JPH02132111A - Production of impact-resistant nitrile resin composition - Google Patents
Production of impact-resistant nitrile resin compositionInfo
- Publication number
- JPH02132111A JPH02132111A JP28374888A JP28374888A JPH02132111A JP H02132111 A JPH02132111 A JP H02132111A JP 28374888 A JP28374888 A JP 28374888A JP 28374888 A JP28374888 A JP 28374888A JP H02132111 A JPH02132111 A JP H02132111A
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- acid
- parts
- resin composition
- peak
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000002825 nitriles Chemical class 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000011342 resin composition Substances 0.000 title claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 55
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 150000001993 dienes Chemical class 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000012736 aqueous medium Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 12
- 229920003244 diene elastomer Polymers 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 abstract description 9
- 230000000977 initiatory effect Effects 0.000 abstract 2
- 239000005003 food packaging material Substances 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 229920000126 latex Polymers 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- -1 aromatic vinyl compound Chemical class 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 239000004816 latex Substances 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 150000001733 carboxylic acid esters Chemical class 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 229940087305 limonene Drugs 0.000 description 2
- 235000001510 limonene Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- JMYZLRSSLFFUQN-UHFFFAOYSA-N (2-chlorobenzoyl) 2-chlorobenzenecarboperoxoate Chemical compound ClC1=CC=CC=C1C(=O)OOC(=O)C1=CC=CC=C1Cl JMYZLRSSLFFUQN-UHFFFAOYSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical class CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- HLOUDBQOEJSUPI-UHFFFAOYSA-N 1-ethenyl-2,3-dimethylbenzene Chemical class CC1=CC=CC(C=C)=C1C HLOUDBQOEJSUPI-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
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- GLVYLTSKTCWWJR-UHFFFAOYSA-N 2-carbonoperoxoylbenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1C(O)=O GLVYLTSKTCWWJR-UHFFFAOYSA-N 0.000 description 1
- OYUNTGBISCIYPW-UHFFFAOYSA-N 2-chloroprop-2-enenitrile Chemical compound ClC(=C)C#N OYUNTGBISCIYPW-UHFFFAOYSA-N 0.000 description 1
- GNUGVECARVKIPH-UHFFFAOYSA-N 2-ethenoxypropane Chemical compound CC(C)OC=C GNUGVECARVKIPH-UHFFFAOYSA-N 0.000 description 1
- RCBGGJURENJHKV-UHFFFAOYSA-N 2-methylhept-1-ene Chemical compound CCCCCC(C)=C RCBGGJURENJHKV-UHFFFAOYSA-N 0.000 description 1
- IRUDSQHLKGNCGF-UHFFFAOYSA-N 2-methylhex-1-ene Chemical compound CCCCC(C)=C IRUDSQHLKGNCGF-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- TWCRBBJSQAZZQB-UHFFFAOYSA-N 3-methylidenehexane Chemical compound CCCC(=C)CC TWCRBBJSQAZZQB-UHFFFAOYSA-N 0.000 description 1
- RYKZRKKEYSRDNF-UHFFFAOYSA-N 3-methylidenepentane Chemical compound CCC(=C)CC RYKZRKKEYSRDNF-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- JOBBTVPTPXRUBP-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS JOBBTVPTPXRUBP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940080284 cetyl sulfate Drugs 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 1
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 1
- TWFQJFPTTMIETC-UHFFFAOYSA-N dodecan-1-amine;hydron;chloride Chemical compound [Cl-].CCCCCCCCCCCC[NH3+] TWFQJFPTTMIETC-UHFFFAOYSA-N 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 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
- 238000001035 drying Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 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
- 239000000446 fuel Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical group CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 1
- LPTIRUACFKQDHZ-UHFFFAOYSA-N hexadecyl sulfate;hydron Chemical compound CCCCCCCCCCCCCCCCOS(O)(=O)=O LPTIRUACFKQDHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000010102 injection blow moulding Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- YHIXOVNFGQWPFW-UHFFFAOYSA-N octadecan-1-amine;hydrobromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[NH3+] YHIXOVNFGQWPFW-UHFFFAOYSA-N 0.000 description 1
- CACRRXGTWZXOAU-UHFFFAOYSA-N octadecane-1-sulfonic acid Chemical compound CCCCCCCCCCCCCCCCCCS(O)(=O)=O CACRRXGTWZXOAU-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920006174 synthetic rubber latex Polymers 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical class CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、耐衝撃性に優れたニトリル系樹脂組成物の製
造方法に関するものである．
〔従来の技術〕
ニトリル系樹脂は、ガス及び蒸気に対するバリャー性、
そして耐溶剤性に優れた熱可塑性重合体であり、近年食
品や農医薬品、化粧品等の分野での包装材料として、そ
の実用価値が認められている．ニトリル系樹脂の製造方
法においては、耐衝撃性を付与する目的でゴム存在下に
不飽和ニトリルを主成分とする単量体混合物をグラフト
重合する方法が一殻的に知られており、それに関する多
数の技術が示されている。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a nitrile resin composition having excellent impact resistance. [Prior art] Nitrile resin has barrier properties against gas and steam,
It is a thermoplastic polymer with excellent solvent resistance, and in recent years its practical value has been recognized as a packaging material in the fields of foods, agricultural medicines, cosmetics, etc. As a method for producing nitrile resins, a method is generally known in which a monomer mixture containing unsaturated nitrile as a main component is graft-polymerized in the presence of rubber for the purpose of imparting impact resistance. A number of techniques have been demonstrated.
