル重合が適しているが、ラジカル重合によシ製
造される重合体の分子量は重合温度、開始剤濃度、モノ
マー濃度、溶媒濃度等の各因子に依存することも亦知ら
れている。Radical polymerization is generally suitable as a polymerization method for producing high molecular weight polymers, but the molecular weight of polymers produced by radical polymerization depends on various factors such as polymerization temperature, initiator concentration, monomer concentration, and solvent concentration. It is also known that it depends on factors.
ここで、ラジカル重合における重合法を、重合状態で分
類すると、塊状重合、溶液重合、懸濁重合、及びエマル
ジ、ン重合になる。Here, when the polymerization method in radical polymerization is classified according to the polymerization state, it is classified into bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization.
しかしながら、分子量１００万以上の高分子量重合体を
製造するためには、溶液重合、懸濁重合を用いることが
出来ない。However, solution polymerization and suspension polymerization cannot be used to produce high molecular weight polymers with a molecular weight of 1 million or more.
何故なら、溶液重合では重合反応中、高分子生長末端に
溶媒が連鎖移動剤として働くため高分子量に成長するの
を阻害するからである。一方、重合開始剤の濃度を下げ
るほど得られる高分子の分子量が大きくなることが知ら
れているが、懸濁重合においては通常モノマーに対して
重合開始剤濃度を１重量係以上にしなければ安定した重
合反応を行なうことが出来ない九め、重量平均分子量（
Ｍ９Ｆ）１００万以上の高分子量重合体が得られないの
でこの方法も用いられない。This is because in solution polymerization, during the polymerization reaction, the solvent acts as a chain transfer agent at the growing end of the polymer, thereby inhibiting its growth to a high molecular weight. On the other hand, it is known that the lower the concentration of polymerization initiator, the higher the molecular weight of the resulting polymer, but suspension polymerization is generally stable unless the concentration of polymerization initiator is 1 weight ratio or more relative to the monomer. Ninth, weight average molecular weight (
M9F) This method cannot be used because a high molecular weight polymer of 1 million or more cannot be obtained.
エマルジ、ン重合では高分子量重合体が得られることは
良く知られているが、界面活性剤を用いるため耐水性等
の最終物性に悪影響があるばかシでなく、媒質として水
を用いる為に乾燥に多大な労力と経費を必要とするとい
う欠点を有する。It is well known that high molecular weight polymers can be obtained by emulsion polymerization, but since it uses a surfactant, it does not have a negative effect on the final physical properties such as water resistance, and because it uses water as a medium, it is dry. The disadvantage is that it requires a great deal of effort and expense.
更に塊状重合については、一般にかかる重合の開始法と
して熱開始、レドックス開始及び光開始がある。Additionally, for bulk polymerizations, common methods of initiating such polymerizations include thermal initiation, redox initiation, and photoinitiation.
一般に重含温度は低いほど高分子量の高分子が得られる
が熱開始は比較的高温で反応を行なう九めに本質的に高
分子量重合体は得られない。In general, the lower the loading temperature is, the higher the molecular weight polymer can be obtained, but if the thermal initiation is carried out at a relatively high temperature, essentially no high molecular weight polymer can be obtained.
杏
レドックス開始においては比較的低温で反応が進行させ
ることが出来る九め高分子量重合体が得られるが、単量
体によっては必須要素である助触媒の触媒毒となる可能
性があシ用いる単量体が限定されるばかシでなく、反応
完了後、残存の助触媒が色相耐候性等の最終物性に悪影
譬があることが知られている。In apricot redox initiation, a polymer with a relatively high molecular weight is obtained, which allows the reaction to proceed at a relatively low temperature. It is known that the cocatalyst remaining after the completion of the reaction may have an adverse effect on the final physical properties such as hue and weather resistance.
（発明が解決しようとする問題点）
過酸化物、アゾ化合物等通常の増感剤を用いて光開始の
塊状重合を行なう場合、増感剤を低濃度にすると高分子
量重合体を製造することが出来るが、著しい発熱反応を
伴い、反応の制御が困難であるばかりでなく時には著し
い発泡を伴い反応物が光透過性を失い収率が低下するこ
ともある。更に、この方法によシ生成する重合物はｒル
状であることが多く、溶剤に不溶であるとか、熱可塑性
を失なりｌ）するという問題点がある。(Problems to be Solved by the Invention) When carrying out photoinitiated bulk polymerization using ordinary sensitizers such as peroxides and azo compounds, it is possible to produce high molecular weight polymers by reducing the concentration of the sensitizer. However, it is accompanied by a significant exothermic reaction, which not only makes it difficult to control the reaction, but also sometimes causes significant foaming, resulting in a loss of light transmittance of the reactant and a decrease in yield. Furthermore, the polymer produced by this method is often in the form of a polymer, and there are problems in that it is insoluble in solvents and loses its thermoplasticity.
