JPH01108209A - Manufacture of graft polymer - Google Patents
Manufacture of graft polymerInfo
- Publication number
- JPH01108209A JPH01108209A JP26540387A JP26540387A JPH01108209A JP H01108209 A JPH01108209 A JP H01108209A JP 26540387 A JP26540387 A JP 26540387A JP 26540387 A JP26540387 A JP 26540387A JP H01108209 A JPH01108209 A JP H01108209A
- Authority
- JP
- Japan
- Prior art keywords
- vinyl
- macromonomer
- polymerization
- monomer
- graft polymer
- 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
- 229920000578 graft copolymer Polymers 0.000 title claims abstract description 57
- 238000004519 manufacturing process Methods 0.000 title claims description 29
- 239000000178 monomer Substances 0.000 claims abstract description 40
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 34
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 26
- 238000010557 suspension polymerization reaction Methods 0.000 claims abstract description 15
- 239000007900 aqueous suspension Substances 0.000 claims abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 21
- 229920000642 polymer Polymers 0.000 abstract description 16
- -1 vinyl aromatic compound Chemical class 0.000 abstract description 14
- 125000000524 functional group Chemical group 0.000 abstract description 4
- 150000008065 acid anhydrides Chemical class 0.000 abstract description 3
- 150000004820 halides Chemical class 0.000 abstract description 3
- 150000007524 organic acids Chemical class 0.000 abstract description 3
- 229920001567 vinyl ester resin Polymers 0.000 abstract description 3
- 238000012644 addition polymerization Methods 0.000 abstract description 2
- 125000002348 vinylic group Chemical group 0.000 abstract 1
- 238000000034 method Methods 0.000 description 22
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000004793 Polystyrene Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 229920002223 polystyrene Polymers 0.000 description 9
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 description 6
- 239000002270 dispersing agent Substances 0.000 description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 description 6
- 239000003999 initiator Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 238000012690 ionic polymerization Methods 0.000 description 4
- 125000005395 methacrylic acid group Chemical group 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical group SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 229920000609 methyl cellulose Polymers 0.000 description 3
- 239000001923 methylcellulose Substances 0.000 description 3
- 235000010981 methylcellulose Nutrition 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 2
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 2
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical compound CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 2
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- IVRFYNSETZKRSJ-UHFFFAOYSA-N ClC=C.N#CC=CC=CC1=CC=CC=C1 Chemical compound ClC=C.N#CC=CC=CC1=CC=CC=C1 IVRFYNSETZKRSJ-UHFFFAOYSA-N 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 102100020870 La-related protein 6 Human genes 0.000 description 2
- 108050008265 La-related protein 6 Proteins 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 101100490446 Penicillium chrysogenum PCBAB gene Proteins 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- DZMJPYGBKWJZIR-UHFFFAOYSA-N chloroethene;styrene Chemical compound ClC=C.C=CC1=CC=CC=C1 DZMJPYGBKWJZIR-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- KKLSEIIDJBCSRK-UHFFFAOYSA-N 1-(chloromethyl)-2-ethenylbenzene Chemical compound ClCC1=CC=CC=C1C=C KKLSEIIDJBCSRK-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
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 1
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 1
- 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
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- MXRGSJAOLKBZLU-UHFFFAOYSA-N 3-ethenylazepan-2-one Chemical compound C=CC1CCCCNC1=O MXRGSJAOLKBZLU-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-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
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 206010008428 Chemical poisoning Diseases 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-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
- 241000978776 Senegalia senegal Species 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- WYGWHHGCAGTUCH-ISLYRVAYSA-N V-65 Substances CC(C)CC(C)(C#N)\N=N\C(C)(C#N)CC(C)C WYGWHHGCAGTUCH-ISLYRVAYSA-N 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000000560 biocompatible material Substances 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003093 cationic surfactant Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- JXCHMDATRWUOAP-UHFFFAOYSA-N diisocyanatomethylbenzene Chemical compound O=C=NC(N=C=O)C1=CC=CC=C1 JXCHMDATRWUOAP-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 1
- 229940043264 dodecyl sulfate Drugs 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000012156 elution solvent Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Chemical class 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 229940067741 sodium octyl sulfate Drugs 0.000 description 1
- WFRKJMRGXGWHBM-UHFFFAOYSA-M sodium;octyl sulfate Chemical compound [Na+].CCCCCCCCOS([O-])(=O)=O WFRKJMRGXGWHBM-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 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
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
Abstract
Description
【発明の詳細な説明】
（イ）発明の目的
〔産業上の利用分野〕
本発明は高分子材料の機能化の為の有力な手段となるグ
ラフトポリマーの製造方法に関し、近年学問的にも工業
的にも注目されているマクロモノマーを用いたグラフト
ポリマーの製造を、工業的に有利な懸濁重合法によって
行わんとするものである０本発明のグラフトポリマーは
、塗料、接着剤、成形材料等の高分子材料として、また
これら高分子材料の改質剤として有用である。Detailed Description of the Invention (a) Purpose of the Invention [Field of Industrial Application] The present invention relates to a method for producing a graft polymer, which is an effective means for functionalizing polymeric materials. The present invention aims to manufacture graft polymers using macromonomers, which are attracting much attention, by an industrially advantageous suspension polymerization method. It is useful as a polymeric material such as, and as a modifier for these polymeric materials.
高分子材料の機能化にブロックポリマーやグラフトポリ
マーを利用する試みはかなり以前からなされていたが、
イオン重合によるブロックポリマーは製造上の制約が多
い為、機能性高分子の発展にはグラフトポリマーの進歩
が要望されていた。Attempts to use block polymers and graft polymers to functionalize polymeric materials have been made for quite some time;
Since block polymers produced by ionic polymerization have many manufacturing constraints, advances in graft polymers have been required for the development of functional polymers.