例えば、共役ジエン系ゴムに不飽和ニトリルとアクリル
酸アルキルエステルをグラフト重合する方法（特公昭４
６−２５００５号公報）あるいは、共役ジエン系ゴムに
不飽和ニトリル及び芳香族ビニル化合物をグラフト重合
する方法（特開昭５０−７５２９４号公報）等が示され
る．
このようなニトリル系樹脂組成物の製造において重要な
点は、耐衝撃性のちととなるゴム相とその周辺のマトリ
ックス相とのグラフト率のコントロール及び加工性を左
右するマトリックス相の分子量コントロールであり、こ
の両物性をいかにバランスよく重合体に１（１与するか
で得られる樹脂の実川性の良否がきまる。For example, a method of graft polymerizing unsaturated nitrile and acrylic acid alkyl ester to conjugated diene rubber (Japanese Patent Publication No. 4
6-25005) or a method of graft polymerizing an unsaturated nitrile and an aromatic vinyl compound to a conjugated diene rubber (Japanese Unexamined Patent Publication No. 50-75294). Important points in the production of such nitrile resin compositions are control of the grafting ratio between the rubber phase, which determines impact resistance, and the surrounding matrix phase, and control of the molecular weight of the matrix phase, which influences processability. The quality of the properties of the resin obtained depends on how well balanced these two physical properties are imparted to the polymer.
耐衝撃性を向上させるには、重合開始前にゴ・ムを単量
体の一部で前膨潤させる方法（特開昭５０−７５２９４
号公報）が示されるものの、一方加工性の向上に関して
はメルカプタン類等の分子ｆｉｌｌ整剤を使用し、更に
分子ｆｆｉ洲節剤の効果を高める為にｐＨｍ節剤を使用
する方法が知られている（特開昭５４−７１８３９号公
報）．
〔発明が解決しようとする課題〕
しかし、重合反応機構に与えるメルカプタンの影響は単
に分子ｉｔｉｌｌ節のみならずグラフト率も左右するた
め、耐衝撃性にも影響を与え、両物性が適度にバランス
した樹脂を得るのは難しく、例えば分子量！Ｉｌ節剤を
増量すれば、加工性は向上するが、耐衝撃性は実用に耐
えぬほど低下する．父上記重合法は、重合体のダイスウ
エリングが不安定で、既知の熱可塑性樹脂材料に使用さ
れる従来の成形方法すなわち押出成形、射出成形、ブロ
ー成形、インフレ製膜等において、成形時の形状、面状
態の悪化等の問題が生じていた．これらの問題点に鑑み
、本発明者らは重合体の転化率が５〜９０ｗｔ％である
間、重合系のｐＨをを５以下に調節し、かつ、分子量調
節剤をも連続あるりは分割して装入する方法を開示した
がいまだ不充分であった．
本発明の目的は、耐衝撃性と加工性のバランスしたニト
リル系樹脂の製造方法を提供することにある．
〔課題を解決する為の手段〕
本発明者らは、更に鋭意検討した結果遂に本発明に到達
した．
すなわち、本発明は、共役ジエン系単量体を５０重量％
以上含むジエン系ゴム状重合体１〜４０重量部の存在下
、不飽和ニトリル及びこれと共重合可能な他の単量体と
の混合物１００重量部を分子量禰整剤とともに水性媒体
中で重合するに際し、重合開始直後から重合ピーク時ま
での重合系のｐ Ｈを５以下にすることを特徴とする耐
衝撃性ニトリル系樹脂組成物の製造方法である．
本発明に用いるジエン系ゴム状重合体とは、共役ジエン
系単量体とこれと共重合可能な不飽和ニトリル、芳香族
ビニル化合物、不飽和カルボン酸エステル等から選ばれ
る、少なくとも一種の単量体との共重合体である．共役
ジエン系単量体としては、１−３ブタジェン、２．３−
ジメチル−１．３−ブタジエン、２．３−ジエチル−１
．３−プタジエン、イソプレン、クロロブレン等が例示
され、好ましくは１３ブタジエンである．不飽和ニトリ
ルとしては、アクリロニトリル、メタクリ口ニトリル、
α−クロロアクリロニトリル等が例示され、好ましくは
アクリロニトリルである．芳香族ビニル化合物としては
、スチレン、α−メチルスチレン、ビニルトルエン、ビ
ニルキシレン類が例示され、好ましくはスチレンである
．不飽和カルボン酸エステルとしては、アクリル酸ある
いはメタクリル酸のメチル、エチル、プロビル、プチル
等の↓ステルを挙げることができる．好ましくはアクリ