ま次、前述した過酸化物、アゾ化合物等の増感剤を用い
ないで光開始の塊状重合を行なう場合において、重合開
始剤の濃度を小さくすることに・よりて高分子量の重合
体が得られることは知られているが、熱、レドックス或
いは光で重合開始剤を解離させ石場合、ラジカルの寿命
は非常に短かく、夫々熱源、助触媒或いは光源を取シ除
くと重合開始剤が失活するし、更に余シ重合開始剤濃度
を小さくすると実質的に反応が進まなくなるという間［
４る。一方、ジチオカーバメート基を有する化合物がラ
ジカル重合開始能を持つことは知られているが、かかる
開始剤を用いて１００万以上の高分子量重合体が得られ
たという報告は未だない。Second, when carrying out photoinitiated bulk polymerization without using the aforementioned sensitizers such as peroxides and azo compounds, it is possible to obtain high molecular weight polymers by reducing the concentration of the polymerization initiator. However, when the polymerization initiator is dissociated by heat, redox, or light, the lifespan of the radicals is very short, and the polymerization initiator disappears when the heat source, cocatalyst, or light source is removed, respectively. Furthermore, if the concentration of the polymerization initiator is reduced, the reaction will not proceed substantially [
4 Ru. On the other hand, although it is known that compounds having a dithiocarbamate group have the ability to initiate radical polymerization, there has been no report yet that a high molecular weight polymer of 1 million or more was obtained using such an initiator.
（ポリマープリプリント、ジャパン、第３２巻、第６号
、第１０４３頁（１９８３年） 、ＰｏｌｙｍｅｒＰｒ
＊ｐｒｌｎｔｓ ｅ Ｊａｐａｎ、 ３２ ＃
４６ ＊ １０４３（１９８３） ）（問題
点の解決手段）
本発明者は、これら従来の問題点を解決すべく鋭意検討
を行なった結果極めて高純度のラジカル重合性ビニルモ
ノマーに対し低濃度でジチオカーバメート基を有する重
合開始剤を添加し、光によシ塊状重合を行なうことによ
ってこれら従来の問題点を克服し、高分子量重合体が得
られることを見出し本発明を完成するに至りた。(Polymer Preprint, Japan, Vol. 32, No. 6, p. 1043 (1983), PolymerPr
*prlnts e Japan, 32 #
46 * 1043 (1983)) (Means for solving the problems) As a result of intensive studies to solve these conventional problems, the present inventor has developed a solution for dithiocarbamate at low concentrations for radically polymerizable vinyl monomers of extremely high purity. The present inventors have discovered that these conventional problems can be overcome and a high molecular weight polymer can be obtained by adding a polymerization initiator having a group and carrying out bulk polymerization using light, and have completed the present invention.
即ち、本発明の高分子量重合体の製造法は、一般式
（式中、Ｒ１及びＲ２はそれぞれ水素又は炭素数１〜ｌ
Ｏのアルキル基を示す。）
で表わされるジチオカーバメート基を有する重合合間始
剤を用いてラジカル重合性ビニル単量体を光によシ塊状
重合させることによシよ多重量平均分子量１００万以上
の高分子量重合体を製造すること、を特徴とするもので
ある。That is, the method for producing a high molecular weight polymer of the present invention is based on the general formula (wherein R1 and R2 are each hydrogen or a carbon number of 1 to 1
Indicates an alkyl group of O. ) A high molecular weight polymer having a multi-weight average molecular weight of 1,000,000 or more is produced by photo-bulk polymerizing a radically polymerizable vinyl monomer using a polymerization initiator having a dithiocarbamate group represented by It is characterized by:
（発明の効果等）
本発明の製造法によれば、分子量が高いはかシでなく、
ｒル分が殆んどなく、溶剤に可溶であシ且つ熱可塑性の
高分子量重合体を安価で且つ容易な方法で製造すること
が出来る。そしてこの方法で得られた高分子量重合体は
、その優れた性能を活用して、接着剤、成型材料、凝集
剤、分散剤として有利に使用することが出来る。(Effects of the invention, etc.) According to the production method of the present invention, it is possible to obtain
It is possible to produce a high-molecular-weight polymer that is soluble in solvents, thermoplastic, and has almost no liquid content at a low cost and by an easy method. The high molecular weight polymer obtained by this method can be advantageously used as an adhesive, a molding material, an aggregating agent, or a dispersant by taking advantage of its excellent performance.