グラフトポリマーは通常放射線や過酸化物によるラジカ
ル重合開始法が行われているが、これらの方法では、ｉ
）技及び幹成分のホモポリマーの含有量が多い、１１）
技幹両成分の分子量、組成のコントロールが困難である
、およびｉｉｉ ）枝成分と幹成分の組み合わせが限定
される等の問題点がある。 構造の明確に規制されたグ
ラフトポリマーの製造法として、Ｍｉｌｋｏｖｉｃｈら
の研究によるマクロモノマーを使用する方法が提案され
た。マクロモノマーとは分子末端に重合性官能基を有す
るオリゴマーまたはポリマーを意味し、Ｍａｃｒｏｍｏ
ｌｅｃｕｒｅＭｏｎｏｍｅｒの略である。彼等の方法は
、スチレン、α−メチルスチレン、ブタジェン、イソプ
レン等の単量体からなるリビングポリマーアニオンに塩
化アリル、エピクロルヒドリン、メタクリル酸りロリド
等を作用させて、様々な末端重合性基例えばアリル基、
スチリル基、メタクリロイルオキシ基或いはグリシジル
基等の重合性基を有するマクロモノマーを合成している
（特公昭５０−１１６５８６ 号公報）。Graft polymers are usually produced by radical polymerization initiation using radiation or peroxide, but these methods
) High content of homopolymer of technique and main component, 11)
There are problems such as it is difficult to control the molecular weight and composition of both the main and technical components, and iii) combinations of the branch and main components are limited. As a method for producing a graft polymer with a clearly regulated structure, a method using macromonomers was proposed according to research by Milkovich et al. Macromonomer means an oligomer or polymer having a polymerizable functional group at the end of the molecule.
It is an abbreviation for lecure Monomer. In their method, living polymer anions made of monomers such as styrene, α-methylstyrene, butadiene, and isoprene are reacted with allyl chloride, epichlorohydrin, methacrylic acid chloride, etc. to form various terminal polymerizable groups such as allyl. base,
A macromonomer having a polymerizable group such as a styryl group, a methacryloyloxy group, or a glycidyl group has been synthesized (Japanese Patent Publication No. 116586/1986).
マクロモノマーが工業的に重要視されたのは、英国ＩＣ
Ｉ社におけるハイソリッドペイント製造の分散剤として
の研究以後である。典型的には連鎖移動剤としてメルカ
プト酢酸の存在下にメチルメタクリレート等のラジカル
重合性モノマーを重合させて末端カルボン酸型のオリゴ
マーを得、メタクリル酸グリシジル（以下ＧＭＡと略記
する）でマクロモノマー化する（特公昭４３−１１２２
４号公報、特公昭４３−１６１４７号公報等）、このＩ
ＣＩの方法と同列な方法として、メルカプトエタノール
の存在下に重合して得られた末端水酸基型オリゴマーと
トルイレンジイソシアナートとを反応させた後、メタク
リル酸ヒドロキシエチルでマクロモノマー化するＤｕ
Ｆｏｎｔの方法がある。Macromonomers were given industrial importance in the British IC.
This was after research at Company I as a dispersant for the production of high-solid paints. Typically, a radically polymerizable monomer such as methyl methacrylate is polymerized in the presence of mercaptoacetic acid as a chain transfer agent to obtain a terminal carboxylic acid type oligomer, which is then macromonomerized with glycidyl methacrylate (hereinafter abbreviated as GMA). (Tokuko Sho 43-1122
4 Publication, Special Publication No. 43-16147, etc.), this I
As a method similar to the CI method, a hydroxyl-terminated oligomer obtained by polymerization in the presence of mercaptoethanol is reacted with toluylene diisocyanate, and then macromonomerized with hydroxyethyl methacrylate.
There is a font method.
我が国においては近年白下らの精力的な研究がなされ、
ここ数年の間に一般的な関心も非常に高まった。彼等は
上述したＭｉｌｋｏｖｉｃｈのイオン重合法やＩＣＩの
ラジカル重合法によって合成したマクロモノマーを用い
て様々なグラフトポリマーを合成し、高分子材料の表面
改質に応用した。彼等の研究によって、構造の明確に規
制されたグラフトポリマーが簡便に製造できること、こ
のグラフトポリマーが高分子材料の表面改質に優れた効
果を発揮すること等の点が明らかとなった（特開昭５７
−１９２４６号公報、Ｍａｃｒｏｍｏｌｅｃｕｌｅ １
３，２１６（１９８０）等）。In Japan, energetic research has been conducted in recent years by Shirashita et al.
Public interest has also increased significantly over the past few years. They synthesized various graft polymers using macromonomers synthesized by the above-mentioned Milkovich ionic polymerization method and ICI radical polymerization method, and applied them to surface modification of polymeric materials. Their research revealed that graft polymers with clearly regulated structures can be easily produced, and that these graft polymers exhibit excellent effects on surface modification of polymeric materials (especially 1977
-19246 publication, Macromolecule 1
3,216 (1980), etc.).
以上述べたように、マクロモノマー及びマクロモノマー
を用いたグラフトポリマーの重要性は明らかであり、か
つここ数年の間にそれらの高分子製造業における重要性
は深く認識されるようになってきている。ところが、従
来のグラフトポリマー製造においては、反応系の均一性
保持を主な理由として、有機溶剤を用いた溶液重合によ
る方法が一般的であった。従って製造されたグラフトポ
リマーを固体状で取り出す必要がある場合には、貧溶剤
を使用した沈澱精製法や、乾燥機を用いた有機溶剤の除
去が必要となる。As mentioned above, the importance of macromonomers and graft polymers using macromonomers is clear, and their importance in the polymer manufacturing industry has been deeply recognized over the past few years. There is. However, in the conventional production of graft polymers, solution polymerization using an organic solvent has been commonly used, mainly to maintain the uniformity of the reaction system. Therefore, if it is necessary to take out the produced graft polymer in solid form, it is necessary to use a precipitation purification method using a poor solvent or to remove the organic solvent using a dryer.
しかしながら、上記の方法においては、グラフトポリマ
ー製造時に、火災、有機溶剤中毒等の危険性があったり
、また製造コストが高価であるという問題が存在してい
る。However, in the above method, there are problems that there is a risk of fire, organic solvent poisoning, etc. during the production of the graft polymer, and the production cost is high.
従って、有機溶剤を使用しない方法でグラフトポリマー
の製造ができるならば、工業的な価値は非常に大きい。Therefore, if a graft polymer could be produced by a method that does not use organic solvents, it would be of great industrial value.