ル酸メチルメタクリル酸メチルである．このジエン系ゴ
ム状重合体は、公知の種ｈの方法で製造できるが、乳化
重合法が好適である．
不飽和ニトリルと共重合可能な他の単量体としては不飽
和カルボン酸エステル、芳香族ビニル化合物、α−オレ
フィン、ビニルエーテル、ビニルエステルが挙げられ、
このうち不飽和ニトリル、不飽和カルボン酸エステル、
芳香族ビニル化合物については、上記例示したものを使
用できる．α−オレフィンとしては、イソブテン、２−
メチル−１−フテン、２−メチル−１−ベンテン、２−
メチル−１−ヘキセン、２−メチル−１−ヘプテン、２
−エチル−１−プテン、２−プロビル−１−プテン等が
挙げられ好ましくは、イソブテンである．
ビニルエーテルとしては、メチルビニルエーテル、エチ
ルビニルエーテル、プロビルビニルエーテル類、プチル
ビニルエーテル類、イソプロビルビニルエーテル等が挙
げられ、好ましくはメチルビニルエーテルである．
ビニルエステルとして、酢酸ビニル、プロビオン酸ビニ
ル、酪酸ビニル類が挙げられ、好ましくは酢酸ビニルで
ある．
ジエン系ゴム状重合体の添加量は１〜４０重量部であり
好ましくは５〜３０重量部である．添加量が４０重量部
を越えると、加工性が悪くなり、１重量部未満では耐衝
撃性が悪くなる．本発明に用いる分子量訓整剤としては
、アルキルメル力ブタン類で、例えばｎ−ドデシルメル
カブタン、Ｌｅｒ ｔ− ドデシルメルカブタン、ｎ−
ドデシルチオールアセタート、ペンタエリスリトールテ
トラキス（β−メルカプトブ口ビオネート）、リモネン
ジメル力ブタン等があり、好ましくはメルカブタン臭が
実質的に無臭であるという点で、分子内に２個以上のメ
ルカプト基を含む有機メルカブト化合物、例えばペンタ
エリスリトールテトラキス（β−メルカプトブロピオネ
ート）、リモネンジメルカブタンである．
分子量調整剤の添加量は、必要とする分子量により決定
されるが、多量に添加すると、耐熱性および機械的性質
の低下をもたらすので、重合させる単量体基準で０．１
〜３重量％が適当である．本発明における重合ピーク時
とは、該重合反応中で反応率が最も高くなった時点をい
い、いいかえれば系内のモノマー消費率が最も高くなっ
た時点である．
重合ピークの起こる時期は、触媒の量、連鎖移動剤の量
等でコントロールすることができるが該重合反応開始後
４時間目までにピークをもってくるのがよい．
重合ピークまでの時間が４時間を越えると、反応が異常
に長引き、消費されるリン酸量も増えコスト高になる．
また、３時間より早い時期に重合ピークがおこる場合は
、急激な反応による発熱がおこり除熱が困難になる．好
ましくは、３時間目から４時間目までである．本発明で
は、重合開始直後から重合ピーク時までの重合系内のｐ
Ｈを５以下とするが、そのために用いるｐＨｌ節剤とし
ては、無機酸、有機酸のいずれでもよく、無機酸として
は、リン酸、硫酸、塩酸、臭化水素酸、硝酸があげられ
、有機酸としては、酢酸、ブロピオン酸、クエン酸、３
−メルカプトプロピオン酸、アスコルビン酸、リン酸エ
ステルなどがあげられる．好ましい酸は、酢酸、クエン
酸、リン酸、３−メルカブトプロビオン酸である．
本発明において、ｐ ｝Ｉの！Ｐｌ節は一般的にｐＨ＝
９〜１０であるゴム状重合体ラテックスを使用してグラ
フト重合をおこなう際に、ｐＨ−６〜８の中性に調節し
て重合を開始する従来の目的とは異なったものであり重
合反応系のＰ Ｈを５以下のほぼ完全酸性域下にするこ
とにより、分子ｆｆｉｇｌ１節剤としてのメルカプタン
が、グラフト反応には影響を与えず、本来の目的である
分子ｔＪｌ節剤コントロールにのみ有効に作用する．こ
のＰＨは、重合反応器等の材質上の問題から好ましくは
、２．５〜４の範囲である．
ｐＨｍ節の時期は、重合開始時のみ、あるいは重合開始
から終了までの長時間に行うのはあまり効果があがらず
、該重合反応における重合開始直後から反応ピーク時ま
での間継続して行うことで所望の重合体が得られる．
本発明において用いられる重合開始剤は、過硫酸、過酢
酸、及び過フタル酸等の過酸触媒、過硫酸カリウム等の
過酸塩触媒、過酸化水素、過酸化ヘンゾイル、過酸化ク
ロルベンゾイル、過酸化アセチル、過酸化ラウリル、過
酸化ジクミル等の過酸化物触媒があり、これらは、単独
あるいは、２種類以上を混合して用いられる．
本発明で好適な乳化剤は、ミリスチン酸、バルミチン酸
、ステアリン酸、ラウリル酸、オレイン酸等のナトリウ
ム又はカリウム塩、セチル硫酸、ラウリル硫酸、オレイ
ンスルホン酸、ステアリルスルホン酸等のナトリウム、
カリウム又はアンモニウム塩、ラウリルアミンヒド口ク
ロリド、ステアリルアミンヒドロブロミド等の高級アミ
ン塩、ポリビニルピロリドン、ポリアクリル酸ナトリウ
ム、メチルセルロース等の高分子物質等がある．本発明
に好適な重合方法は、乳化重合でありＯ〜１００゜Ｃの
任意の温度で、ラジカル重合開始剤存在下で重合を行い
、重合生成物はラテックスとして得られる．このラテッ
クスを常法により凝固、水洗、乾燥して重合体を得る．
得られた重合体は熱可塑性樹脂であり、通常の配合剤で
ある酸化防止剤、安定剤、着色剤、滑剤等を加えて、押