本発明で対象とする原料のラジカル重合性ビニル単量体
としては、ラジカル重合性を有しているものであれば何
んでも用いることが出来る。このような単量体の例とし
ては１例えば、（メタ）アクリル酸オクチル〔（メタ）
アクリル酸メチルとはメタアクリル酸メチル又はアクリ
ル酸メチルのこと金いう。以下同様。〕、（メタ）アク
リル酸エチル、（メタ）アクリ／Ｉ／酸ｎ−プロピル、
（メタ）アクリル酸インプロピル、（メタ）アクリル酸
グリシジルエステルなどの低級アルキル（メタ）アクリ
レート；（メタ）アクリル酸イソブチル、（メタ）アク
リル酸イソブチル、（メタ）アクリル酸ｔｅｒｔ−ブチ
ル、（メタ）アクリル酸ｎ−ヘキシル、（メタ）アクリ
ル酸シクロヘキシル、（メタ）アクリル酸２−エチルヘ
キシル、（メタ）アクリル酸オクチル、（メタ）アクリ
ル酸ラウリル、（メタ）アクリル酸ステアリルなどの高
級アルキル（メタ）アクリレート；酢酸ビニル、プロピ
オン酸ビニルなどの低級脂肪酸ビニルエステル；酪酸ビ
ニル、カプロン酸ビニル、２−エチルヘキサンビニル、
ラウリン酸ビニル、ステアリン酸ビニルなどの高級脂肪
酸ビニルエステル；スチレン、ビニルトルエン、ビニル
ピロリドンなどの芳香族ビニル型単量体；（メタ）アク
リルアミド、Ｎ−メチロール（メタ）アクリルアミド、
Ｎ−メトキシメチル（メタ）アクリルアミドなどのアミ
ド基含有ビニル現単量体；（メタ）アクリル酸ヒト四キ
シエチル、（メタ）アクリル酸ヒドロキシプロピル、ア
リルアルコールなどの水酸基含有ビニル型単量体；（メ
タ）アクリル酸、イタコン酸、クロトン酸、フマル酸、
マレイン酸などのカルダン酸基含有ビニル型単量体；ブ
タジェン；塩化ビニル；塩化ビニリデン；（メタ）アク
リロニトリル；フマル酸ジプチル；無水マレイン酸；ド
デシル無水コハク醜；（メタ）アリルグリシジルエーテ
ル；イタコン酸、（メタ）アクリル酸、クロトン酸など
のラジカル重合性不飽和カルボン酸のアルカリ金属塩、
アンモニウム塩、有機アミン塩：スチレンスルホン酸の
ようなスルホン酸基を有するラジカル重合性不飽和単量
体、及びそれらのアルカリ金属塩、アンモニウム塩、有
機アミン塩；２−ヒドロキシ−３−メタクリルオキシプ
ロピルトリメチルアンモニウムクロライドのような（メ
タ）アクリル酸から誘導される第四級アンモニウム塩；
メタアクリル酸ジエチルアミノエステルのような第三級
アミノ基を有するアルコールのメタアクリル酸エステル
、及びそれらの第四級アンモニウム塩；パーフルオロア
ルキル（メタ）アクリレート、パーフルオロアルキレン
（メタ）アクリレート等の含弗素ビニルモノマー等があ
る。As the radically polymerizable vinyl monomer that is the raw material targeted in the present invention, any material can be used as long as it has radical polymerizability. Examples of such monomers include octyl (meth)acrylate [(meth)
Methyl acrylate refers to methyl methacrylate or methyl acrylate. Same below. ], (meth)ethyl acrylate, (meth)acrylic/I/n-propyl acid,
Lower alkyl (meth)acrylates such as inpropyl (meth)acrylate and glycidyl (meth)acrylate; isobutyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, (meth)acrylate; Higher alkyl (meth)acrylates such as n-hexyl acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate. lower fatty acid vinyl esters such as vinyl acetate and vinyl propionate; vinyl butyrate, vinyl caproate, 2-ethylhexane vinyl,
Higher fatty acid vinyl esters such as vinyl laurate and vinyl stearate; Aromatic vinyl monomers such as styrene, vinyltoluene, and vinylpyrrolidone; (meth)acrylamide, N-methylol (meth)acrylamide,
Vinyl monomers containing amide groups such as N-methoxymethyl (meth)acrylamide; Vinyl monomers containing hydroxyl groups such as human tetraxethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and allyl alcohol; ) acrylic acid, itaconic acid, crotonic acid, fumaric acid,
Cardanic acid group-containing vinyl monomers such as maleic acid; butadiene; vinyl chloride; vinylidene chloride; (meth)acrylonitrile; diptyl fumarate; maleic anhydride; dodecyl succinic anhydride; (meth)allyl glycidyl ether; itaconic acid, Alkali metal salts of radically polymerizable unsaturated carboxylic acids such as (meth)acrylic acid and crotonic acid,
Ammonium salts, organic amine salts: radically polymerizable unsaturated monomers having sulfonic acid groups such as styrene sulfonic acid, and their alkali metal salts, ammonium salts, organic amine salts; 2-hydroxy-3-methacryloxypropyl Quaternary ammonium salts derived from (meth)acrylic acid, such as trimethylammonium chloride;
Methacrylic esters of alcohols having a tertiary amino group such as diethylamino methacrylic ester, and quaternary ammonium salts thereof; fluorine-containing materials such as perfluoroalkyl (meth)acrylates and perfluoroalkylene (meth)acrylates There are vinyl monomers, etc.
また、本発明にいうＭｗｌＯＯ万以上の高分子量重合体
を得るためには、原料のビニル単量体として高純度のも
のを用いることが望ましく、通常９９．９憾以上、好ま
しくは、９９．９９憾以上のものを使用するのが適当で
ある。この高純度の原料単量体は通常蒸留によシ得られ
る。In addition, in order to obtain a high molecular weight polymer having a molecular weight of 10,000 or more, it is desirable to use a high-purity vinyl monomer as a raw material, usually 99.9 or more, preferably 99.99 or more. It is appropriate to use something more than regrettable. This highly pure raw material monomer is usually obtained by distillation.
なお、本発明の製造法によれば、ホモ重合体のみならず
、原料として二種類以上のビニル単量体を用いれば、ラ
ンダム共重合体も容易に製造し得る。According to the production method of the present invention, not only a homopolymer but also a random copolymer can be easily produced by using two or more types of vinyl monomers as raw materials.
