JPS6146007B2 - - Google Patents
Info
- Publication number
- JPS6146007B2 JPS6146007B2 JP19844981A JP19844981A JPS6146007B2 JP S6146007 B2 JPS6146007 B2 JP S6146007B2 JP 19844981 A JP19844981 A JP 19844981A JP 19844981 A JP19844981 A JP 19844981A JP S6146007 B2 JPS6146007 B2 JP S6146007B2
- Authority
- JP
- Japan
- Prior art keywords
- polycarbonate
- polyphenylene oxide
- free radical
- group
- general formula
- 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.)
- Expired
Links
- 239000004417 polycarbonate Substances 0.000 claims description 41
- 229920000515 polycarbonate Polymers 0.000 claims description 41
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 19
- 150000003254 radicals Chemical class 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 3
- 230000005865 ionizing radiation Effects 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 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 8
- 150000002989 phenols Chemical class 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 7
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 241000790917 Dioxys <bee> Species 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- YQUQWHNMBPIWGK-UHFFFAOYSA-N 4-isopropylphenol Chemical compound CC(C)C1=CC=C(O)C=C1 YQUQWHNMBPIWGK-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- -1 diphenol compound Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920005668 polycarbonate resin Polymers 0.000 description 4
- 239000004431 polycarbonate resin Substances 0.000 description 4
- 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 3
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical class OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 3
- 229940045803 cuprous chloride Drugs 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 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
- VLJSLTNSFSOYQR-UHFFFAOYSA-N 3-propan-2-ylphenol Chemical compound CC(C)C1=CC=CC(O)=C1 VLJSLTNSFSOYQR-UHFFFAOYSA-N 0.000 description 2
- 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 2
- CIRRFAQIWQFQSS-UHFFFAOYSA-N 6-ethyl-o-cresol Chemical compound CCC1=CC=CC(C)=C1O CIRRFAQIWQFQSS-UHFFFAOYSA-N 0.000 description 2
- 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 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- KYPYTERUKNKOLP-UHFFFAOYSA-N Tetrachlorobisphenol A Chemical compound C=1C(Cl)=C(O)C(Cl)=CC=1C(C)(C)C1=CC(Cl)=C(O)C(Cl)=C1 KYPYTERUKNKOLP-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- METWAQRCMRWDAW-UHFFFAOYSA-N 2,6-diethylphenol Chemical compound CCC1=CC=CC(CC)=C1O METWAQRCMRWDAW-UHFFFAOYSA-N 0.000 description 1
- ATGFTMUSEPZNJD-UHFFFAOYSA-N 2,6-diphenylphenol Chemical compound OC1=C(C=2C=CC=CC=2)C=CC=C1C1=CC=CC=C1 ATGFTMUSEPZNJD-UHFFFAOYSA-N 0.000 description 1