出成形、射出成形、カレンダー成形、ブロー成形等の加
工成形が可能である．
本発明の方法によって得られる樹脂は、従来技術による
ゴム強化ニトリル系重合体にくらべ、高耐衝撃性であり
、かつ易加工性であり耐溶剤性及び蒸気、ガスに対する
遮断性も備えていることから、食品、農医薬品、化粧品
等のボトル、フィルム、シート等の成形材料として有用
である。In order to improve the impact resistance, a method of pre-swelling the rubber with a part of the monomer before the start of polymerization (Japanese Patent Application Laid-open No. 75294-1983)
However, in order to improve processability, it is known to use molecular fill modifiers such as mercaptans, and to further enhance the effect of molecular ffi modifiers, to use pH modifiers. (Japanese Unexamined Patent Publication No. 54-71839). [Problem to be solved by the invention] However, the influence of mercaptan on the polymerization reaction mechanism affects not only the molecular weight but also the grafting ratio, which also affects the impact resistance, making it difficult to maintain a proper balance between both physical properties. It is difficult to obtain resin, for example, molecular weight! If the amount of Il moderating agent is increased, the processability will improve, but the impact resistance will decrease to an extent that it cannot be used for practical purposes. However, the above polymerization method has unstable die swelling of the polymer, and the conventional molding methods used for known thermoplastic resin materials, such as extrusion molding, injection molding, blow molding, and inflation film forming, are unstable during molding. Problems such as deterioration of the shape and surface condition occurred. In view of these problems, the present inventors adjusted the pH of the polymerization system to 5 or less while the conversion rate of the polymer was 5 to 90 wt%, and added the molecular weight regulator either continuously or in portions. Although we have disclosed a method for charging the fuel, it is still insufficient. An object of the present invention is to provide a method for producing a nitrile resin that has a good balance between impact resistance and processability. [Means for Solving the Problems] The present inventors have finally arrived at the present invention after further intensive study. That is, in the present invention, the conjugated diene monomer is contained in an amount of 50% by weight.