重合開始剤
本発明の高分子量重合体の製造に用いられる前記の一般
式で表わされるジチオカーバメート基（官能基）？：有
する開始剤としては、前記のように官能基を１個有する
単官能開始剤が使用できるし、官能基を２個又はそれ以
上有する二官能又は多官能開始剤も使用できる。Polymerization initiator A dithiocarbamate group (functional group) represented by the above general formula used in the production of the high molecular weight polymer of the present invention? As the initiator, a monofunctional initiator having one functional group as described above can be used, and a difunctional or polyfunctional initiator having two or more functional groups can also be used.
その使用できる単官能開始剤としては、一般式〔式中、
Ｘは有機基であシ、Ｒ１及びＲ２は前記の一般式（１）
におけるＲ及びＲとそれぞれ同じである。〕
で表わされる化合物があげられる。そして、その有機基
Ｘは、飽和又は不飽和の炭化水素基であってもよいし、
カルがニル基やエステル基やエーテル基等を含む炭化水
素基であっても差支えがない。The monofunctional initiator that can be used includes the general formula [wherein,
X is an organic group, R1 and R2 are the above general formula (1)
are the same as R and R, respectively. ] Examples include compounds represented by the following. The organic group X may be a saturated or unsaturated hydrocarbon group,
There is no problem even if Cal is a hydrocarbon group including a nyl group, an ester group, an ether group, or the like.
前記一般式（Ｉｔ）で表わされる単官能開始剤の具体例
としては、たとえば下記の化合物があげられる。Specific examples of the monofunctional initiator represented by the general formula (It) include the following compounds.
（ｉ−ブチルＮ、Ｎ−ゾメチルジチオカーパメート）（
ベンジルジチオカーバメート）
（ベンジルＮ−メチルジチオカーバメート）（ヘンシル
Ｎ、Ｎ−ゾメチルジチオヵーパメート）（ベンジルＮ−
エチルジチオカーバメート）（ベンジルＮ、Ｎ−ジエチ
ルジチオカーバメート）また、使用できる多官能開始剤
としては、一般式
〔式中、ｎは１〜４の整数、Ｒ１及びＲ２は前記一般式
（りにおけるＲ及びＲとそれぞれ同じである。〕で表わ
される化合物、及び一般式
〔式中、Ｙは有機基であシ、Ｒ１及びＲ２は前記一般式
（１）におけるＲ１及びＲ２とそれぞれ同じであり、ｍ
は２〜４０の整数である。〕
で表わされる化合物があげられる。(i-Butyl N, N-zomethyldithiocarpamate) (
(benzyl N-methyldithiocarbamate) (benzyl N, N-zomethyldithiocarbamate) (benzyl N-
(ethyl dithiocarbamate) (benzyl N, N-diethyldithiocarbamate) In addition, the polyfunctional initiator that can be used includes the general formula [where n is an integer of 1 to 4, R1 and R2 are R and R are the same as each other, and compounds represented by the general formula [wherein, Y is an organic group, R1 and R2 are the same as R1 and R2 in the general formula (1), and m
is an integer from 2 to 40. ] Examples include compounds represented by the following.
そして、前記一般式（２）で表わされる化合物の具体例
としては、下記の化合物があげられる。Specific examples of the compound represented by the general formula (2) include the following compounds.
（チウラムジスルフィド）
（Ｎ、Ｎ’−ジメチルチウラムジスルフィド）（Ｎ、Ｎ
、Ｎ’、Ｎ’−テトラメチルチク２ムシスルフイｒ）（
Ｎ、Ｎ’ −ｒエチルチクラムジスルフィド）（Ｎ、Ｎ
、Ｎ’、Ｎ’−テトラエチルチウラムジスルフィド）（
ｋ、Ｎ、Ｎ’、Ｎ’−テトラエチルチウラムモノスルフ
ィド）（Ｎ、Ｎ、Ｎ’、Ｎ’−テトラエチルチウラムテ
トラスルフィド）また、前記一般式（財）で表わされる
化合物の具体例としては、下記の化合物があけられる。(thiuram disulfide) (N,N'-dimethylthiuram disulfide) (N,N
, N', N'-tetramethylthiku2mucisulfur) (
N, N' -r ethyl thiclam disulfide) (N, N
, N', N'-tetraethylthiuram disulfide) (
k,N,N',N'-tetraethylthiuram monosulfide) (N,N,N',N'-tetraethylthiuram tetrasulfide) Also, specific examples of the compound represented by the general formula (goods) are as follows: compound can be opened.
