JPH026514A - Preparation of thermoplastic graft copolymer - Google Patents
Preparation of thermoplastic graft copolymerInfo
- Publication number
- JPH026514A JPH026514A JP63154801A JP15480188A JPH026514A JP H026514 A JPH026514 A JP H026514A JP 63154801 A JP63154801 A JP 63154801A JP 15480188 A JP15480188 A JP 15480188A JP H026514 A JPH026514 A JP H026514A
- Authority
- JP
- Japan
- Prior art keywords
- maleic anhydride
- maleimide
- polycarbonate
- bis
- graft copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000578 graft copolymer Polymers 0.000 title claims description 10
- 229920001169 thermoplastic Polymers 0.000 title claims description 7
- 239000004416 thermosoftening plastic Substances 0.000 title claims description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 22
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000004417 polycarbonate Substances 0.000 claims abstract description 14
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 21
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 238000007334 copolymerization reaction Methods 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 abstract description 10
- 239000012986 chain transfer agent Substances 0.000 abstract description 9
- 239000000178 monomer Substances 0.000 abstract description 6
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 abstract description 4
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 239000003607 modifier Substances 0.000 abstract description 3
- WUQYBSRMWWRFQH-UHFFFAOYSA-N 2-prop-1-en-2-ylphenol Chemical compound CC(=C)C1=CC=CC=C1O WUQYBSRMWWRFQH-UHFFFAOYSA-N 0.000 abstract description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 abstract 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract 1
- 210000000988 bone and bone Anatomy 0.000 abstract 1
- 239000001294 propane Substances 0.000 abstract 1
- 229910052717 sulfur Inorganic materials 0.000 abstract 1
- 239000011593 sulfur Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 25
- 239000004431 polycarbonate resin Substances 0.000 description 13
- 229920005668 polycarbonate resin Polymers 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 10
- -1 hydroxybenzoic acid allyl ester Chemical group 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 5
- 150000002989 phenols Chemical class 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 239000004793 Polystyrene Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000012662 bulk polymerization Methods 0.000 description 3
- FZFAMSAMCHXGEF-UHFFFAOYSA-N chloro formate Chemical compound ClOC=O FZFAMSAMCHXGEF-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- BDFAOUQQXJIZDG-UHFFFAOYSA-N 2-methylpropane-1-thiol Chemical compound CC(C)CS BDFAOUQQXJIZDG-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical group S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N Methyl ethyl ketone Natural products CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000006085 branching agent Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 238000010559 graft polymerization reaction Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 150000002898 organic sulfur compounds Chemical class 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- GRTWTVFDPBKQNU-MQQKCMAXSA-N (2e,4e)-hexa-2,4-dienoyl chloride Chemical compound C\C=C\C=C\C(Cl)=O GRTWTVFDPBKQNU-MQQKCMAXSA-N 0.000 description 1
- URFNSYWAGGETFK-UHFFFAOYSA-N 1,2-bis(4-hydroxyphenyl)ethane Natural products C1=CC(O)=CC=C1CCC1=CC=C(O)C=C1 URFNSYWAGGETFK-UHFFFAOYSA-N 0.000 description 1
- MKRBAPNEJMFMHU-UHFFFAOYSA-N 1-benzylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1CC1=CC=CC=C1 MKRBAPNEJMFMHU-UHFFFAOYSA-N 0.000 description 1
- QOVCUELHTLHMEN-UHFFFAOYSA-N 1-butyl-4-ethenylbenzene Chemical compound CCCCC1=CC=C(C=C)C=C1 QOVCUELHTLHMEN-UHFFFAOYSA-N 0.000 description 1
- JNPCNDJVEUEFBO-UHFFFAOYSA-N 1-butylpyrrole-2,5-dione Chemical compound CCCCN1C(=O)C=CC1=O JNPCNDJVEUEFBO-UHFFFAOYSA-N 0.000 description 1
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 1
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 description 1
- JSWLXPQVSUEOJQ-UHFFFAOYSA-N 1-nonylperoxynonane Chemical compound CCCCCCCCCOOCCCCCCCCC JSWLXPQVSUEOJQ-UHFFFAOYSA-N 0.000 description 1
- DABFKTHTXOELJF-UHFFFAOYSA-N 1-propylpyrrole-2,5-dione Chemical compound CCCN1C(=O)C=CC1=O DABFKTHTXOELJF-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 150000003923 2,5-pyrrolediones Chemical class 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
- LXUNZSDDXMPKLP-UHFFFAOYSA-N 2-Methylbenzenethiol Chemical compound CC1=CC=CC=C1S LXUNZSDDXMPKLP-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- KRDXTHSSNCTAGY-UHFFFAOYSA-N 2-cyclohexylpyrrolidine Chemical compound C1CCNC1C1CCCCC1 KRDXTHSSNCTAGY-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- JJRDRFZYKKFYMO-UHFFFAOYSA-N 2-methyl-2-(2-methylbutan-2-ylperoxy)butane Chemical compound CCC(C)(C)OOC(C)(C)CC JJRDRFZYKKFYMO-UHFFFAOYSA-N 0.000 description 1
- ZTMADXFOCUXMJE-UHFFFAOYSA-N 2-methylbenzene-1,3-diol Chemical compound CC1=C(O)C=CC=C1O ZTMADXFOCUXMJE-UHFFFAOYSA-N 0.000 description 1
- XLLXMBCBJGATSP-UHFFFAOYSA-N 2-phenylethenol Chemical group OC=CC1=CC=CC=C1 XLLXMBCBJGATSP-UHFFFAOYSA-N 0.000 description 1
- YMTYZTXUZLQUSF-UHFFFAOYSA-N 3,3'-Dimethylbisphenol A Chemical compound C1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=CC=2)=C1 YMTYZTXUZLQUSF-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- UJTRCPVECIHPBG-UHFFFAOYSA-N 3-cyclohexylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C2CCCCC2)=C1 UJTRCPVECIHPBG-UHFFFAOYSA-N 0.000 description 1