In the presence of 1 to 40 parts by weight of the diene-based rubbery polymer containing the above, 100 parts by weight of a mixture of unsaturated nitrile and other monomers copolymerizable with it are polymerized in an aqueous medium together with a molecular weight regulator. This is a method for producing an impact-resistant nitrile resin composition, which comprises controlling the pH of the polymerization system from immediately after the start of polymerization to the peak of polymerization to 5 or less. The diene-based rubbery polymer used in the present invention refers to at least one monomer selected from a conjugated diene-based monomer and an unsaturated nitrile copolymerizable with the same, an aromatic vinyl compound, an unsaturated carboxylic acid ester, etc. It is a copolymer with the body. Conjugated diene monomers include 1-3 butadiene, 2,3-
Dimethyl-1,3-butadiene, 2,3-diethyl-1
．． Examples include 3-butadiene, isoprene, and chlorobrene, with 13-butadiene being preferred. Examples of unsaturated nitriles include acrylonitrile, methacrylonitrile,
Examples include α-chloroacrylonitrile, and acrylonitrile is preferred. Examples of aromatic vinyl compounds include styrene, α-methylstyrene, vinyltoluene, and vinylxylenes, with styrene being preferred. Examples of unsaturated carboxylic acid esters include esters of acrylic acid or methacrylic acid such as methyl, ethyl, proyl, and butyl. Methyl acrylate and methyl methacrylate are preferred. This diene-based rubbery polymer can be produced by the known method of type h, but emulsion polymerization is preferred. Other monomers copolymerizable with unsaturated nitriles include unsaturated carboxylic acid esters, aromatic vinyl compounds, α-olefins, vinyl ethers, and vinyl esters.
Among these, unsaturated nitriles, unsaturated carboxylic acid esters,
As for the aromatic vinyl compound, those exemplified above can be used. α-olefins include isobutene, 2-
Methyl-1-phthene, 2-methyl-1-bentene, 2-
Methyl-1-hexene, 2-methyl-1-heptene, 2
-ethyl-1-butene, 2-propyl-1-butene, etc., and isobutene is preferred. Examples of the vinyl ether include methyl vinyl ether, ethyl vinyl ether, probyl vinyl ethers, butyl vinyl ethers, isopropyl vinyl ether, and the like, with methyl vinyl ether being preferred. Vinyl esters include vinyl acetate, vinyl probionate, and vinyl butyrate, with vinyl acetate being preferred. The amount of the diene rubbery polymer added is 1 to 40 parts by weight, preferably 5 to 30 parts by weight. If the amount added exceeds 40 parts by weight, processability will deteriorate, and if it is less than 1 part by weight, impact resistance will deteriorate. The molecular weight adjusting agent used in the present invention includes alkyl mercaptanes, such as n-dodecylmercabutane, Ler t-dodecylmercabutane, and n-dodecylmercabutane.
Examples include dodecylthiol acetate, pentaerythritol tetrakis (β-mercaptobionate), limonene dimerbutane, etc., and preferably organic compounds containing two or more mercapto groups in the molecule, in that the mercaptan odor is substantially odorless. Mercabut compounds such as pentaerythritol tetrakis (β-mercaptopropionate) and limonene dimercabutane. The amount of the molecular weight regulator to be added is determined by the required molecular weight, but adding a large amount will result in a decrease in heat resistance and mechanical properties, so it should be 0.1% based on the monomer to be polymerized.