［ｐ−キシレンビス（ジチオカーバメート）〕〕Ｃｐ−
キシレンビスＮ−メチルジチオカーノ々メート）〕（〕
ｐ−キシレンビスＮ、Ｎ−ジエチルジチオカーバメート
）：］（］ｐ−キシレンビスＮ、Ｎ−ジエチルジチオカ
ーバメート）〕（〕１．２−ビスＮ、Ｎ−ジエチルジチ
オカー９ぐミル）エタン〕（１，２−ビス（Ｎ、Ｎ−ジ
エチルジチオカーパミル）エタン〕（１，２，３−トリ
＜Ｎ、Ｎ−ジエチルジチオカーバミル）７６０パン〕ベ
ンゼン〕
又ジチオカーバメート金属塩を利用でき一般式〔式中、
Ｍは１価〜４価のアルカリ金属するいはアルカリ土類金
属あるいは遷移金属であ＃）ｔ−１〜４であシ、Ｒ及び
Ｒは前記一般式（１）にシけるＲ１及びＲとそれぞれ同
じである〕
で表わされる化合物があけられる。[p-xylene bis(dithiocarbamate)]]Cp-
xylene bis N-methyldithiocaranomate)〕(〕
p-xylenebisN,N-diethyldithiocarbamate):](]p-xylenebisN,N-diethyldithiocarbamate)](]1.2-bisN,N-diethyldithiocar9gumyl)ethane]( 1,2-bis(N,N-diethyldithiocarpamyl)ethane](1,2,3-tri<N,N-diethyldithiocarbamyl)760pan]benzene] Also, dithiocarbamate metal salts can be used and general formula [in the formula,
M is a monovalent to tetravalent alkali metal, alkaline earth metal, or transition metal; R and R are R1 and R in the general formula (1); Each is the same] Compounds represented by the following are opened.
前記一般式（Ｖ）で表わされるジチオカーバメート金属
塩の具体例としては、たとえば下記の化合物があげられ
る。Specific examples of the dithiocarbamate metal salt represented by the general formula (V) include the following compounds.
（Ｎ、Ｎ−ジエチルジチオカルバミン酸ナトリウム）（
Ｎ、Ｎ−ジエチルジチオカルバミン酸亜鉛）（Ｎ、Ｎ−
ジメチルジチオカルバミン酸第二鉄）ま九、本発明のジ
チオカーバメート基を有する重合開始剤は、本発明のラ
ジカル重合性ビニル単量体１００重量部に対して１通常
０．００１〜０．５重量部、好ましくはｏ、ｏｏｓ〜０
．１重量部、特に好ましくは０．０１〜０．０５重量部
用いるのが適当である。(N,N-sodium diethyldithiocarbamate) (
Zinc N,N-diethyldithiocarbamate) (N,N-
(ferric dimethyldithiocarbamate) The polymerization initiator having a dithiocarbamate group of the present invention is usually 0.001 to 0.5 parts by weight per 100 parts by weight of the radically polymerizable vinyl monomer of the present invention. , preferably o, oos~0
．． It is appropriate to use 1 part by weight, particularly preferably 0.01 to 0.05 part by weight.
なお、本発明で使用するジチオカーバメート基を有する
開始剤は、一般に、工業用に製造されている試薬をその
まま用いるか又はジチオカルバミン酸ナトリウムと対応
する有機ハロゲン化物とを反応させることによって収率
よ〈合成することができる。たとえば、ｐ−キジレンジ
ブロマイドとＮ、Ｎ−ジエチルジチオカルバミン酸ナト
リウムとを反応させれば、ｐ−１シレンビス（Ｎ、Ｎ−
ジエチルジチオカーバメート）が得られる。The initiator having a dithiocarbamate group used in the present invention is generally used as an industrially produced reagent as it is, or by reacting sodium dithiocarbamate with a corresponding organic halide to improve the yield. Can be synthesized. For example, if p-quizylene dibromide and sodium N,N-diethyldithiocarbamate are reacted, p-1 silene bis(N,N-
diethyldithiocarbamate) is obtained.
光照射
本発明による高分子量重合体の製造は、単量体中に添加
され次ジチオカーバメート基を有する重合開始剤に加熱
又は紫外線を照射することによシ活性化せしめ、単量体
の重合を開始せしめることによシ行われる。特に、紫外
線照射によって重合開始させるのが望ましく、この時の
紫外線照射は、通常の紫外線ランプを用いればよく、照
射強度、照射時間等は用いる単量体及び重合開始剤の種
類によシ異なりて来るが、一般的には紫外線としては、
３００〜４００ ｎｍの範囲が好ましく、紫外線ランプ
としては、ｌＯ〜２００ ｗ／ｃＷＬ、好ましくは３０
〜１２０ Ｗ／ｃＩＬ、照射時間０．５〜２０時間、ラ
ング−反応物間隔５〜１００ｃｆＩＬである。又、反応
温度は通常−２０〜７０℃であるが、好ましくは２０〜
５０℃である。Light irradiation In the production of high molecular weight polymers according to the present invention, a polymerization initiator having a dithiocarbamate group added to the monomers is activated by heating or irradiating with ultraviolet rays to initiate polymerization of the monomers. This is done by starting the process. In particular, it is desirable to initiate polymerization by irradiation with ultraviolet rays, and a normal ultraviolet lamp may be used for irradiating ultraviolet rays, and the irradiation intensity, irradiation time, etc. will vary depending on the type of monomer and polymerization initiator used. However, in general, as ultraviolet rays,
The range of 300 to 400 nm is preferable, and as an ultraviolet lamp, the range of 1O to 200 w/cWL, preferably 30
~120 W/cIL, irradiation time 0.5-20 hours, Lang-reactant spacing 5-100 cfIL. Further, the reaction temperature is usually -20 to 70°C, preferably 20 to 70°C.