（ロ）発明の構成
〔問題点を解決する為の手段〕
本発明者らは、上記のような従来技術の問題点を考慮し
て、工業的に有利なグラフトポリマーの製造法を確立す
ることを目的として鋭意検討した結果、マクロモノマー
とビニル単量体を水性媒体中で懸濁重合させることによ
って、高純度のグラフトポリマーが容易に製造できるこ
とを発見し本発明を完成するに至った。(B) Structure of the Invention [Means for Solving the Problems] The present inventors have established an industrially advantageous method for producing a graft polymer, taking into consideration the problems of the prior art as described above. As a result of extensive research aimed at this purpose, the present invention was completed by discovering that a highly pure graft polymer can be easily produced by suspension polymerizing a macromonomer and a vinyl monomer in an aqueous medium.
即ち、本発明は、ビニル単量体と該ビニル単量体に可溶
性のマクロモノマーとを、水系懸濁重合により共重合さ
せることを特徴とするグラフトポリマーの製造方法であ
る。That is, the present invention is a method for producing a graft polymer, which is characterized by copolymerizing a vinyl monomer and a macromonomer soluble in the vinyl monomer by aqueous suspension polymerization.
以下、本発明について更に詳細に説明する。The present invention will be explained in more detail below.
本発明におけるマクロモノマーとは、分子鎖の片末端に
ビニル付加重合しうる官能基を有する、数平均分子量が
１０００〜２００００程度の比較的低分子量のポリマー
を意味する。The macromonomer in the present invention means a relatively low molecular weight polymer having a number average molecular weight of about 1,000 to 20,000, which has a functional group capable of vinyl addition polymerization at one end of its molecular chain.
本発明におけるマクロモノマーの骨格構造は、ビニル重
合性モノマーの重合体骨格であり、重合の際に使用でき
るモノマーユニットとしては、酢酸ビニルの如き有機酸
のビニルエステル、スチレン、スチレン置換体並びにビ
ニルピリジン、ビニルナフタレンの如きビニル芳香族化
合物、（メタ）アクリル酸エステル、（メタ）アクリロ
ニトリル、アクロレイン、Ｎ−ビニルピローＩ７ドン及
ヒＮ−ビニルカプロラクタムの如きＮ−ビニル化合物、
無水マレイン酸の如き不飽和酸無水物、Ｎ−フェニルマ
レイミドの如きＮ−置換マレイミド、塩化ビニル、塩化
ビニリデンの如き不飽和ハロゲン化物等が使用でき、こ
れらのモノマーは単独で或いは２種類以上共用して共重
合体として使用することができる。The skeleton structure of the macromonomer in the present invention is a polymer skeleton of a vinyl polymerizable monomer, and monomer units that can be used during polymerization include vinyl esters of organic acids such as vinyl acetate, styrene, styrene-substituted products, and vinylpyridine. , vinyl aromatic compounds such as vinylnaphthalene, (meth)acrylic acid esters, (meth)acrylonitrile, acrolein, N-vinyl compounds such as N-vinylpyro I7 and N-vinylcaprolactam,
Unsaturated acid anhydrides such as maleic anhydride, N-substituted maleimides such as N-phenylmaleimide, unsaturated halides such as vinyl chloride and vinylidene chloride, etc. can be used, and these monomers may be used alone or in combination of two or more. It can be used as a copolymer.
好適には、得られたマクロモノマーが水に不溶性となる
ようなモノマーであることが望ましく、スチレン、スチ
レン置換体、（メタ）アクリル酸エステル、（メタ）ア
クリロニトリルが使用される。Preferably, the obtained macromonomer is a monomer that is insoluble in water, and styrene, styrene-substituted products, (meth)acrylic acid esters, and (meth)acrylonitrile are used.
本発明におけるマクロモノマーの分子量は、製造された
マクロモノマーが重合性を損なうことがない範囲であれ
ば良く、分子量としては数平均で１０００〜５００００
であり、好ましくは２０００〜４００００である。分子
量が１０００未満ではポリマー単位としての重合度が低
すぎ、原料として用いたマクロモノマーの物性がグラフ
トポリマーの物性に反映されない為好ましく無く、又５
００００を超えるとグラフトポリマー製造時の重合性が
低下し反応系の相分離を起こし易くなる等の不都合を生
じ易い為好ましくない。The molecular weight of the macromonomer in the present invention may be within a range that does not impair the polymerizability of the produced macromonomer, and the number average molecular weight is 1000 to 50000.
and preferably 2,000 to 40,000. If the molecular weight is less than 1000, the degree of polymerization as a polymer unit is too low, and the physical properties of the macromonomer used as a raw material are not reflected in the physical properties of the graft polymer, which is undesirable.
If it exceeds 0,000, it is not preferable because it tends to cause problems such as a decrease in polymerizability during production of the graft polymer and a tendency to cause phase separation in the reaction system.
上記マクロモノマーの数平均分子量は、ゲルパーミニ−
シランクロマトグラフィ−（以下ＧＰＣという）による
ポリスチレン換算分子量であり、測定条件は次のとおり
である。The number average molecular weight of the above macromonomer is Gel Permini-
It is a polystyrene equivalent molecular weight measured by silane chromatography (hereinafter referred to as GPC), and the measurement conditions are as follows.
装置：高速液体クロマトグラフィー（例えば東洋曹達工
業■製画品名ＨＬＣ−８０２ＵＲ）カラム：ポリスチレ
ンのゲル（例えば東洋曹達工業■製画品名Ｇ４０００Ｈ
８及びＧ３０００）１Ｂ ）溶出溶媒：テトラヒドロフ
ラン（以下ＴＨＦと略記する）
流出速度： １．Ｏｍｌ／ｗｉｎ
カラム温度：４０°Ｃ
検出器：ＲＩ検出器
本発明におけるマクロモノマーの製造法としては、ラジ
カル重合法およびイオン重合法が挙げられる。Equipment: High performance liquid chromatography (e.g. Toyo Soda Kogyo ■Product name HLC-802UR) Column: Polystyrene gel (e.g. Toyo Soda Kogyo ■Product name G4000H
8 and G3000) 1B) Elution solvent: Tetrahydrofuran (hereinafter abbreviated as THF) Outflow rate: 1. Oml/win Column temperature: 40°C Detector: RI detector Methods for producing macromonomers in the present invention include radical polymerization and ionic polymerization.