~3% by weight is appropriate. In the present invention, the polymerization peak time refers to the time point during the polymerization reaction when the reaction rate is the highest, or in other words, the time point when the monomer consumption rate in the system is the highest. The timing at which the polymerization peak occurs can be controlled by adjusting the amount of catalyst, the amount of chain transfer agent, etc., but it is preferable that the peak occur by 4 hours after the start of the polymerization reaction. If the time until the polymerization peak exceeds 4 hours, the reaction will take an abnormally long time, and the amount of phosphoric acid consumed will increase, resulting in high costs.
Furthermore, if the polymerization peak occurs earlier than 3 hours, heat generation occurs due to rapid reaction, making it difficult to remove heat. Preferably from the 3rd hour to the 4th hour. In the present invention, p in the polymerization system from immediately after the start of polymerization to the time of the polymerization peak is
H is set to 5 or less, and the pHl moderator used for this purpose may be either an inorganic acid or an organic acid. Examples of inorganic acids include phosphoric acid, sulfuric acid, hydrochloric acid, hydrobromic acid, and nitric acid; Acids include acetic acid, propionic acid, citric acid, 3
- Examples include mercaptopropionic acid, ascorbic acid, and phosphoric acid esters. Preferred acids are acetic acid, citric acid, phosphoric acid, and 3-mercabutoprobionic acid. In the present invention, p }I! The Pl node is generally pH=
This is different from the conventional purpose of graft polymerization using a rubbery polymer latex with a pH of 9 to 10, in which the pH is adjusted to a neutral pH of -6 to 8 to initiate polymerization. By bringing the pH of the molecule to below 5, an almost completely acidic range, mercaptan, which acts as a molecular ffigl1 moderator, does not affect the grafting reaction, but effectively acts only on its original purpose of controlling the molecular tJl moderator. do. This pH is preferably in the range of 2.5 to 4 due to problems with the materials of the polymerization reactor and the like. Regarding the timing of the pHm section, it is not very effective to perform it only at the start of polymerization or for a long time from the start to the end of polymerization. The desired polymer is obtained. Polymerization initiators used in the present invention include peracid catalysts such as persulfuric acid, peracetic acid, and perphthalic acid, persalt catalysts such as potassium persulfate, hydrogen peroxide, henzoyl peroxide, chlorobenzoyl peroxide, and There are peroxide catalysts such as acetyl oxide, lauryl peroxide, and dicumyl peroxide, and these can be used alone or in combination of two or more. Suitable emulsifiers in the present invention include sodium or potassium salts of myristic acid, valmitic acid, stearic acid, lauric acid, oleic acid, etc., sodium salts such as cetyl sulfate, lauryl sulfate, oleinsulfonic acid, stearylsulfonic acid, etc.
These include potassium or ammonium salts, higher amine salts such as laurylamine hydrochloride and stearylamine hydrobromide, and polymeric substances such as polyvinylpyrrolidone, sodium polyacrylate, and methylcellulose. A polymerization method suitable for the present invention is emulsion polymerization, in which polymerization is carried out at any temperature from 0 to 100°C in the presence of a radical polymerization initiator, and the polymerization product is obtained as a latex. This latex is coagulated by conventional methods, washed with water, and dried to obtain a polymer.
The obtained polymer is a thermoplastic resin, and it can be processed and molded by extrusion molding, injection molding, calendar molding, blow molding, etc. by adding ordinary compounding ingredients such as antioxidants, stabilizers, colorants, and lubricants. It is possible. The resin obtained by the method of the present invention has higher impact resistance and easier processing than rubber-reinforced nitrile polymers produced by conventional techniques, and also has solvent resistance and vapor and gas barrier properties. Therefore, it is useful as a molding material for bottles, films, sheets, etc. for foods, agricultural medicines, cosmetics, etc.