The temperature is 50°C.
なお、平均分子量の制御は、原料のビニル単量体の純度
、重合開始剤の種類と量、紫外線の照射強度と照射時間
及び重合温度によシ行なうことが出来る。そして、°重
合によシ得られた高分子量重合体は例えば一旦溶剤に溶
解し、未反応モノマー及び重合開始剤を除去することに
よシ容易に精製することが出来る。The average molecular weight can be controlled by controlling the purity of the raw vinyl monomer, the type and amount of the polymerization initiator, the intensity and time of ultraviolet ray irradiation, and the polymerization temperature. The high molecular weight polymer obtained by polymerization can be easily purified, for example, by once dissolving it in a solvent and removing unreacted monomers and polymerization initiators.
本発明の方法によシ得られた重合体の構造は。The structure of the polymer obtained by the method of the present invention is as follows.
用いる開始剤の構造によって異なる。即ち、１分子中に
ジチオカーバメート基を１個含有する開始剤を用いれ場
合、片末端にジチオカーバメート基含有する直鎖状の重
合体が得られ、１分子中にジチオカーバメート基２個含
有する開始剤を用いた場合１両末端にジチオカーバメー
ト基を有する直鎖状の重合体が得られ、更に１分子中に
ジチオカーバメート基３個あるいは４個含有する開始剤
を用いた場合、各末端にジチオカーバメート基を有する
星型の重合体が得られる。It depends on the structure of the initiator used. That is, when an initiator containing one dithiocarbamate group in one molecule is used, a linear polymer containing a dithiocarbamate group at one end is obtained, and an initiator containing two dithiocarbamate groups in one molecule is obtained. When an initiator is used, a linear polymer having dithiocarbamate groups at both ends is obtained, and when an initiator containing three or four dithiocarbamate groups in one molecule is used, a dithiocarbamate group is obtained at each end. A star-shaped polymer with carbamate groups is obtained.
いずれの重合体も繰返し単位は用いた単量体の繰返し単
位となる。In either polymer, the repeating unit is that of the monomer used.
そして、得られ比重合体は、殆んど分岐もなく、その重
合度は平均して、１０．０００〜Ｚｏｏ、０００程度の
ものである。The specific polymer obtained has almost no branching and has an average degree of polymerization of about 10,000 to Zoo,000.
（実施例等）
以下に実施例及び比較例をあげてさらに詳述すゐが、本
発明はこれらの例によって限定されるものではない。(Examples, etc.) The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
実施例１゜
構造式
で表わされるｐ−キシレンビス（Ｎ、Ｎ−ジエチルジチ
オカーバメート）（以下、単に「ＸＤＣ」と略称する）
０．１０Ｉｔ−メタクリル酸メチル５′００ｇに完全に
溶解させてｉ４イレックスガラス製の１１容器に入れ、
容器内の残存気体を充分にＮ−置換した後密栓し、４０
０Ｗの紫外線ランプ（東芝■製Ｈ４００Ｌ水銀ランプ）
から１５ｃｍ離れた位置に置いて約１５時間紫外線照射
した。その照射後１ｓｏｏｙのトルエンに溶解させたと
ころ完全に溶解し、グル分はなかりた。かかる重合体ト
ルエン溶液を約ｌＯ１のへキサンにて再沈精製をし、沈
でん物Ｑ１００℃にて１２時間減圧乾燥させ九ところ生
成物の収量は４６１１１であシ、ｒルミ４−ミエーシ、
ンクロマトグラフィ（ＧＰＣ）によるポリスチレン換算
の数平均分子ｉｔ （Ｍｎ）は２，３１０，０００であ
シ、同重量平均分子量（Ｍｙ ）は４．７３０．０００
でありた。Example 1 p-xylene bis(N,N-diethyldithiocarbamate) represented by the structural formula (hereinafter simply abbreviated as "XDC")
Completely dissolve in 5'00g of 0.10It-methyl methacrylate and place in 11 containers made of i4 Ilex glass.
After sufficiently replacing the remaining gas in the container with N, the container was tightly capped and heated for 40 minutes.
0W ultraviolet lamp (Toshiba H400L mercury lamp)
It was placed 15 cm away from the surface and irradiated with ultraviolet rays for about 15 hours. After the irradiation, when it was dissolved in 1 sooy of toluene, it was completely dissolved and there was no glue component. The toluene solution of the polymer was purified by reprecipitation with about 101 hexane, and the precipitate was dried under reduced pressure at 100°C for 12 hours.The yield of the product was 46111, rlumi4-mie,
The number average molecular weight (Mn) in terms of polystyrene determined by chromatography (GPC) is 2,310,000, and the weight average molecular weight (My) is 4.730.000.
It was.
実施例２゜
実施例１のメタクリル酸メチル５ｏｏＩＩの代シにスチ
レン５００ＩＩ？用いる以外は実施例１と同じ条件で重
合を行ない更に同じ条件でトルエンに溶解させ友ところ
完全に溶解しｒル分はなかった。Example 2 Styrene 500II instead of methyl methacrylate 5ooII in Example 1? Polymerization was carried out under the same conditions as in Example 1 except for the use of the polymer, and the polymer was further dissolved in toluene under the same conditions.However, it was completely dissolved and there was no trace amount.