- VISOTGQYFFULBK-UHFFFAOYSA-N 3-hydroxy-4-phenylpyrrole-2,5-dione Chemical group O=C1C(=O)NC(O)=C1C1=CC=CC=C1 VISOTGQYFFULBK-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- ODJUOZPKKHIEOZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3,5-dimethylphenyl)propan-2-yl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=C(C)C=2)=C1 ODJUOZPKKHIEOZ-UHFFFAOYSA-N 0.000 description 1
- OPSUNPUMLMJDTH-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)-2,2-diphenylethyl]phenol Chemical compound C1=CC(O)=CC=C1CC(C=1C=CC(O)=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 OPSUNPUMLMJDTH-UHFFFAOYSA-N 0.000 description 1
- VHLLJTHDWPAQEM-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)-4-methylpentan-2-yl]phenol Chemical compound C=1C=C(O)C=CC=1C(C)(CC(C)C)C1=CC=C(O)C=C1 VHLLJTHDWPAQEM-UHFFFAOYSA-N 0.000 description 1
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- JAGRUUPXPPLSRX-UHFFFAOYSA-N 4-prop-1-en-2-ylphenol Chemical compound CC(=C)C1=CC=C(O)C=C1 JAGRUUPXPPLSRX-UHFFFAOYSA-N 0.000 description 1
- DUZJXKYBSMFDIU-UHFFFAOYSA-N 4-tert-butyl-2-methylbenzenethiol Chemical compound CC1=CC(C(C)(C)C)=CC=C1S DUZJXKYBSMFDIU-UHFFFAOYSA-N 0.000 description 1
- XHDJYQWGFIBCEP-UHFFFAOYSA-N 5-Chloro-1H-indole-2,3-dione Chemical compound ClC1=CC=C2NC(=O)C(=O)C2=C1 XHDJYQWGFIBCEP-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
- 229930185605 Bisphenol Natural products 0.000 description 1
- VOWWYDCFAISREI-UHFFFAOYSA-N Bisphenol AP Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=CC=C1 VOWWYDCFAISREI-UHFFFAOYSA-N 0.000 description 1
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 241000168022 Elaphurus davidianus Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- GHAZCVNUKKZTLG-UHFFFAOYSA-N N-ethyl-succinimide Natural products CCN1C(=O)CCC1=O GHAZCVNUKKZTLG-UHFFFAOYSA-N 0.000 description 1
- HDFGOPSGAURCEO-UHFFFAOYSA-N N-ethylmaleimide Chemical compound CCN1C(=O)C=CC1=O HDFGOPSGAURCEO-UHFFFAOYSA-N 0.000 description 1
- 229920001890 Novodur Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- PCKPVGOLPKLUHR-UHFFFAOYSA-N OH-Indolxyl Natural products C1=CC=C2C(O)=CNC2=C1 PCKPVGOLPKLUHR-UHFFFAOYSA-N 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- YMOONIIMQBGTDU-VOTSOKGWSA-N [(e)-2-bromoethenyl]benzene Chemical compound Br\C=C\C1=CC=CC=C1 YMOONIIMQBGTDU-VOTSOKGWSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- 150000007824 aliphatic compounds 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
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- AOGYCOYQMAVAFD-UHFFFAOYSA-N chlorocarbonic acid Chemical class OC(Cl)=O AOGYCOYQMAVAFD-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- JYGFTBXVXVMTGB-UHFFFAOYSA-N indolin-2-one Chemical compound C1=CC=C2NC(=O)CC2=C1 JYGFTBXVXVMTGB-UHFFFAOYSA-N 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- ASHGTJPOSUFTGB-UHFFFAOYSA-N methyl resorcinol Natural products COC1=CC=CC(O)=C1 ASHGTJPOSUFTGB-UHFFFAOYSA-N 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- JESXATFQYMPTNL-UHFFFAOYSA-N mono-hydroxyphenyl-ethylene Chemical group OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- CYTJMBLSQUBVMS-UHFFFAOYSA-N n-[[2-cyanopropan-2-yl(formyl)amino]hydrazinylidene]formamide Chemical compound N#CC(C)(C)N(C=O)NN=NC=O CYTJMBLSQUBVMS-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- SJDACOMXKWHBOW-UHFFFAOYSA-N oxyphenisatine Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2NC1=O SJDACOMXKWHBOW-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 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)
- Macromonomer-Based Addition Polymer (AREA)
- Optical Record Carriers And Manufacture Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、平均一分子当り少なくとも一つの不飽和末端
基を有する芳香族ポリカーボネート樹脂とスチレン系モ
ノマーとのラジカル共重合反応系中に、分子量調節剤と
無水マレイン酸又はマレイミドとを連続的又は間欠的に
供給してラジカル共重合を行うことを特徴とする無水マ
レイン酸又はマレイミド成分を含有するスチレン系樹脂
とポリカーボネートとの熱可塑性グラフ共重合体を得る
ものであり、簡便な操作により優れた透明性、高流動性
、優れた相溶性及び低減化された光学歪を有する組成物
を提供できるものであり、光ディスク、光学用レンズ、
光カード、光テープ或は車両のヘッドランプ、テールラ
ンプ、密閉形照明器具、計器板或は樹脂の相溶化剤等に
も好適に使用可能なものである。Detailed Description of the Invention [Industrial Field of Application] The present invention provides a radical copolymerization reaction system of an aromatic polycarbonate resin having at least one unsaturated end group per molecule on average and a styrene monomer. Thermoplastic graph copolymerization of a styrenic resin containing a maleic anhydride or maleimide component and polycarbonate, characterized by carrying out radical copolymerization by continuously or intermittently supplying a modifier and maleic anhydride or maleimide. It can provide a composition with excellent transparency, high fluidity, excellent compatibility, and reduced optical distortion through simple operations, and can be used for optical discs, optical lenses,
It can also be suitably used for optical cards, optical tapes, vehicle headlamps, taillamps, closed lighting fixtures, instrument panels, resin compatibilizers, and the like.
従来、光学用透明成形品の材料としては、アクリル樹脂
が透明性、流動性が良く複屈折が小さいなどの特徴から
光学用透明成形品の材料として知られている(特開昭5
6−131654号他)。しかし、アクリル樹脂は耐熱
性が約70℃と低く、耐衝撃性も低く、水分により反り
を生じ易いという欠点がある。Conventionally, acrylic resin has been known as a material for optical transparent molded products because of its transparency, good fluidity, and low birefringence (Japanese Patent Application Laid-Open No.