以下、実施例により本発明を説明する．なお、以下の「
部」及び［％』は重量基準による．
Ｊ瞳上
（Ａ）ジエン系ゴムラテックスの製造
下配成分からなる混合物をステンレス製重合反応器にて
、窒素雰囲気で、攪拌をし４５゜Ｃで２０時間重合を行
い、転化率９０％で重合を終了した．重合終了後、過剰
の単量体をストリッピングにより除き、固形分濃度３０
％の合成ゴムラテックスを得た．
アクリロニトリル ４０ 部１−３ブタジ
エン ６０ 部脂肪酸セッケン
２．４部アゾビスイソブチロニトリル ０．３
部クーシャルドデシルメルカブタン０．５部水
２００部また、ラテッ
クスを乾燥後、固形分を回収し、元素分析によりゴム中
のアクリロニトリル含量を求めたところ３１３ｗｔ％で
あった．
（Ｂ）グラフト重合体の製造
重合反応器に下記の組成の原料を仕込み窒素雰囲気化で
攪拌しながら５８゜Ｃで重合を開始した．重合開始時の
ｐｌ１は７．４であった．水
２００部アクリロニトリル
７５ 部メチルアクリレート ２５ 部上
記（Ａ）のゴムラテックス ３３ 部（固形分 １０
部）
ジオクチルスルホコハク酸ナトリウム
１．３１部
ポリビニルビロリドン ０．４７部過硫酸カリ
ウム ０．０６部ターシャルドデシルメ
ル力ブタン２．０部重合開始３０分から重合系にリン酸
を連続的に添加して反応ピーク時までＰ Ｈ ＝ ３を
保持し、さらに５８゜Ｃで５時間重合を行った．
なお、反応ピークは重合開始から３時間目に起こった．
得られたラテックスを希硫酸アルミニウム水溶液（ｉｌ
１度４５％）を加えて凝固させ、水洗、乾燥して粉末状
重合体を得た．
この重合体を１７０゜Ｃ， １４０ ｋｇ／ｃイで加圧
成形し透明、淡黄色のシートを得た．このシ一トより作
成した試験片のアイゾット衝撃強度（２３゜Ｃ ＡＳ
ＴＭ Ｄ２５６に準ず）及び得られた重合体のメルト
インデックス（ＡＳＴＭ Ｄ１２３８）を測定した結
果を第１表に示す．
〔比較例！〕
実施例１において、重合系のＰＨ調節を行わない点を除
いては実施例１と同様にして重合した。The present invention will be explained below with reference to Examples. In addition, the following “
"Parts" and "%" are based on weight. J Pupil Top (A) Production of diene-based rubber latex The mixture consisting of the sub-components was stirred in a stainless steel polymerization reactor in a nitrogen atmosphere and polymerized at 45°C for 20 hours, resulting in polymerization with a conversion rate of 90%. has finished. After the polymerization is completed, excess monomer is removed by stripping, and the solid content concentration is reduced to 30.
% of synthetic rubber latex was obtained. Acrylonitrile 40 parts 1-3 Butadiene 60 parts Fatty acid soap
2.4 parts Azobisisobutyronitrile 0.3
0.5 parts water
200 parts After drying the latex, the solid content was collected, and the acrylonitrile content in the rubber was determined by elemental analysis and found to be 313 wt%. (B) Preparation of graft polymer Raw materials having the following composition were charged into a polymerization reactor and polymerization was started at 58°C with stirring under a nitrogen atmosphere. pl1 at the start of polymerization was 7.4. water
200 parts acrylonitrile
75 parts Methyl acrylate 25 parts Rubber latex of (A) above 33 parts (solid content 10
1.31 parts of sodium dioctyl sulfosuccinate 0.47 parts of polyvinyl pyrrolidone 0.06 parts of potassium persulfate 2.0 parts of tertiary dodecylbutane 30 minutes after the start of polymerization, phosphoric acid was continuously added to the polymerization system. P H = 3 was maintained until the reaction peak, and polymerization was further carried out at 58°C for 5 hours. Note that the reaction peak occurred 3 hours after the start of polymerization. The obtained latex was dissolved in a dilute aluminum sulfate aqueous solution (il
45%) was added to solidify, washed with water, and dried to obtain a powdered polymer. This polymer was pressure molded at 170°C and 140 kg/cm to obtain a transparent, pale yellow sheet. Izod impact strength (23°C AS
Table 1 shows the results of measuring the melt index (according to TM D256) and the melt index (ASTM D1238) of the obtained polymer. [Comparative example! ] Polymerization was carried out in the same manner as in Example 1, except that the pH of the polymerization system was not adjusted.