又、同じ条件でヘキサンにて再沈精製乾燥したところ収
量は４５７１１であＦ） Ｍｎは２，４５０，０００で
あり、ＭｗＦｉ５，１００，０００であった。Further, when the product was reprecipitated and purified and dried in hexane under the same conditions, the yield was 45,711, Mn was 2,450,000, and MwFi was 5,100,000.
実施例３゜
実施例１のメタクリル酸メチル５００ｇの代シにアクリ
ル酸メチル５ｏｏｙｖ用いる以外は実施例１と同じ条件
で重合を行ない、更に同じ条件でトルエンに溶解させた
ところ完全に溶解しｒル分はなかった。又、同じ条件で
ヘキサンにて再沈精製乾燥したところ収量は４６３９で
あυＭｎは２、３８０．０００であシ、Ｍｙは４，７０
０．ＯＯＯでありｆｔ。Example 3 Polymerization was carried out under the same conditions as in Example 1, except that 500 g of methyl acrylate was used in place of 500 g of methyl methacrylate in Example 1. Furthermore, when it was dissolved in toluene under the same conditions, it was completely dissolved. There was no time. In addition, when reprecipitation purification and drying was performed with hexane under the same conditions, the yield was 4639, υMn was 2,380.000, and My was 4,70.
0. OOO and ft.
実施例４゜
実施例１のメタクリル酸メチル５００Ｉの代シに酢酸ビ
ニル５ｏｏｙｉ用いる以外は実施例１と同じ条件で重合
を行ない、更に同じ条件でトルエンに溶解させたところ
完全に溶解しグル分はなかった。又、同じ条件でヘキサ
ンにて再沈精製乾燥したところ収量は４７０ｇであｌ）
Ｍｎは２，４７０．ＯＯＯであり Ｍｙは４，８００
，０００でラッ友。Example 4 Polymerization was carried out under the same conditions as in Example 1 except that vinyl acetate 5ooyi was used in place of methyl methacrylate 500I in Example 1, and when it was dissolved in toluene under the same conditions, it was completely dissolved and the glue content was There wasn't. In addition, when reprecipitation purification and drying was carried out with hexane under the same conditions, the yield was 470 g.
Mn is 2,470. OOO and My is 4,800
,000 is my friend.
実施例５゜
実施例１のＸＤＣ０，１、Ｆの代シに構造式で表わされ
るベンジル）Ｉ、Ｎ−ジエチルジチオカーパメー）０．
０６０．Ｆｔ−用いる以外は実施例１と同じ条件で重合
を行ない、更に同じ条件でトルエンに溶解させたととる
完全に溶解してダル分はなかりた。又、同じ条件でヘキ
サンにて再沈精製乾燥したところ、収量は４５５ｇであ
シＭｎは２，４１０，０００であシ、Ｍｙは４，９３０
．ＯＯＯであった。Example 5 Benzyl)I,N-diethyldithiocarpame)0.
060. Polymerization was carried out under the same conditions as in Example 1 except that Ft was used, and furthermore, it was dissolved in toluene under the same conditions.It was completely dissolved and there was no dull content. In addition, when reprecipitation purification and drying was performed with hexane under the same conditions, the yield was 455 g, Mn was 2,410,000, and My was 4,930.
．． It was OOO.
実施例６゜
実施例１のＸＤＣ０，１１００代シに構造式で表わされ
るＮ、Ｎ、Ｎ’、Ｎ’−テトラエチルチウラムジスルフ
ィドを０．０７４．９を用いる以外は実施例１と同一の
条件で重合を行ない、更に同じ条件でトルエンに溶解さ
せ九ところ完全に溶解しｒル分はなかりた。又、同じ条
件でヘキサンにて再沈精製乾燥したところ、収量は４５
１１１であシＭｎは２．４９０，０００であシＭｙは４
，９７０．０００であった。Example 6゜N,N,N',N'-tetraethylthiuram disulfide represented by the structural formula in XDC0,1100 of Example 1 was used under the same conditions as Example 1 except that 0.074.9 was used. Polymerization was carried out, and the polymer was further dissolved in toluene under the same conditions, and completely dissolved in 90 minutes, with no traces remaining. In addition, when reprecipitation purification and drying was carried out with hexane under the same conditions, the yield was 45
111 and Mn is 2.490,000 and My is 4
,970.000.
実施例７゜
実施例１のＸＤＣ０，１Ｎの代シに構造式で表わされる
ナトリウムＮ、Ｎ−ジエチルジチオカーバメート０．０
４３＃ｔ−用いる以外は実施例１と同じ条件で重合を行
ない、更に同じ条件でトルエンに溶解させ友ところ完全
に溶解してグル分はなかった。又、同じ条件でヘキサン
にて再沈精製乾燥したところ収量は４５１ｙであ＃）Ｍ
ｎは２．３８０，０００であＦ） Ｍｗは４，６７０，
０００であった。Example 7 Sodium N,N-diethyldithiocarbamate 0.0 represented by the structural formula in place of XDC0,1N in Example 1
Polymerization was carried out under the same conditions as in Example 1, except that 43#t- was used, and the polymer was further dissolved in toluene under the same conditions.It was completely dissolved and no glue was present. In addition, when reprecipitation purification and drying was carried out with hexane under the same conditions, the yield was 451y.
n is 2.380,000 and F) Mw is 4,670,
It was 000.