No. 6-131654, etc.). However, acrylic resin has drawbacks such as low heat resistance of about 70° C., low impact resistance, and easy warping due to moisture.
上記の欠点をなくす為、粘度平均分子量15.000〜
18.000のポリカーボネート樹脂をディスクやしン
ズなどの成形材料として用いること(特開昭58−18
0553号)が検討されているが、尚流動性が不十分有
り、重要視されている複屈折が大きい等の欠点を有し、
その使用には限界がある。In order to eliminate the above drawbacks, the viscosity average molecular weight is 15.000~
18,000 polycarbonate resin as a molding material for discs, resins, etc.
No. 0553) is being considered, but it still has drawbacks such as insufficient fluidity and large birefringence, which is considered important.
There are limits to its use.
上記の理由から、芳香族ポリカーボネート樹脂の持つ優
れた特徴を維持し、光学的歪を解消する方法が検討され
ている。For the above reasons, methods of maintaining the excellent characteristics of aromatic polycarbonate resins and eliminating optical distortion are being investigated.
流動性の改良からは、芳香族ポリカーボネート樹脂とビ
ニル芳香族ポリマーとを配合してなる組成物は周知であ
るが、相溶性に難点が有り、この改良方法が種々検討さ
れ、例えば、変性ポリスチレンと2価のフェノール類と
を共重合させる方法(J、Polymer Sci、
Pt、−1,vol、 7 1339〜1347(19
69)等)、フェノール性水酸基含有変性ポリスチレン
存在下に2価のフェノール類を重合させる方法、変性ポ
リカーボネート樹脂とスチレンモノマーを溶液重合させ
る方法(特公昭48−2506公報、特開昭55−50
009号公報等)がある。Compositions made by blending aromatic polycarbonate resins and vinyl aromatic polymers are well known for improving flowability, but they have problems with compatibility, and various methods for improving this have been studied. Method for copolymerizing divalent phenols (J, Polymer Sci,
Pt, -1, vol, 7 1339-1347 (19
69), etc.), a method of polymerizing dihydric phenols in the presence of modified polystyrene containing phenolic hydroxyl groups, a method of solution polymerizing modified polycarbonate resin and styrene monomer (Japanese Patent Publication No. 48-2506, JP-A No. 55-50)
No. 009, etc.).
これらの方法は優れたものであるが、光学的な均一性、
耐熱性から満足なものといえない。Although these methods are excellent, optical uniformity,
It cannot be said that the heat resistance is satisfactory.
本発明者らは、上記の欠点を改良する方法について鋭意
検討した結果、不飽和末端基を有する芳香族ポリカーボ
ネートとスチレン系モノマーの共重合反応系に連鎖移動
剤、無水マレイン酸及びマレイミド成分を連続的または
間欠的に供給して共重合する方法を見いだし、本発明を
完成するに至った。As a result of intensive studies on methods to improve the above-mentioned drawbacks, the present inventors discovered that a chain transfer agent, maleic anhydride, and maleimide components were continuously added to a copolymerization reaction system of an aromatic polycarbonate having an unsaturated end group and a styrene monomer. The present inventors discovered a method of copolymerizing by supplying the compound periodically or intermittently, and completed the present invention.
すなわち、平均一分子当り少なくとも一つの不飽和末端
基を有する芳香族ポリカーボネートとスチレン系モノマ
ーとのラジカル共重合反応系中に、分子量調節剤と無水
マレイン酸又はマレイミドとを連続的または間欠的に供
給してラジカル共重合を行うことを特徴とする無水マレ
イン酸又はマレイミド成分を含有するスチレン系樹脂と
ポリカーボネートとの熱可塑性グラフト共重合体の製造
法である。That is, a molecular weight regulator and maleic anhydride or maleimide are continuously or intermittently supplied into a radical copolymerization reaction system of an aromatic polycarbonate having at least one unsaturated end group per molecule on average and a styrene monomer. This is a method for producing a thermoplastic graft copolymer of a styrene resin containing a maleic anhydride or maleimide component and polycarbonate, which is characterized by carrying out radical copolymerization.
以下、本発明の構成について説明する。The configuration of the present invention will be explained below.
本発明の平均一分子当り少なくとも一つの不飽和末端基
を有する芳香族ポリカーボネートの製法は、連鎖移動剤
もしくは末端停止剤として不飽和二重結合を有する一官
能性化合物を、またはこれと従来の末端停止剤を併用し
てもちいる他は従来の芳香族ポリカーボネート樹脂と同
様の製法、界面重合法、ピリジン法、クロロホルメート
法等の溶液法で製造されるものであり、粘度平均分子量
2、000〜100,000 、好ましくは5.000
〜50.000、特に6.000〜30.000のもの
である。The process for producing an aromatic polycarbonate having at least one unsaturated end group per molecule of the present invention uses a monofunctional compound having an unsaturated double bond as a chain transfer agent or end stopper, or a monofunctional compound having an unsaturated double bond in combination with a conventional end end group. It is manufactured by the same method as conventional aromatic polycarbonate resins, except that a terminator is used in combination, and by a solution method such as an interfacial polymerization method, a pyridine method, or a chloroformate method, and has a viscosity average molecular weight of 2,000. ~100,000, preferably 5.000
~50,000, especially those between 6,000 and 30,000.