生成した重合体のアイゾソト衝撃強度とメルトインデッ
クスの値を第１表に示す．
〔比較例２〕
実施例ｌにおいて、重合開始時において重合系のＰＨを
３に合わせた後、それ以後のｐＨｇＪｌ節を行わない点
を除いてはは実施例１と同様にして重合した．
生成した重合体のアイゾット衝撃強度とメルトインデッ
クスの値を第１表に示す．
〔比較例３〕
実施例１において、重合開始時において重合系のＰＨを
３に合わせた後、重合終了時までの重合系のｐＨを３に
維持するようリン酸を連続的に添加した．
生成した重合体のアイゾット衝撃強度とメルトインデッ
クスの値を第１表に示す．
〔実施例２〕
実施例１において重合開始から重合ピーク時までの重合
系のｐＨを４にあわせる点を除いては実施例ｌと同様に
して重合を行った．
生成した重合体のアイゾット衝撃強度とメルトインデッ
クスの値を第１表に示す．
第１表
〔発明の効果〕
本発明により得られるニトリル系樹脂組成物は、従来技
術による樹脂に比べ耐ｆｌｉ ｕ性に優れており工業的
に価値が大である．
特許出願人 三井東圧化学株式会社
■ＺＯＤ：アイゾッド衝撃強度（ ｋｇ−ｃｖａ／ Ｃ
ｌ）：メルトインデックス（
ｇ／１０ｍｉｎTable 1 shows the isosotho impact strength and melt index values of the produced polymer. [Comparative Example 2] Polymerization was carried out in the same manner as in Example 1, except that the pH of the polymerization system was adjusted to 3 at the start of polymerization, and the subsequent pHgJl section was not performed. Table 1 shows the Izod impact strength and melt index values of the produced polymer. [Comparative Example 3] In Example 1, after adjusting the pH of the polymerization system to 3 at the start of polymerization, phosphoric acid was continuously added to maintain the pH of the polymerization system at 3 until the end of polymerization. Table 1 shows the Izod impact strength and melt index values of the produced polymer. [Example 2] Polymerization was carried out in the same manner as in Example 1, except that the pH of the polymerization system was adjusted to 4 from the start of polymerization to the peak of polymerization in Example 1. Table 1 shows the Izod impact strength and melt index values of the produced polymer. Table 1 [Effects of the Invention] The nitrile resin composition obtained by the present invention has excellent fli u resistance compared to resins made by the prior art and is of great industrial value. Patent applicant Mitsui Toatsu Chemical Co., Ltd. ZOD: Izod impact strength (kg-cva/C
l): Melt index (g/10min
Claims (1)
ゴム状重合体１〜４０重量部の存在下、不飽和ニトリル
及びこれと共重合可能な他の単量体との混合物１００重
量部を分子量調整剤とともに水性媒体中で重合するに際
し、重合開始直後から重合ピーク時までの重合系のｐＨ
を５以下に調節することを特徴とする耐衝撃性ニトリル
系樹脂組成物の製造方法。1. 100 parts by weight of a mixture of unsaturated nitrile and other monomers copolymerizable with it in the presence of 1 to 40 parts by weight of a diene rubbery polymer containing 50% by weight or more of a conjugated diene monomer When polymerizing with a molecular weight regulator in an aqueous medium, the pH of the polymerization system from immediately after the start of polymerization to the time of polymerization peak.
1. A method for producing an impact-resistant nitrile resin composition, the method comprising adjusting the nitrile resin composition to 5 or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28374888A JPH02132111A (en) | 1988-11-11 | 1988-11-11 | Production of impact-resistant nitrile resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28374888A JPH02132111A (en) | 1988-11-11 | 1988-11-11 | Production of impact-resistant nitrile resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02132111A true JPH02132111A (en) | 1990-05-21 |
| JPH0551609B2 JPH0551609B2 (en) | 1993-08-03 |
Family
ID=17669599
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28374888A Granted JPH02132111A (en) | 1988-11-11 | 1988-11-11 | Production of impact-resistant nitrile resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02132111A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100620478B1 (en) * | 1999-05-24 | 2006-09-13 | 텍스트론 인크. | Drive system |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52139187A (en) * | 1976-05-17 | 1977-11-19 | Standard Oil Co | Activation of mercaptan by acid in copolymerization of acrylonitrile |
-
1988
- 1988-11-11 JP JP28374888A patent/JPH02132111A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52139187A (en) * | 1976-05-17 | 1977-11-19 | Standard Oil Co | Activation of mercaptan by acid in copolymerization of acrylonitrile |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100620478B1 (en) * | 1999-05-24 | 2006-09-13 | 텍스트론 인크. | Drive system |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0551609B2 (en) | 1993-08-03 |
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