比較例１゜
実施例１のＸＤＣＯ，１１／の代わシにベンゾイルパー
オキサイド０．１ｇを用いる以外は実施例１と同じ条件
で重合を行表い、更に同じ条件でトルエンに溶解させた
ところ、一部ｒル分が生じ完全に溶解しなかつ友。更に
、ｒル分を含んだまま同じ条件でヘキサンにて再沈精製
乾燥し九ところ収量は３４７ｇであシネ溶分が多い為Ｇ
ＰＣ測定はできなかつ九。Comparative Example 1゜ Polymerization was carried out under the same conditions as in Example 1, except that 0.1 g of benzoyl peroxide was used in place of XDCO, 11/ in Example 1, and when it was further dissolved in toluene under the same conditions, Some liquid may be present and not completely dissolved. Furthermore, the product was reprecipitated and purified and dried in hexane under the same conditions while containing the r-ole content.The yield was 347 g, and the G
PC measurement is not possible.
、出願人 三菱油化株式会社, Applicant Mitsubishi Yuka Co., Ltd.
Claims (1)
〜１００アルキル基を示す。） で表わされるジチオカーバメート基を有する重合開始剤
を用いてラジカル重合性ビニル単量体を光により塊状重
合させることにより重量平均分子量１００万以上の高分
子量重合体を製造することを特徴とする高分子量重合体
の製造法。(1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^1 and R^2 are each hydrogen or carbon number 1
~100 represents an alkyl group. ) A high molecular weight polymer having a weight average molecular weight of 1 million or more is produced by bulk polymerizing a radically polymerizable vinyl monomer with light using a polymerization initiator having a dithiocarbamate group represented by Method for producing molecular weight polymers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11418887A JPS63278910A (en) | 1987-05-11 | 1987-05-11 | Manufacture of high-molecular weight polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11418887A JPS63278910A (en) | 1987-05-11 | 1987-05-11 | Manufacture of high-molecular weight polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63278910A true JPS63278910A (en) | 1988-11-16 |
Family
ID=14631402
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11418887A Pending JPS63278910A (en) | 1987-05-11 | 1987-05-11 | Manufacture of high-molecular weight polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63278910A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0466149A1 (en) | 1990-07-12 | 1992-01-15 | Canon Kabushiki Kaisha | Toner, developer, and image forming method |
| US5217760A (en) * | 1990-07-20 | 1993-06-08 | Loctite Corporation | Free radically curable formulations employing dithiolate catalysts |
| US5318999A (en) * | 1989-12-21 | 1994-06-07 | Minnesota Mining And Manufacturing Company | Dental compositions prepared by polymeric photoiniferter polymerization of the dental compositions and shaped dental articles produced thereby |
| KR20020031741A (en) * | 2000-10-23 | 2002-05-03 | 유응렬 | A Novel Radical Initiator for Heterogeneous Phase Polymerization |
| WO2006044910A1 (en) * | 2001-08-02 | 2006-04-27 | Johnson & Johnson Vision Care, Inc. | Process for the synthesis of soluble, high molecular weight polymers |
| WO2008117772A1 (en) * | 2007-03-26 | 2008-10-02 | Nissan Chemical Industries, Ltd. | Curable material containing photopolymerizable polymer and cured object |
-
1987
- 1987-05-11 JP JP11418887A patent/JPS63278910A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5318999A (en) * | 1989-12-21 | 1994-06-07 | Minnesota Mining And Manufacturing Company | Dental compositions prepared by polymeric photoiniferter polymerization of the dental compositions and shaped dental articles produced thereby |
| EP0466149A1 (en) | 1990-07-12 | 1992-01-15 | Canon Kabushiki Kaisha | Toner, developer, and image forming method |
| US5620824A (en) * | 1990-07-12 | 1997-04-15 | Canon Kabushiki Kaisha | Toner, developer and image forming method |
| US5217760A (en) * | 1990-07-20 | 1993-06-08 | Loctite Corporation | Free radically curable formulations employing dithiolate catalysts |
| US5411995A (en) * | 1990-07-20 | 1995-05-02 | Loctite Corporation | Free radically curable formulations employing dithiolate catalysts |
| KR20020031741A (en) * | 2000-10-23 | 2002-05-03 | 유응렬 | A Novel Radical Initiator for Heterogeneous Phase Polymerization |
| WO2006044910A1 (en) * | 2001-08-02 | 2006-04-27 | Johnson & Johnson Vision Care, Inc. | Process for the synthesis of soluble, high molecular weight polymers |
| US7485672B2 (en) | 2001-08-02 | 2009-02-03 | Johnson & Johnson Vision Care, Inc. | Process for the synthesis of soluble, high molecular weight polymers |
| WO2008117772A1 (en) * | 2007-03-26 | 2008-10-02 | Nissan Chemical Industries, Ltd. | Curable material containing photopolymerizable polymer and cured object |
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