本発明のポリカーボネート樹脂構造単位の製造に使用す
る二価フェノール系化合物として好ましものは、具体的
にはビス(4−ヒドロキシフェニル)メタン、1.1−
ビス (4−ヒドロキシフェニル)エタン、1.1−ビ
ス(4−ヒドロキシフェニル)プロパン、2.2−ビス
(4−ヒドロキシフェニル)プロパン、2.2−ビス(
4−ヒドロキシフェニル)ブタン、2゜2−ビス(4−
ヒドロキシフェニル)ペンタン、2.2−ビス(4−ヒ
ドロキシフェニル)インペンタン、2゜2−ビス(4−
ヒドロキシフェニル)ヘキサン、2.2−ビス(4−ヒ
ドロキシフェニル)イソヘキサン、4゜4′−ジヒドロ
キシトリフェニルメタン、4,4°−ジヒドロキシテト
ラフェニルメタン、2.2−ビス(4−ヒドロキシ−3
−メチルフェニル)プロパン、2.2−ビス(4−ヒド
ロキシ−3,5−ジメチルフェニル)プロパン、1,1
−ビス(4−ヒドロキシフェニル)シクロヘキサン、1
,1−ビス(4−ヒドロキシフェニル)−1−フェニル
エタン、ビス(4−ヒドロキシフェニル)ジフェニルエ
タン、ジヒドロキシジフェニルスルホン、ジヒドロキシ
ジフェニルスルフィド、ジヒドロキシジフェニルエーテ
ル等のビスフェノール類及びハイドロキノン、レゾルシ
ン、ローメチルレゾルシン、0−クミルレゾルシンとい
った二価のフェノール類が例示され、2,2−ビス(4
−ヒドロキシフェニル)プロパンの使用は特に好ましい
。Preferred dihydric phenol compounds used in the production of the polycarbonate resin structural unit of the present invention include bis(4-hydroxyphenyl)methane, 1.1-
Bis(4-hydroxyphenyl)ethane, 1.1-bis(4-hydroxyphenyl)propane, 2.2-bis(4-hydroxyphenyl)propane, 2.2-bis(
4-hydroxyphenyl)butane, 2゜2-bis(4-
hydroxyphenyl)pentane, 2.2-bis(4-hydroxyphenyl)inpentane, 2゜2-bis(4-
hydroxyphenyl)hexane, 2,2-bis(4-hydroxyphenyl)isohexane, 4°4'-dihydroxytriphenylmethane, 4,4°-dihydroxytetraphenylmethane, 2,2-bis(4-hydroxy-3
-methylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 1,1
-bis(4-hydroxyphenyl)cyclohexane, 1
, 1-bis(4-hydroxyphenyl)-1-phenylethane, bis(4-hydroxyphenyl)diphenylethane, dihydroxydiphenyl sulfone, dihydroxydiphenyl sulfide, dihydroxydiphenyl ether, and other bisphenols, and hydroquinone, resorcinol, low methylresorcinol, 0 -Dihydric phenols such as cumylresorcin are exemplified, and 2,2-bis(4
-hydroxyphenyl)propane is particularly preferred.
又、不飽和末端基を導入するための不飽和二重結合を有
する一官能性化合物としてはアクリル酸クロライド、メ
タアクリル酸クロライド、ソルビン酸クロライド、アリ
ルアルコールクロロホルメート及ヒイソプロペニルフェ
ノールクロロホルメートなどの酸クロライドやクロロホ
ルメート:イソプロペニルフェノール、ヒドロキシスチ
レン、ヒドロキシフェニイルマレイミド、ヒドロキシ安
息香酸アリルエステル及びヒドロキシ安息香酸メチルア
リルエステルなどの不飽和基を有するフェノール類等が
挙げられる。これらの化合物は従来の末端停止剤と併用
してもよいものであり、上記した二価フエーノル化合物
1モルに対して、1〜25モル%、好ましくは1.5〜
10モル%の範囲で使用される。In addition, examples of monofunctional compounds having an unsaturated double bond for introducing an unsaturated terminal group include acrylic acid chloride, methacrylic acid chloride, sorbic acid chloride, allyl alcohol chloroformate, and hyisopropenylphenol chloroformate. acid chlorides and chloroformates: phenols having unsaturated groups such as isopropenylphenol, hydroxystyrene, hydroxyphenylmaleimide, hydroxybenzoic acid allyl ester, and hydroxybenzoic acid methyl allyl ester. These compounds may be used in combination with conventional terminal capping agents, and are used in an amount of 1 to 25 mol %, preferably 1.5 to 25 mol %, based on 1 mol of the above-mentioned dihydric phenol compound.
It is used in a range of 10 mol%.
本発明のポリカーボネート樹脂は上記の成分を必須とし
て製造するものであるが、分岐化剤を上記の二価フェノ
ール系化合物に対して、0.01〜3モル%、特に0.
1〜1モル%の範囲で併用して分岐化ポリカーボネート
とすることもできる。The polycarbonate resin of the present invention is produced with the above-mentioned components as essential, but the branching agent is added in an amount of 0.01 to 3 mol%, especially 0.01 to 3 mol%, based on the dihydric phenol compound mentioned above.
A branched polycarbonate can also be obtained by using them together in a range of 1 to 1 mol %.
このような分岐化剤としてはフロログリシン、2.6−
シメチルー2.4.6− )リ (4−ヒドロキシフェ
ニル)へブテン−3,4,6−シメチルー2.4.6−
トリ (4−ヒドロキシフェニル)へブテン−2,1,
3,5−1−IJ(2−ヒドロキシフェニル)ペンゾー
ル、1.1.1−トリ (4−ヒドロキシフェニル)エ
タン、2.6−ビス(2−ヒドロキシ−5−メチルベン
ジル)−4−メチルフェノール、α、α°、α−トリ
(4−ヒドロキシフエ= Jlz) −1,3,5−)
IJイソプロピルベンゼンなどで例示されるポリヒド
ロキシ化合物及び3,3−ビス(4−ヒドロキシアリー
ル)オキシインドール(=イサチンビスフェノール)、
5−クロルイサチン、5.7−ジクロルイサチン、5−
ブロムイサチン等が例示される。Such branching agents include phloroglycin, 2.6-
cymethyl-2.4.6-)li(4-hydroxyphenyl)hebutene-3,4,6-cymethyl-2.4.6-
tri(4-hydroxyphenyl)hebutene-2,1,
3,5-1-IJ(2-hydroxyphenyl)penzole, 1.1.1-tri(4-hydroxyphenyl)ethane, 2.6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol , α, α°, α−tri
(4-hydroxyfe=Jlz) -1,3,5-)
Polyhydroxy compounds exemplified by IJ isopropylbenzene and 3,3-bis(4-hydroxyaryl)oxindole (=isatin bisphenol),
5-chloroisatin, 5.7-dichlorisatin, 5-
Bromyisatin and the like are exemplified.