ラジカル重合法によるマクロモノマーの代表的な製造法
としては、カルボキシル基を有するメルカプタン系連鎖
移動剤の存在下で、ラジカル重合性モノマーをラジカル
重合して、片末端にカルボキシル基を持つポリマー（以
下、プレポリマーと略記する）を得、その後、エポキシ
基を含有するビニル化合物等と反応させる方法が挙げら
れる。A typical method for producing a macromonomer by radical polymerization is to radically polymerize a radically polymerizable monomer in the presence of a mercaptan chain transfer agent having a carboxyl group to form a polymer having a carboxyl group at one end (hereinafter referred to as Examples include a method of obtaining a prepolymer (abbreviated as prepolymer) and then reacting it with a vinyl compound containing an epoxy group.
この際、カルボキシル基を有するメルカプタン系連鎖移
動剤としては、メルカプト酢酸、２−メルカプトプロピ
オン酸、３−メルカプトプロピオン酸等が用いられる。In this case, as the mercaptan chain transfer agent having a carboxyl group, mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, etc. are used.
重合の方法としては、ラジカル重合開始剤の存在下或い
は非存在下で、溶液重合法・バルク重合法・懸濁重合法
・エマルジョン重合法のいずれかを用いることができる
。As the polymerization method, any one of solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization can be used in the presence or absence of a radical polymerization initiator.
この際使用するラジカル重合開始剤としては、通常のア
ゾ系開始剤や過酸化物開始剤が使用できるが、メルカプ
タン化合物との反応を避ける為アゾ系開始剤が好ましい
。アゾ系開始剤としては、２．２−アゾビスイソブチロ
ニトリル（以下ＡＩＢＮと略記する） 、４．４−アゾ
ビス−４−シアノバレリックアシド（以下ＡＣＶＡと略
記する）、１−アゾビス−１−シクロヘキサンカルボニ
トリル（以下ＡＣＨＮと略記する）等が挙げられる。As the radical polymerization initiator used in this case, ordinary azo initiators and peroxide initiators can be used, but azo initiators are preferable in order to avoid reaction with mercaptan compounds. Examples of azo initiators include 2,2-azobisisobutyronitrile (hereinafter abbreviated as AIBN), 4,4-azobis-4-cyanovaleric acid (hereinafter abbreviated as ACVA), 1-azobis-1 -cyclohexanecarbonitrile (hereinafter abbreviated as ACHN) and the like.
プレポリマーと反応させるエポキシ基含有ビニル化合物
としては、グリシジル（メタ）アクリレート、アリルグ
リシジルエーテル、クロルメチルビニルベンゼン等を使
用することができるが、これらはグラフトポリマー製造
時のビニル単量体との共重合性を考慮して選べば良い。As the epoxy group-containing vinyl compound to be reacted with the prepolymer, glycidyl (meth)acrylate, allyl glycidyl ether, chloromethylvinylbenzene, etc. can be used, but these can be used in combination with the vinyl monomer during the production of the graft polymer. It may be selected by considering polymerizability.
プレポリマーとエポキシ基含有ビニル化合物との反応に
おいては、触媒としては、三級アミン、四級アンモニウ
ム塩等を使用出来る。In the reaction between the prepolymer and the epoxy group-containing vinyl compound, tertiary amines, quaternary ammonium salts, etc. can be used as catalysts.
また、イオン重合によってマクロモノマーを得る方法と
しては、ビニル単量体のりピングアニオン重合によって
得たりピングアニオン末端に、リビングアニオンと反応
する官能基を有するビニル化合物、例えば（メタ）アク
リル酸クロリド、塩化アリル、ビニルベンジルクロリド
等を反応させる方法が挙げられる。この際、副反応を押
さえる為リビングアニオンをエチレンオキシド等で処理
した後、上記ビニル化合物と反応させることもできる。In addition, as a method for obtaining a macromonomer by ionic polymerization, it can be obtained by pasting anionic polymerization of a vinyl monomer, or by using a vinyl compound having a functional group that reacts with a living anion at the end of a vinyl monomer, such as (meth)acrylic acid chloride, chloride, etc. Examples include a method of reacting allyl, vinylbenzyl chloride, and the like. At this time, in order to suppress side reactions, the living anion can be treated with ethylene oxide or the like and then reacted with the vinyl compound.
〔マクロモノマー法によるグラフトポリマー〕前記した
マクロモノマーを使用してグラフトポリマーを製造する
方法を、マクロモノマー法と称する。このようなマクロ
モノマー法によるグラフトポリマーの製造法は、
ｉ）技及び幹成分のホモポリマーの含有量が少ない。[Graft polymer by macromonomer method] The method for producing a graft polymer using the above-mentioned macromonomer is called the macromonomer method. The method for producing a graft polymer using such a macromonomer method has the following features: i) The content of the homopolymer of the polymer and the main component is small.
ｉｉ）枝成分の分子量、グラフトポリマー全体の分子量
、技と幹の割合が容易にコントロールできる。ii) The molecular weight of the branch component, the overall molecular weight of the graft polymer, and the ratio of the technique and the trunk can be easily controlled.
ｉｉｉ ）目的に応じて枝成分と幹成分の組合せを自由
に選ぶことができる。iii) The combination of branch components and trunk components can be freely selected depending on the purpose.
等の特徴があり、従来の方法では得られない高性能なグ
ラフトポリマーを容易に得ることができる為、最近非常
に注目されているものである。It has been attracting a lot of attention recently because it can easily obtain high-performance graft polymers that cannot be obtained by conventional methods.
本発明のグラフトポリマーの製造法は、上に述べたマク
ロモノマーと他のビニル単量体とからなるグラフトポリ
マーの製造を、懸濁重合よって行うことを特徴とするも
のである。The method for producing a graft polymer of the present invention is characterized in that the graft polymer comprising the above-mentioned macromonomer and another vinyl monomer is produced by suspension polymerization.