- YXZPTVOCJLCMRO-UHFFFAOYSA-N 2-bromo-6-methylphenol Chemical compound CC1=CC=CC(Br)=C1O YXZPTVOCJLCMRO-UHFFFAOYSA-N 0.000 description 1
- KUNNUNBSGQSGDY-UHFFFAOYSA-N 2-butyl-6-methylphenol Chemical compound CCCCC1=CC=CC(C)=C1O KUNNUNBSGQSGDY-UHFFFAOYSA-N 0.000 description 1
- XBQRPFBBTWXIFI-UHFFFAOYSA-N 2-chloro-4-[2-(3-chloro-4-hydroxyphenyl)propan-2-yl]phenol Chemical compound C=1C=C(O)C(Cl)=CC=1C(C)(C)C1=CC=C(O)C(Cl)=C1 XBQRPFBBTWXIFI-UHFFFAOYSA-N 0.000 description 1
- XNJCFOQHSHYSLG-UHFFFAOYSA-N 2-chloro-6-ethylphenol Chemical compound CCC1=CC=CC(Cl)=C1O XNJCFOQHSHYSLG-UHFFFAOYSA-N 0.000 description 1
- YPNZJHFXFVLXSE-UHFFFAOYSA-N 2-chloro-6-methylphenol Chemical compound CC1=CC=CC(Cl)=C1O YPNZJHFXFVLXSE-UHFFFAOYSA-N 0.000 description 1
- AKZFZHNJLYDHKN-UHFFFAOYSA-N 2-ethyl-6-propylphenol Chemical compound CCCC1=CC=CC(CC)=C1O AKZFZHNJLYDHKN-UHFFFAOYSA-N 0.000 description 1
- WBHAUHHMPXBZCQ-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound COC1=CC=CC(C)=C1O WBHAUHHMPXBZCQ-UHFFFAOYSA-N 0.000 description 1
- PGJXFACHLLIKFG-UHFFFAOYSA-N 2-methyl-6-phenylphenol Chemical compound CC1=CC=CC(C=2C=CC=CC=2)=C1O PGJXFACHLLIKFG-UHFFFAOYSA-N 0.000 description 1
- KFETUQFRWIVAMU-UHFFFAOYSA-N 2-methyl-6-propan-2-ylphenol Chemical compound CC(C)C1=CC=CC(C)=C1O KFETUQFRWIVAMU-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-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
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- SUCTVKDVODFXFX-UHFFFAOYSA-N 4-(4-hydroxy-3,5-dimethylphenyl)sulfonyl-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(S(=O)(=O)C=2C=C(C)C(O)=C(C)C=2)=C1 SUCTVKDVODFXFX-UHFFFAOYSA-N 0.000 description 1
- AZZWZMUXHALBCQ-UHFFFAOYSA-N 4-[(4-hydroxy-3,5-dimethylphenyl)methyl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(CC=2C=C(C)C(O)=C(C)C=2)=C1 AZZWZMUXHALBCQ-UHFFFAOYSA-N 0.000 description 1
- BWCAVNWKMVHLFW-UHFFFAOYSA-N 4-[1-(4-hydroxy-3,5-dimethylphenyl)cyclohexyl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C2(CCCCC2)C=2C=C(C)C(O)=C(C)C=2)=C1 BWCAVNWKMVHLFW-UHFFFAOYSA-N 0.000 description 1
- OBZFGWBLZXIBII-UHFFFAOYSA-N 4-[3-(4-hydroxy-3,5-dimethylphenyl)-3-methylbutyl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(CCC(C)(C)C=2C=C(C)C(O)=C(C)C=2)=C1 OBZFGWBLZXIBII-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
- GIXXQTYGFOHYPT-UHFFFAOYSA-N Bisphenol P Chemical compound C=1C=C(C(C)(C)C=2C=CC(O)=CC=2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 GIXXQTYGFOHYPT-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000012696 Interfacial polycondensation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- AOGYCOYQMAVAFD-UHFFFAOYSA-N chlorocarbonic acid Chemical group OC(Cl)=O AOGYCOYQMAVAFD-UHFFFAOYSA-N 0.000 description 1