本発明のスチレン系モノマーとは、具体的にはスチレン
、0−メチルスチレン、p−メチルスチレンα−メチル
スチレン、0−ブチルスチレン、p−ブチルスチレン、
クロロスチレン、ブロモスチレン、2.4−ジメチルス
チレン等が挙げられる。The styrenic monomer of the present invention specifically includes styrene, 0-methylstyrene, p-methylstyrene α-methylstyrene, 0-butylstyrene, p-butylstyrene,
Examples include chlorostyrene, bromostyrene, 2,4-dimethylstyrene, and the like.
上記した末端不飽和基を有する芳香族ポリカーボネート
樹脂とスチレン系モノマーとの使用量比は特に制限はな
いものであるが、通常、重世比で芳香族ポリカーボネー
ト樹脂:スチレン系モノマー=3:97〜70 : 3
0、好ましくは5二95〜60 : 40の割合である
。The ratio of the aromatic polycarbonate resin having the above-mentioned terminal unsaturated group and the styrene monomer is not particularly limited, but the ratio of aromatic polycarbonate resin to styrene monomer is usually 3:97 to 3:97. 70:3
The ratio is preferably 5295 to 60:40.
本発明ではスチレン系モノマーに併用して無水マレイン
酸又はマレイミド成分を使用する。In the present invention, a maleic anhydride or maleimide component is used in combination with the styrenic monomer.
無水マレイン酸又はマレイミド成分の具体的な例として
無水マレイン酸、α−メチル無水マレイン酸などの無水
マレイン酸;N−メチルマレイミド、N−エチルマレイ
ミド、N−プロピルマレイミド、N−ブチルマレイミド
、N−シクロへキシルマレイミド、N−ベンジルマレイ
ミド、N−フェニルマレイミドなどのマレイミドが挙げ
られ、無水マレイン酸、N−シクロへキシルマレイミド
、N−フェニルマレイミドの使用は特に好ましい。Specific examples of maleic anhydride or maleimide components include maleic anhydride such as maleic anhydride and α-methylmaleic anhydride; N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N- Examples include maleimides such as cyclohexylmaleimide, N-benzylmaleimide, and N-phenylmaleimide, and the use of maleic anhydride, N-cyclohexylmaleimide, and N-phenylmaleimide is particularly preferred.
無水マレイン酸又はマレイミド成分の使用量はスチレン
系モノマーとの合計重量対して1〜50モル%、好まし
くは2〜45モル%、特に3〜40モル%が好ましい。The amount of maleic anhydride or maleimide component to be used is preferably 1 to 50 mol%, preferably 2 to 45 mol%, particularly 3 to 40 mol%, based on the total weight with the styrene monomer.
本発明のラジカル共重合における分子量調節の手段とし
ては■熱重合温度による方法、■後述する開始剤濃度に
よる方法及び■分子量調節剤による方法が挙げられる。Means for controlling the molecular weight in the radical copolymerization of the present invention include (1) a method using a thermal polymerization temperature, (2) a method using an initiator concentration as described below, and (2) a method using a molecular weight regulator.
前記の各々の方法を併用して用いることも有効であるが
分子量調節剤を利用する方法は、本発明のグラフト重合
において特に効果的である。Although it is effective to use each of the above methods in combination, the method using a molecular weight regulator is particularly effective in the graft polymerization of the present invention.
分子量調節剤としては有機硫黄系化合物を用いられる。An organic sulfur compound is used as the molecular weight regulator.
好ましい有機硫黄系化合物としては炭素数1〜30の脂
肪族または芳香族化合物であり、具体的にはロープチル
メルカプタン、イソブチルメルカプタン、n−オクチル
メルカプタン、n−ドデシルメルカプタン、5ec−ブ
チルメルカプタン、5ec−ドデシルメルカプタン、t
ert−ブチルメルカプタンなどの第一、二、三級のメ
ルカプタン;フェニルメルカプタン、チオクレゾール、
4−tert−ブチルチオクレゾールなどの芳香族メル
カプタン;チオグリコール酸とそのエステル;エチレン
チオグリコール等のごとき炭素数3〜18のメルカプタ
ンを挙げることができ、n−ブチルメルカプタン、te
rt−ブチルメルカプタン及びn−オクチルメルカプタ
ンが最も好ましい。その使用量は、用いる末端不飽和基
を有する芳香族ポリカーボネート樹脂とスチレン系モノ
マー並びに無水マレイン酸及びマレイミド成分との合計
景の5重量%以下、好ましくは(L 0004〜2重量
%の範囲である。5重量%を越えて使用した場合、重合
度が低くなり、機械的物性などが低下するので好ましく
ない。Preferred organic sulfur compounds are aliphatic or aromatic compounds having 1 to 30 carbon atoms, and specific examples include ropetyl mercaptan, isobutyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, 5ec-butyl mercaptan, and 5ec- dodecyl mercaptan, t
Primary, secondary, and tertiary mercaptans such as ert-butyl mercaptan; phenyl mercaptan, thiocresol,
Examples include aromatic mercaptans such as 4-tert-butylthiocresol; thioglycolic acid and its esters; mercaptans having 3 to 18 carbon atoms such as ethylene thioglycol;
Most preferred are rt-butyl mercaptan and n-octyl mercaptan. The amount used is 5% by weight or less, preferably in the range of (L 0004 to 2% by weight) based on the total weight of the aromatic polycarbonate resin having a terminal unsaturated group, the styrene monomer, and the maleic anhydride and maleimide components used. If it is used in an amount exceeding 5% by weight, the degree of polymerization will decrease and mechanical properties will deteriorate, which is not preferable.