本発明におけるグラフトポリマー〇枝成分はビニル重合
性モノマーの重合体骨格であり、モノマーユニットとし
て、〔マクロモノマー〕の項で述べたような各種のモノ
マーユニットを単独或いは共重合体として使用できる。The branch component of the graft polymer in the present invention is a polymer skeleton of a vinyl polymerizable monomer, and as the monomer unit, various monomer units as described in the section [Macromonomer] can be used alone or as a copolymer.
幹成分は、グラフトポリマー製造時にマクロモノマーと
共重合させるビニル単量体に基づくビニル重合体骨格で
ある。The backbone component is a vinyl polymer backbone based on vinyl monomers that are copolymerized with macromonomers during graft polymer production.
上記ビニル単量体としては、酢酸ビニルの如き有機酸の
ビニルエステル、スチレン、スチレン置換体並びにビニ
ルピリジン、ビニルナフタレンの如きビニル芳香族化合
物、（メタ）アクリル酸エステル、（メタ）アクリロニ
トリル、アクロレイン、Ｎ−ビニルピロリドン及びＮ−
ビニルカプロラクタムの如きＮ−ビニル化合物、無水マ
レイン酸の如き不飽和酸無水物、Ｎ−フェニルマレイミ
ドの如きＮ−ｇ換マレイミド、塩化ビニル、塩化ビニリ
デンの如き不飽和ハロゲン化物等が使用でき、これらの
モノマーは単独で或いは２種類以上併用して使用するこ
とができる。Examples of the vinyl monomer include vinyl esters of organic acids such as vinyl acetate, styrene, styrene-substituted products, vinyl aromatic compounds such as vinylpyridine and vinylnaphthalene, (meth)acrylic acid esters, (meth)acrylonitrile, acrolein, N-vinylpyrrolidone and N-
N-vinyl compounds such as vinyl caprolactam, unsaturated acid anhydrides such as maleic anhydride, N-g-converted maleimides such as N-phenylmaleimide, unsaturated halides such as vinyl chloride and vinylidene chloride, etc. can be used. The monomers can be used alone or in combination of two or more.
これらのビニル単量体或いは単量体混合物は、グラフト
ポリマー製造時の重合温度で液体であり、その９０％以
上が水に不溶性でり、且つマクロモノマーを溶解し得る
ものである必要がある。水に溶解する成分が１０％以上
あると、水中での重合がおこりグラフトポリマーの純度
を低下させる為好ましくない。These vinyl monomers or monomer mixtures must be liquid at the polymerization temperature used to produce the graft polymer, at least 90% of which must be insoluble in water, and must be capable of dissolving the macromonomer. If the proportion of components soluble in water is 10% or more, polymerization occurs in water and the purity of the graft polymer decreases, which is not preferable.
本発明のグラフトポリマーの製造方法は、水を媒体とす
る懸濁重合によるものであって、−船釣な水系懸濁重合
法に準じて行えば良く、−例を示せば、所定量の水、分
散剤、界面活性剤を仕込んだ重合器中に、マクロモノマ
ー及び重合開始剤を溶解させたビニル単量体溶液を、初
期−括仕込み、分割仕込みまたは連続仕込みし、反応液
を所定の反応温度、所定の撹拌速度で数時間重合するこ
とによりグラフトポリマーを製造することができる。The method for producing the graft polymer of the present invention is based on suspension polymerization using water as a medium. A vinyl monomer solution in which a macromonomer and a polymerization initiator are dissolved is initially charged, dividedly, or continuously into a polymerization vessel containing a dispersant, a surfactant, and the reaction solution is subjected to a predetermined reaction. A graft polymer can be produced by polymerizing for several hours at a given temperature and stirring speed.
上記懸濁重合において使用するマクロモノマーとビニル
単量体の重ｉｔ組成は、０．５／９９．５〜７０／３０
であることが好ましく、５／９５〜５０１５０であるこ
とが更に好ましい。マクロモノマーの仕込み組成が０．
５％以下では、製造したグラフトポリマーの物性に、マ
クロモノマーのグラフト効果が十分反映されない為好ま
しくなく、７０％以上ではマクロモノマーが溶解しない
か、或いは溶解した場合でもビニル単量体溶液の粘度が
高くなりすぎ、懸濁重合の際にブロッキングを生じやす
く、好ましくない。The polymer composition of the macromonomer and vinyl monomer used in the suspension polymerization is 0.5/99.5 to 70/30.
It is preferable that it is, and it is more preferable that it is 5/95-50150. The charging composition of macromonomer is 0.
If it is less than 5%, the grafting effect of the macromonomer will not be sufficiently reflected in the physical properties of the produced graft polymer, which is undesirable. If it is more than 70%, the macromonomer will not dissolve, or even if it is dissolved, the viscosity of the vinyl monomer solution will decrease. This is not preferable because it becomes too high and tends to cause blocking during suspension polymerization.
本発明において使用できる分散剤としては、ポリビニル
アルコール、部分ケン化ポリビニルアルコール、メチル
セルロース、ヒドロキシエチルセルロース、ヒドロキシ
プロピルセルロース、ヒドロキシプロピルメチルセルロ
ース、アクリル酸重合体、ポリビニルピロリドン、無水
マレイン酸−酢酸ビニル共重合体等の合成高分子物質、
デンプン、ゼラチン、アラビアゴム等の天然高分子物質
、カルシウム、バリウム、ストロンチウム、マグネシウ
ム、アルミニウム、鉄又はコバルトの燐酸塩のような難
溶性の燐酸金属塩（ただし２成分以上縮合したポリリン
酸を含む）の１種類又は２種類以上の混合物等を挙げる
ことができる。好ましい分散剤としては、ポリビニルア
ルコール、部分ケン化ポリビニルアルコール、メチルセ
ルロース、難溶性燐酸金属塩等を挙げることができる。Dispersants that can be used in the present invention include polyvinyl alcohol, partially saponified polyvinyl alcohol, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, acrylic acid polymer, polyvinylpyrrolidone, maleic anhydride-vinyl acetate copolymer, etc. synthetic polymer materials,
Natural polymeric substances such as starch, gelatin, and gum arabic, sparingly soluble phosphate metal salts such as phosphates of calcium, barium, strontium, magnesium, aluminum, iron, or cobalt (including polyphosphoric acid condensed with two or more components) Examples include one type or a mixture of two or more types. Preferred dispersants include polyvinyl alcohol, partially saponified polyvinyl alcohol, methyl cellulose, sparingly soluble phosphate metal salts, and the like.