本発明において使用可能な重合開始剤としては例えば、
ジーtert−ブチルパーオキサイド、ジノニルパーオ
キサイド、メチルエチルケトンパーオキサイド、ジーt
ert−ブチルシバーフタレート、ラウロイルパーオキ
サイド、ジーtert−アミルパーオキサイド、ジクミ
ルパーオキサイド、tert−ブチルクミルパーオキサ
イド、ベンゾイルパーオキサイドの有機過酸化物;2,
2−アゾビスイソブチロニトリル、1,1−アゾビスシ
クロヘキサンカルボニトリル、2−シアノ−2−プロピ
ルアゾホルムアミド等のアゾ化合物を挙げることができ
、使用量は一般的には0〜1重量%の範囲である。Examples of polymerization initiators that can be used in the present invention include:
G-tert-butyl peroxide, dinonyl peroxide, methyl ethyl ketone peroxide, G-t
Organic peroxides of tert-butyl ciber phthalate, lauroyl peroxide, di-tert-amyl peroxide, dicumyl peroxide, tert-butyl cumyl peroxide, benzoyl peroxide; 2,
Examples include azo compounds such as 2-azobisisobutyronitrile, 1,1-azobiscyclohexanecarbonitrile, and 2-cyano-2-propylazoformamide, and the amount used is generally 0 to 1% by weight. is within the range of
又、本発明においては重合反応は塊状重合で実施するた
め溶媒は必須成分ではないが希釈剤として使用すること
が出来る。使用し得る溶媒としてポリカーボネート樹脂
やポリスチレン等の溶媒として公知のものが使用可能で
あり、例えば、塩化メチレン、トルエン、キシレン、ベ
ンゼン、メチルエチルケトン、メチルイソブチルケトン
、シクロヘキサノン、酢酸ブチル等が挙げられる。Further, in the present invention, since the polymerization reaction is carried out by bulk polymerization, the solvent is not an essential component, but can be used as a diluent. Usable solvents include those known as solvents such as polycarbonate resins and polystyrene, such as methylene chloride, toluene, xylene, benzene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, butyl acetate, and the like.
グラフト重合の方法は、以上説明した成分を用い、使用
原料が溶融又は可塑化状態を維持出来る条件であり、温
度40〜250℃、好ましくは60〜180℃、特に7
0〜150℃で10時間以内、好ましくは20分〜6時
間が好適である。The method of graft polymerization uses the components explained above, and the conditions are such that the raw materials used can maintain a molten or plasticized state, at a temperature of 40 to 250°C, preferably 60 to 180°C, especially 70°C.
Suitable time is 0 to 150°C for 10 hours or less, preferably 20 minutes to 6 hours.
重合の方法は溶媒を用いない塊状重合又は溶媒の存在下
での溶液重合等で行われるが経済性等の点から塊状重合
が好ましい。The polymerization may be carried out by bulk polymerization without using a solvent or solution polymerization in the presence of a solvent, but bulk polymerization is preferred from the economic point of view.
芳香族ポリカーボネート及びスチレンの仕込方法方法は
重合初期に一括して仕込んでも良いし、一部分を連続的
に反応系へ供給してもよい。Aromatic polycarbonate and styrene may be charged all at once at the initial stage of polymerization, or a portion may be continuously supplied to the reaction system.
本発明の重合の特色は、グラフト共重合体が熱可塑性で
あることである。これを確実にするため、無水マレイン
酸又はマレイミド成分の仕込方法は重合反応全般にわた
って連続的または間欠的に供給する。例えば、反応初期
に一括して上記成分を仕込んだ場合、グラフト共重合体
中のスチレン−無水マレイン酸(マレイミド成分)交互
共重合体構成単位の生成が先行し、ポリマーが不溶化し
、反応が均一に進行しない。又、著しい場合にはグラフ
ト共重合体はゲル化または架橋化して熱可塑性でなくな
る。A feature of the polymerization of the present invention is that the graft copolymer is thermoplastic. To ensure this, the maleic anhydride or maleimide component is fed continuously or intermittently throughout the polymerization reaction. For example, if the above components are added all at once at the beginning of the reaction, the formation of the styrene-maleic anhydride (maleimide component) alternating copolymer constituent units in the graft copolymer precedes the formation of the polymer, making the polymer insolubilized and ensuring a uniform reaction. does not proceed. Also, in severe cases, the graft copolymer gels or crosslinks and ceases to be thermoplastic.
一方、連鎖移動剤の仕込み方法は、重合反応全般にわた
って連続的または間欠的に供給しなければならない。も
し連鎖移動剤の供給が絶たれると反応系中の連鎖移動剤
は短時間で消費され、以後生成するポリスチレン鎮を含
有するグラフト共重合体は分子量が調節されないため、
高分子化或いはゲル化または架橋して熱可塑性でなくな
る。On the other hand, the chain transfer agent must be fed continuously or intermittently throughout the entire polymerization reaction. If the supply of chain transfer agent is cut off, the chain transfer agent in the reaction system will be consumed in a short period of time, and the molecular weight of the graft copolymer containing polystyrene produced thereafter will not be controlled.
It becomes polymerized, gels, or crosslinks and becomes non-thermoplastic.
無水マレイン酸又はマレイミド成分の均一な分布及び分
子量分布の整ったグラフト共重合体を得る為に単位時間
当りのスチレンと無水マレイン酸又はマレイミド成分と
の反応世と単位時間当りの連鎖移動剤の供給量の比をで
きるだけ一定に近ずけることが望ましい。そのためには
、(1)無水マレイン酸又はマレイミド成分並びに連鎖
移動剤の供給速度を一定にし、スチレン系モノマーの重
合による消費速度を一定にすべくスチレン系モノマー及
び開始剤の供給方法等を工夫する。或いは(2)スチレ
ン系モノマーの消費速度に合せて無水マレイン酸及びマ
レイミド成分並びに連鎖移動剤の供給速度を変化させる
ことであり、この二つの方法から選択し実施すれば良い
。In order to obtain a graft copolymer with uniform distribution of the maleic anhydride or maleimide component and a well-organized molecular weight distribution, the reaction between styrene and the maleic anhydride or maleimide component per unit time and the supply of a chain transfer agent per unit time are performed. It is desirable to keep the ratio of amounts as close to constant as possible. To achieve this, (1) the supply rate of the maleic anhydride or maleimide component and the chain transfer agent should be kept constant, and the method of supplying the styrenic monomer and initiator should be devised to keep the consumption rate of the styrenic monomer by polymerization constant; . Alternatively, (2) the supply rate of maleic anhydride, maleimide components, and chain transfer agent may be changed in accordance with the consumption rate of the styrene monomer, and the method may be selected from these two methods.