界面活性剤としては、ドデシルベンゼンスルホン酸ナト
リウム、ナトリウムオクチルスルフアート、ナトリウム
スルホコハク酸のジオクチルエスチル、アルカリラウリ
ルスルフアート又は脂肪酸のアルカリ塩等のアニオン系
界面活性剤や、カチオン系、ノニオン系界面活性剤が挙
げられ、これらを単独で又は２種類以上併用して使用す
ることができる。好ましくはドデシルベンゼンスルホン
酸ナトリウムが使用される。Examples of surfactants include anionic surfactants such as sodium dodecylbenzenesulfonate, sodium octyl sulfate, dioctyl ester of sodium sulfosuccinate, alkali lauryl sulfate, or alkali salts of fatty acids, cationic surfactants, and nonionic surfactants. Examples include surfactants, and these can be used alone or in combination of two or more. Preferably sodium dodecylbenzenesulfonate is used.
重合開始剤としては、過酸化ベンゾイル、過酸化ラウロ
イル、ｔ−ブチルパーベンゾニー）、ｔ−７’チルパー
オクトエート等のような油溶性有機過酸化物、ＡＩＢＮ
、 ＡＣＶＡ、 ＡＣＨＮ等の油溶性アゾ系化合物を用
いることができる。マクロモノマー中の連鎖移動切片の
酸化反応を防ぐ為、好ましくは油溶性アゾ系開始剤が使
用される。As a polymerization initiator, oil-soluble organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butyl perbenzony), t-7' chill peroctoate, etc., AIBN
, ACVA, ACHN, and other oil-soluble azo compounds can be used. Preferably, an oil-soluble azo initiator is used to prevent oxidation reactions of chain transfer fragments in the macromonomer.
また懸濁液は、安定剤、着色剤等の他の添加剤を含有し
ても構わない。The suspension may also contain other additives such as stabilizers and colorants.
重合温度は、３０℃〜１００°Ｃであることが好ましく
、５０℃〜９０℃であることが更に好ましい。反応温度
が３０℃以下では重合速度が遅い過ぎる為好ましくなく
、１００℃以上では分散媒体が沸騰し易く懸濁安定性が
低下する為好ましくない。The polymerization temperature is preferably 30°C to 100°C, more preferably 50°C to 90°C. A reaction temperature of 30° C. or lower is undesirable because the polymerization rate is too slow, and a reaction temperature of 100° C. or higher is undesirable because the dispersion medium tends to boil and the suspension stability decreases.
重合終了後のグラフトポリマーの単離は、通常のＱｉ重
合において実施されていると同様な濾過、水洗および乾
燥等の操作によって行うことができる。Isolation of the graft polymer after completion of polymerization can be carried out by operations such as filtration, washing with water, drying, etc., which are similar to those carried out in ordinary Qi polymerization.
本発明の方法により製造されたグラフトポリマーは、そ
れ自体で接着剤や塗料、成形材料、エラストマー等とし
て利用できるほか、−ｉ的な高分子の高機能、高性能化
のための改質剤として用いることもできる。The graft polymer produced by the method of the present invention can be used by itself as an adhesive, paint, molding material, elastomer, etc., and can also be used as a modifier for improving the functionality and performance of -i polymers. It can also be used.
改質剤として用いる例としては、各種高分子材料の表面
及び界面改質剤、ポリマーブレンド相溶化剤、分散剤、
乳化剤、生体適合性材料や選択的透過膜材料等の機能導
入等の、グラフトポリマーの持つ界面活性や多相構造を
利用した用途を挙げることができる。Examples of use as modifiers include surface and interface modifiers for various polymeric materials, polymer blend compatibilizers, dispersants,
Applications that utilize the surface activity and multiphase structure of graft polymers include the introduction of functions such as emulsifiers, biocompatible materials, and selectively permeable membrane materials.
以下に実施例及び比較例を挙げ本発明をより具体的に説
明する。なお各偶に記載の％はすべて重量％を表し、部
は重量部を表す。EXAMPLES The present invention will be described in more detail below with reference to Examples and Comparative Examples. In addition, all the percentages described in each case represent % by weight, and the parts represent parts by weight.
実施例１ スチレン−ＭＭＡ グラフトポリマーの製
造Ｉ
撹拌基、還流冷却器１滴下ロート及び温度針を取りつけ
たガラスフラスコに、蒸溜水４００部、ポリビニルアル
コール（クラレ■製ポバール４２０） ノ５％水溶液４
部、燐酸カルシウム懸濁液（日本化学工業■製スーパー
タイＩ−１０） １０部、ドデシルベンゼンスルホン酸
ナトリウム（花王■製エマール２Ｆ）の５χ水溶液０．
２部を仕込んだ。末端メタクリル型のＭＭＡマクロモノ
マー（東亜合成■製マクロモノマーＡＡ−６）２０部、
ＡＩＢＮ ２部をスチレンモノマー８０部に溶解した溶
液を滴下ロートに入れ、フラスコを加熱昇温しで内液の
温度を８０°Ｃに設定した後、滴下ロートよりモノマー
混合物を１分かけて滴下した。その後、８０°Ｃで８時
間保ち、重合を完結させた。この間撹拌機の回転数は２
００ ｒｐｍに保った。反応中はブロッキング等の不都
合は生じなかった。Example 1 Production of styrene-MMA graft polymer I In a glass flask equipped with a stirring group, a reflux condenser, a dropping funnel, and a temperature needle, 400 parts of distilled water and a 5% aqueous solution of polyvinyl alcohol (Poval 420 manufactured by Kuraray ■) were added.
10 parts of calcium phosphate suspension (Supertie I-10, manufactured by Nihon Kagaku Kogyo ■), 0.0 parts of a 5χ aqueous solution of sodium dodecylbenzenesulfonate (Emar 2F, manufactured by Kao ■).
I prepared the second part. 20 parts of MMA macromonomer with methacrylic terminal (macromonomer AA-6 manufactured by Toagosei ■),
A solution of 2 parts of AIBN dissolved in 80 parts of styrene monomer was placed in a dropping funnel, and the temperature of the flask was raised to set the temperature of the internal liquid at 80°C, after which the monomer mixture was added dropwise from the dropping funnel over a period of 1 minute. . Thereafter, the mixture was kept at 80°C for 8 hours to complete the polymerization. During this time, the rotation speed of the stirrer was 2.
00 rpm. No problems such as blocking occurred during the reaction.
反応後、濾過、酸洗、水洗して、減圧乾燥させ固体状の
スチレン−ＭＭＡ グラフトポリマー９６部を得た。After the reaction, the mixture was filtered, pickled, washed with water, and dried under reduced pressure to obtain 96 parts of a solid styrene-MMA graft polymer.
ＧＰＣによるポリスチレン換算分子量は、Ｍｎ−４３０
００ＭＷ＝１６００００であり、ＧＰＣチャートに残存
マクロモノマーのピークは観察されなかった。The polystyrene equivalent molecular weight by GPC is Mn-430
00MW=160000, and no residual macromonomer peak was observed in the GPC chart.
実施例２ スチレン−ＭＭＡ グラフトポリマーの製
造■
ＡＩＢＮを１部使用すること以外は実施例１と全く同様
の方法で懸濁重合、後処理し、固体状のスチレン−ＭＭ
Ａ グラフトポリマー９７部を得た。Example 2 Production of styrene-MMA graft polymer■ Suspension polymerization and post-treatment were carried out in exactly the same manner as in Example 1 except that one part of AIBN was used, and solid styrene-MM was obtained.
A: 97 parts of graft polymer were obtained.
ＧＰＣによるポリスチレン換算分子量はＭｎ＝５１００
０Ｍｓｖ＝１８４０００であり、ＧＰＣチャートに残存
マクロモノマーのピークは観察されなかった。又重合時
の分散安定性にも問題なかった。Polystyrene equivalent molecular weight by GPC is Mn=5100
0Msv=184000, and no residual macromonomer peak was observed in the GPC chart. Further, there was no problem in dispersion stability during polymerization.
実施例３ スチレン−ＭＭＡ グラフトポリマーの製
造■
スチレンモノマーを７０部、ＭＭＡマクロモノマーを３
０部、ＡＩＢＮを２部使用すること以外は実施例１と全
（同様の方法で懸濁重合、後処理し、固体状のスチレン
−ＭＭＡ グラフトポリマー９５部を得た。ｃｐｃに
よるポリスチレン換算分子量はＭｎ＝３６０００ Ｍｗ
＝１７００００であり、ＣＰＣチャートに残存マクロモ
ノマーのピークは観察されなかった。Example 3 Production of styrene-MMA graft polymer ■ 70 parts of styrene monomer and 3 parts of MMA macromonomer
Suspension polymerization and post-treatment were carried out in the same manner as in Example 1 except that 0 parts and 2 parts of AIBN were used to obtain 95 parts of a solid styrene-MMA graft polymer.The molecular weight in terms of polystyrene by CPC was Mn=36000 Mw
= 170,000, and no peak of residual macromonomer was observed in the CPC chart.
又重合時の分散安定性にも問題なかった。Further, there was no problem in dispersion stability during polymerization.
実施例４ スチレン−ＭＭＡ グラフトポリマーの製
造■
スチレンモノマーを７０部、ＭＭＡマクロモノマーを３
０部、ＡＩＢＮを１部使用すること以外は実施例１と全
く同様の方法で懸濁重合、後処理し、固体状のスチレン
−ＭＭＡ グラフトポリマー９８部を得た。ＧＰＣに
よるポリスチレン換算分子量はＭｎ＝５９０００ Ｍｗ
＝２８８０００であり、ＧＰＣチャートに残存マクロモ
ノマーのピークは観察されなかった。Example 4 Production of styrene-MMA graft polymer ■ 70 parts of styrene monomer and 3 parts of MMA macromonomer
Suspension polymerization and post-treatment were carried out in exactly the same manner as in Example 1, except that 0 part of AIBN and 1 part of AIBN were used to obtain 98 parts of a solid styrene-MMA graft polymer. Polystyrene equivalent molecular weight by GPC is Mn=59000 Mw
= 288,000, and no peak of residual macromonomer was observed in the GPC chart.
又重合時の分散安定性にも問題なかった。Further, there was no problem in dispersion stability during polymerization.
実施例５ スチレン−ＢＡ グラフトポリマーの製造
スチレンモノマーを７０部、末端メタクリル型のＢＡマ
クロモノマー（東亜合成■製マクロモノマーＡＢ−６）
を３０部、＾ＩＢＮを１部使用すること以外は実施例１
と全く同様の方法で懸濁重合、後処理し、固体状のスチ
レン−ＢＡ グラフトポリマー９８部を得た。ＧＰＣ
によるポリスチレン換算分子量は、Ｍｎ＝５８０００
Ｍｗ＝２１８０００であり、ＧＰＣチャートに残存マク
ロモノマーのピークは観察されなかった。又重合時の分
散安定性にも問題なかった。Example 5 Production of styrene-BA graft polymer 70 parts of styrene monomer, methacrylic terminal BA macromonomer (macromonomer AB-6 manufactured by Toagosei ■)
Example 1 except that 30 parts of and 1 part of ^IBN were used.
Suspension polymerization and post-treatment were carried out in exactly the same manner as above to obtain 98 parts of a solid styrene-BA graft polymer. GPC
The polystyrene equivalent molecular weight is Mn=58000
Mw=218,000, and no residual macromonomer peak was observed in the GPC chart. Further, there was no problem in dispersion stability during polymerization.