又、本発明のグラフト共重合体を光学用途等に使用する
場合には、所望に応じて、反応に先だって使用原料を精
製してもちいること、精製した重合物から微細なダスト
を除くために、適宜溶媒を使用して精密濾過遠心分離な
どの手段を使用してもよい。In addition, when the graft copolymer of the present invention is used for optical purposes etc., the raw materials used may be purified prior to the reaction, if desired, and in order to remove fine dust from the purified polymer. Means such as microfiltration and centrifugation using appropriate solvents may also be used.
本発明のグラフト共重合体は上記のごときものであるが
、必要に応じて、その他の樹脂、酸化防止剤、光安定剤
、着色剤、無機或は有機の充填剤類、炭素繊維、ガラス
繊維等の補強剤、滑剤、帯電防止剤などを適宜併用して
も良いものである。The graft copolymer of the present invention is as described above, but if necessary, it may contain other resins, antioxidants, light stabilizers, colorants, inorganic or organic fillers, carbon fibers, glass fibers. Reinforcing agents, lubricants, antistatic agents, etc. may be used in combination as appropriate.
以下、実施例等によって具体的に説明する。 Hereinafter, this will be explained in detail using examples and the like.
尚、実施例等の粘度平均分子壷、全光線透過率、曇価、
ビカット軟化温度及び粗分散は、下記の方法により求め
たものである。In addition, the viscosity average molecular bottle, total light transmittance, haze value,
The Vicat softening temperature and coarse dispersion were determined by the following method.
(1)、粘度平均分子量
*溶液粘度の測定
試料溶液=a度 1g/100m1の塩化メチレン溶液
。(1), Viscosity average molecular weight *Measurement of solution viscosity Sample solution = a methylene chloride solution of 1 g/100 ml.
粘度計 :溶媒のみのフロータイム(T、) 72.3
6秒の毛細管式改良ウベローデ型粘度計
測定温度:20℃±0.01℃
この測定により、濃度0.6g/100 rnlのフロ
ータイム(T)を測定する。Viscometer: Flow time of solvent only (T,) 72.3
Measurement temperature using a capillary improved Ubbelohde viscometer for 6 seconds: 20° C.±0.01° C. Through this measurement, the flow time (T) at a concentration of 0.6 g/100 rnl is determined.
**計算
上記の測定から、式■、■よりη1.5、η8P、内を
算出し、■(Schellの式)よりMvを求める。**Calculation From the above measurements, calculate η1.5 and η8P from formulas (1) and (2), and obtain Mv from (2) (Schell's formula).
η、、= T/T、 −1(ηreL =T/T、)
−−−■η、P/C= [ηコ +に’ [η]
2/C−−−■[ηコ :極限(固有)粘度
[η] =に、Mv ・・・■に
、、 : 1.23x 10−’
α :0.83
(2)、全光線透過率及び曇価
*サンプル:厚み3胴の成形品
(3)、ビカット軟化温度
JIS K 7206 A 法1kg荷重で実施。η,, = T/T, -1(ηreL =T/T,)
−−−■η, P/C= [η co +ni' [η]
2/C---■[ηko: limit (intrinsic) viscosity [η] =, Mv...■,,: 1.23x 10-' α: 0.83 (2), total light transmittance and haze value *Sample: Molded product (3) with thickness of 3 cylinders, Vicat softening temperature JIS K 7206 A method Conducted with 1 kg load.
(4)、 ミlu相分散 電子顕微鏡による観察。(4), Milu phase dispersion, observation using an electron microscope.
参考例1〜3
水酸化ナトリウム220gを水2.651に溶解し、2
0℃に保ちながら、2,2−ビス(4−ヒドロキシフェ
ニル)プロパン(以下、BPAと記す) 456g、
ハイドロサルファイド 0.5gを溶解した。Reference Examples 1 to 3 220g of sodium hydroxide was dissolved in 2.65ml of water,
While maintaining at 0°C, 456 g of 2,2-bis(4-hydroxyphenyl)propane (hereinafter referred to as BPA),
0.5 g of hydrosulfide was dissolved.
これにメチレンクロライド(以下、MCと記す)1.5
1を加えて撹伴しつつホスゲンを吹き込ミ、30分後に
p−イソプロペニルフェノール19.5gを含むMC1
250gを加え、更にホスゲンを30分間吹き込んだ。Add to this 1.5 methylene chloride (hereinafter referred to as MC)
After 30 minutes, MC1 containing 19.5 g of p-isopropenylphenol was added.
250 g was added, and phosgene was further blown in for 30 minutes.
ホスゲン吹き込み終了後、激しく撹伴して反応液を乳化
させ、乳化後、1%トリエチルアミンのMC溶液30
mlを加え、約1時間撹伴を続は重合させた。After the completion of phosgene blowing, the reaction solution was emulsified by stirring vigorously, and after emulsification, 1% triethylamine MC solution 30
ml was added, and the mixture was stirred for about 1 hour to continue polymerization.
重合液を水槽と有機相に分離し、有機相をリン酸で中和
した後、数回水洗を繰り返した後、メタノールへ適下し
て共重合体を沈澱させ、濾過し、乾燥して白色粉末を得
た。Separate the polymerization solution into a water tank and an organic phase, neutralize the organic phase with phosphoric acid, repeat water washing several times, drop into methanol to precipitate the copolymer, filter, and dry to white. A powder was obtained.
この粉末のMCの溶液の粘度測定からの粘度平均分子量
は16.000であった。The viscosity average molecular weight of this powder was found to be 16.000 by measuring the viscosity of a MC solution.
末端停止剤の使用量等を変化させる他は同様にして、粘
度平均分子量は9.800.25.100の末端不飽和
ポリカーボネートを得た。以下、これらを粘度平均分子
量の低いものから順にPCI、 PC2,PC3と呼ぶ
。A terminally unsaturated polycarbonate having a viscosity average molecular weight of 9.800.25.100 was obtained in the same manner except that the amount of the terminal capping agent used was changed. Hereinafter, these will be referred to as PCI, PC2, and PC3 in descending order of viscosity average molecular weight.