実施例６ 塩化ビニル−スチレン グラフトポリマーの
製造
内容積５１のオートクレーブに純水１４０部、ポリビニ
ルアルコール（クラレ■製ポバール４２０）０．２０部
、メチルセルロース（信越化学■製メトローズ６０ＳＨ
５０） ０．１０部を添加し、３時間撹拌した。Example 6 Production of vinyl chloride-styrene graft polymer In an autoclave with an internal volume of 51, 140 parts of pure water, 0.20 parts of polyvinyl alcohol (Poval 420 manufactured by Kuraray ■), and methylcellulose (Metrose 60SH manufactured by Shin-Etsu Chemical ■)
50) 0.10 part was added and stirred for 3 hours.
上記分散剤が完全に溶解したことを確認した後、末端メ
タクリル型のスチレンマクロモノマー（東亜合成■製マ
クロモノマーＡＳ−６） ２０部と２．２′−アゾビス
−（２，４−ジメチルバレロニトリル）（和光純薬■製
Ｖ−６５） ０．３０部を添加した。窒素で系内を置換
し、−６００ｍｍＨｇにまで脱気した後塩化ビニルモノ
マー８０部を仕込んだ、更に８０℃に昇温し、８時間撹
拌して重合を完結させた。重合終了後、濾過、水洗し、
熱風乾燥して粗粒状の塩化ビニル−スチレン グラフト
ポリマー８０部を得た。ＧＰＣによるポリスチレン換算
分子量は、Ｍｎ＝７５００ＭＧ１＝５７０００であり、
ＧＰＣチャートに残存マクロモノマーのピークは観察さ
れなかった。またキシレン抽出（室温、３時間）の結果
、抽出率は１．２ｚであった。After confirming that the above dispersant was completely dissolved, 20 parts of methacrylic terminal styrene macromonomer (Macromonomer AS-6 manufactured by Toagosei ■) and 2,2'-azobis-(2,4-dimethylvaleronitrile) were added. ) (V-65 manufactured by Wako Pure Chemical Industries, Ltd.) 0.30 part was added. After purging the system with nitrogen and degassing to -600 mmHg, 80 parts of vinyl chloride monomer was charged, and the temperature was further raised to 80°C and stirred for 8 hours to complete polymerization. After polymerization, filter, wash with water,
The mixture was dried with hot air to obtain 80 parts of coarsely granulated vinyl chloride-styrene graft polymer. The polystyrene equivalent molecular weight by GPC is Mn = 7500 MG1 = 57000,
No residual macromonomer peak was observed in the GPC chart. Further, as a result of xylene extraction (room temperature, 3 hours), the extraction rate was 1.2z.
実施例７ 塩化ビニル−スチレン−アクリロニトリルグ
ラフトポリマーの製造
塩化ビニルモノマーを８０部、末端メタクリル型のスチ
レン−アクリロニトリル共重合体マクロモノマー（東亜
合成■製マクロモノマーＡＮ−６）を２０部使用するこ
と以外は実施例６と全く同様の方法で懸濁重合、後処理
し、粗粒状の塩化ビニル−スチレン−アクリロニトリル
グラフトポリマー８０部を得たＧＰＣによるポリスチ
レン換算分子量は、Ｍｎ＝１３０００ Ｍｗ−１０００
００であり、ＧＰＣチャートに残存マクロモノマーのピ
ークは観察されなかった。またキシレン抽出（室温、３
時間）の結果、抽出率は１．０χであった。Example 7 Production of vinyl chloride-styrene-acrylonitrile graft polymer Other than using 80 parts of vinyl chloride monomer and 20 parts of styrene-acrylonitrile copolymer macromonomer with methacrylic terminal (Macromonomer AN-6 manufactured by Toagosei ■) was subjected to suspension polymerization and post-treatment in exactly the same manner as in Example 6 to obtain 80 parts of coarse-grained vinyl chloride-styrene-acrylonitrile graft polymer.The molecular weight in terms of polystyrene by GPC was Mn=13000 Mw-1000.
00, and no residual macromonomer peak was observed in the GPC chart. Also, xylene extraction (room temperature, 3
time), the extraction rate was 1.0χ.
（ハ）発明の効果
本発明によれば、懸濁重合によって容易に高純度のグラ
フトポリマーを製造することができるため、有機溶剤を
使用する溶液重合法によるのと比べ、火災、中毒等の危
険性が無くまた特殊な乾燥設備が不要であることから製
造コスト面でも有利となるので、本発明は産業上極めて
有用である。(C) Effects of the Invention According to the present invention, a highly pure graft polymer can be easily produced by suspension polymerization, so there is a greater risk of fire, poisoning, etc. compared to solution polymerization using an organic solvent. The present invention is industrially extremely useful since it is advantageous in terms of production costs since it has no drying properties and does not require special drying equipment.
Claims (1)
ノマーとを、水系懸濁重合により共重合させることを特
徴とするグラフトポリマーの製造方法。1. A method for producing a graft polymer, which comprises copolymerizing a vinyl monomer and a macromonomer soluble in the vinyl monomer by aqueous suspension polymerization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26540387A JPH01108209A (en) | 1987-10-22 | 1987-10-22 | Manufacture of graft polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26540387A JPH01108209A (en) | 1987-10-22 | 1987-10-22 | Manufacture of graft polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01108209A true JPH01108209A (en) | 1989-04-25 |
Family
ID=17416682
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26540387A Pending JPH01108209A (en) | 1987-10-22 | 1987-10-22 | Manufacture of graft polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01108209A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991004994A1 (en) * | 1989-10-02 | 1991-04-18 | Mitsui Petrochemical Industries, Ltd. | Acrylate copolymer and production and use of the same |
| WO2021083729A3 (en) * | 2019-10-31 | 2021-08-12 | Agfa Nv | A lithographic printing plate precursor and method for making hydrophobic resin particles |
-
1987
- 1987-10-22 JP JP26540387A patent/JPH01108209A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991004994A1 (en) * | 1989-10-02 | 1991-04-18 | Mitsui Petrochemical Industries, Ltd. | Acrylate copolymer and production and use of the same |
| WO2021083729A3 (en) * | 2019-10-31 | 2021-08-12 | Agfa Nv | A lithographic printing plate precursor and method for making hydrophobic resin particles |
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