実施例1
参考例1で合成したPC125g、スチレンモノマー(
以下、Stと記す)100gを耐圧容器に入れ窒素置換
を行った後、撹伴下に120℃まで昇温し、n−ドデシ
ルメルカプタン(以下、NDSと記す) 0.11g
及び無水マレイン酸(以下、MAと記す)1、54gを
含むSt 15gの溶液を添加しつつ、100分間反応
した。Example 1 125g of PC synthesized in Reference Example 1, styrene monomer (
After putting 100 g of n-dodecyl mercaptan (hereinafter referred to as NDS) into a pressure container and purging with nitrogen, the temperature was raised to 120°C with stirring, and 0.11 g of n-dodecyl mercaptan (hereinafter referred to as NDS)
The mixture was reacted for 100 minutes while adding a solution of 15 g of St containing 1.54 g of maleic anhydride (hereinafter referred to as MA).
反応終了後、生成物を塩化メチレンに溶解しメタノール
へ加え沈澱下し PC/PS/MA= 61.9/34
.3/3.8(重量比)のポリマー40.3gを得た。After the reaction was completed, the product was dissolved in methylene chloride and added to methanol for precipitation. PC/PS/MA=61.9/34
.. 40.3 g of polymer having a weight ratio of 3/3.8 was obtained.
このポリマーを用い、(株)東邦インターナショナル製
、油圧成形機TT−2004Aで3mm厚の成形品を得
、24時間放置後、全光線透過率(%)、曇価(%)、
ビカット軟化温度及び相分散を測定した。結果を第1表
に示した。Using this polymer, a molded product with a thickness of 3 mm was obtained using a hydraulic molding machine TT-2004A manufactured by Toho International Co., Ltd., and after being left for 24 hours, the total light transmittance (%), haze value (%),
Vicat softening temperature and phase dispersion were measured. The results are shown in Table 1.
実施例2〜8及び比較例1
用いるポリカーボネート樹脂の種類、その他の条件を第
1表に示したように変更する他は実施例1に準じて成形
品の製造及び測定を行った。Examples 2 to 8 and Comparative Example 1 Molded articles were manufactured and measured in accordance with Example 1, except that the type of polycarbonate resin used and other conditions were changed as shown in Table 1.
結果を第1表に示した。The results are shown in Table 1.
比較例2
実施例1にふいて、MA成分を一括仕込み原料として反
応系に仕込む他は同様にして反応を試みたところ、反応
液の粘度が急速に上昇し、反応を続けることが出来なく
なった。Comparative Example 2 When a reaction was attempted in the same manner as in Example 1 except that the MA component was charged all at once into the reaction system as a raw material, the viscosity of the reaction solution increased rapidly and the reaction could not be continued. .
Claims (1)
芳香族ポリカーボネートとスチレン系モノマーとのラジ
カル共重合反応系中に、分子量調節剤と無水マレイン酸
又はマレイミドとを連続的または間欠的に供給してラジ
カル共重合を行うことを特徴とする無水マレイン酸又は
マレイミド成分を含有するスチレン系樹脂とポリカーボ
ネートとの熱可塑性グラフト共重合体の製造法。A molecular weight regulator and maleic anhydride or maleimide are continuously or intermittently supplied into a radical copolymerization reaction system of an aromatic polycarbonate having at least one unsaturated end group per molecule on average and a styrene monomer. A method for producing a thermoplastic graft copolymer of a styrene resin containing a maleic anhydride or maleimide component and polycarbonate, which comprises performing radical copolymerization.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63154801A JP2658199B2 (en) | 1988-06-24 | 1988-06-24 | Method for producing thermoplastic graft copolymer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63154801A JP2658199B2 (en) | 1988-06-24 | 1988-06-24 | Method for producing thermoplastic graft copolymer |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH026514A true JPH026514A (en) | 1990-01-10 |
JP2658199B2 JP2658199B2 (en) | 1997-09-30 |
Family
ID=15592189
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP63154801A Expired - Lifetime JP2658199B2 (en) | 1988-06-24 | 1988-06-24 | Method for producing thermoplastic graft copolymer |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2658199B2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0700940A1 (en) * | 1994-08-24 | 1996-03-13 | Bayer Ag | Maleic anhydride grafted polycarbonate having allylphenol end groups, and their use for the manufacture of blends with polyamides, and these blends |
CN116234846A (en) * | 2020-09-25 | 2023-06-06 | 株式会社可乐丽 | Resin composition and molded article |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5891716A (en) * | 1981-11-27 | 1983-05-31 | Mitsubishi Petrochem Co Ltd | Production of modified thermoplastic polymer particle |
JPS62138514A (en) * | 1985-12-11 | 1987-06-22 | Hitachi Chem Co Ltd | Resin material for optical use |
JPS63258914A (en) * | 1987-04-16 | 1988-10-26 | Sumitomo Naugatuck Co Ltd | Production of copolymer |
-
1988
- 1988-06-24 JP JP63154801A patent/JP2658199B2/en not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5891716A (en) * | 1981-11-27 | 1983-05-31 | Mitsubishi Petrochem Co Ltd | Production of modified thermoplastic polymer particle |
JPS62138514A (en) * | 1985-12-11 | 1987-06-22 | Hitachi Chem Co Ltd | Resin material for optical use |
JPS63258914A (en) * | 1987-04-16 | 1988-10-26 | Sumitomo Naugatuck Co Ltd | Production of copolymer |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0700940A1 (en) * | 1994-08-24 | 1996-03-13 | Bayer Ag | Maleic anhydride grafted polycarbonate having allylphenol end groups, and their use for the manufacture of blends with polyamides, and these blends |
CN116234846A (en) * | 2020-09-25 | 2023-06-06 | 株式会社可乐丽 | Resin composition and molded article |
Also Published As
Publication number | Publication date |
---|---|
JP2658199B2 (en) | 1997-09-30 |
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