- NFDFQCUYFHCNBW-SCGPFSFSSA-N dienestrol Chemical class C=1C=C(O)C=CC=1\C(=C/C)\C(=C\C)\C1=CC=C(O)C=C1 NFDFQCUYFHCNBW-SCGPFSFSSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tertâbutyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
Description
æ¬çºæã¯ããªã«ãŒãããŒãå
±éåäœã®è£œé æ³ã«
é¢ãã詳ããã¯ç¹å®ã®æ«ç«¯åºãæããããªã«ãŒã
ããŒããšããªããšãã¬ã³ãªãã·ããéé¢åºçºçæ
段ã®ä»åšäžã«åå¿ãããããšã«ãã€ãŠãèç±æ§ã
èè¬åæ§çã«ãããããŸã補èæ§ãæ圢æ§çã®è¯
奜ãªããªã«ãŒãããŒãå
±éåäœãå¹çãããã€æ
æã®å
±éåæ¯ã§èªåšã«è£œé ããããšã®ã§ããæ¹æ³
ã«é¢ããã
åŸæ¥ããããªã«ãŒãããŒãæš¹èã¯ãããããæ©
械çãç±çãé»æ°çæ§è³ªããšããããã®èè¡ææ§
ã«ãããšã³ãžãã¢ãªã³ã°æš¹èãšããŠããç¥ããã
æ©æ¢°éšåãé»æ°éšåãªã©ã«ãã䜿ãããŠãããã
ãããªãããããªã«ãŒãããŒãæš¹èã¯ãã¢ã»ã
ã³ãããã¿ã³ãåå¡©åççŽ ãªã©ãšæ¥è§Šãããšçœå
ãã¯ã¬ãŒãºãçããããã«å¿åäžã§ã¯ã¯ã©ãã¯ã
çºçãããšããæ¬è³ªçãªæ¬ ç¹ãæããŠããããã
ããããç¹æ§ãæããæš¹èã§ãããªãããã®å©
çšãå¿çšåéã倧ããå¶éãããŠããããŸããã®
ããªã«ãŒãããŒãæš¹èã¯ããªã¹ãã¬ã³ç³»æš¹èãªã©
ã®ä»ã®ç±å¯å¡æ§æš¹èãšãã¬ã³ãããéã«çžæº¶æ§ã
ååã§ãªããªã©ã®æ¬ ç¹ããã€ãã
ãããã®æ¬ ç¹ã解æ¶ããããã«ãããªã«ãŒãã
ãŒãæš¹èã«ããªããšãã¬ã³ãªãã·ããæ©æ¢°çã«æ··
åããæ¹æ³ãããã¯æº¶æ¶²ãšããŠæ··åããæ¹æ³ãæ
æ¡ãããŠããïŒç¹å
¬æ42â15782å·å
¬å ±ïŒãããã
ãªããããã®æ¹æ³ã¯åãªãç©ççãªæ··åã«ãã
ããçžæº¶æ§ãååã§ãªãåŸãããçµæç©ã¯äžéæ
ãšãªããšå
±ã«åäžæ§ã«å£ããšããåé¡ç¹ãããã
ãããã®åŸæ¥æè¡ã®æ¬ ç¹ã解æ¶ããç®çã§æ¬çº
æè
ãã¯æ¢ã«ããªã«ãŒãããŒããšããªããšãã¬ã³
ãªãã·ããããªããããã¯å
±éåäœãªãã³ã«ãã®
補é æ³ã®éçºã«æåããŠããïŒç¹é¡æ56â66556
å·æ现æžïŒã
æ¬çºæè
ãã¯ããªã«ãŒãããŒããšããªããšãã¬
ã³ãªãã·ããããªãå
±éåäœãããå¹çãããã
ããææã®å
±éåæ¯ã«ãŠèªåšã«è£œé ããããšã®ã§
ããæ¹æ³ãéçºãã¹ãéæç 究ãéããããã®çµ
æãæ«ç«¯ã«ç¹å®ã®å®èœåºãæããããªã«ãŒãããŒ
ããçšããããã«ããªããšãã¬ã³ãªãã·ããåå¿
ãããããšã«ããç®çãéæãããããšãèŠåº
ããæ¬çºæãå®æããã«è³ã€ããããªãã¡æ¬çºæ
ã¯ã
äžè¬åŒ
ãåŒäžãã¯æ°ŽçŽ ãŸãã¯ææã®çœ®æåºã瀺ãã
R1ããã³R2ã¯ããããã¢ã«ãã«åºãããã¯ã¢ãª
ãŒã«åºã瀺ããã
ã§è¡šããããæ«ç«¯åºãæããããªã«ãŒãããŒããš
ããªããšãã¬ã³ãªãã·ããéé¢åºçºçæ段ãä»åš
ãããŠåå¿ãããããšãç¹åŸŽãšããããªã«ãŒãã
ãŒãå
±éåäœã®è£œé æ³ãæäŸãããã®ã§ããã
æ¬çºæã®æ¹æ³ã«çšããããªã«ãŒãããŒãã¯åè¿°
ã®åŠããæ«ç«¯ã«äžè¬åŒïŒïŒã§è¡šããããå®èœåº
ãæãããã®ã§ãªããã°ãªããªããåŒäžïŒ²ã¯ç¹ã«
å¶éã¯ãªãæ°ŽçŽ ååãããã¯ææã®çœ®æåºã§ãã
ããéåžžã¯æ°ŽçŽ ååãããã²ã³ååãããã¯ã¢ã«
ãã«åºããé©å®éžå®ãããããŸããR1ïŒR2ã¯ã
ãããã¡ãã«åºããšãã«åºããããã«åºçã®ã¢ã«
ãã«åºãããã¯ã¢ãªãŒã«åºã§ããããç¹ã«R1ïŒ
R2ãå
±ã«ã¡ãã«åºã§ããå Žåãæãäžè¬çã§ã
ãã
äžèšã®åŠãã®æ«ç«¯åºãæããããªã«ãŒãããŒã
ã®æ¬äœã¯ãæ§ã
ãªãã®ãèããããåçš®ãžããšã
ãŒã«ååç©ãšãã¹ã²ã³ãããã¯ãžããšãã«ã«ãŒã
ããŒããåå¿ãããŠåŸããããã®ãªã©ãçšããã
ããããã§ãžããšããŒã«ååç©ãšããŠã¯ãéåžž
ã¯ã
äžè¬åŒ
ãããã¯
äžè¬åŒ
ãåŒäžãRâ²ã¯ççŽ æ°ïŒãïŒã®çœ®æãããã¯é
眮æã¢ã«ãã¬ã³åºãââïŒââïŒâSO2âãŸã
ã¯âCOâã§ãããY1ããã³Y2ã¯æ°ŽçŽ ãŸãã¯ãã
ã²ã³ååãïœããã³ïœã¯ïŒãïŒã®æŽæ°ã§ãããã
ã§è¡šãããããã®ããããããšãã§ãããããã
äžèšäžè¬åŒïŒïŒãããã¯ïŒïŒã§è¡šãããããž
ããšããŒã«ååç©ã®äŸãšããŠã¯ãïŒïŒ4â²âãžãã
ããã·ãžããšãã«ïŒïŒïŒïŒâãã¹âïŒïŒâããã
ãã·ããšãã«ïŒâãããã³ïŒãã¹ããšããŒã«
ïŒïŒïŒïŒïŒâãã¹âïŒïŒâããããã·ããšã
ã«ïŒâïŒâã¡ãã«ãã¿ã³ïŒïŒïŒïŒâãã¹âïŒïŒâã
ãããã·ããšãã«ïŒâã·ã¯ããããµã³ïŒÎ±ïŒÎ±â²â
ãã¹âïŒïŒâããããã·ããšãã«ïŒâïœâãžã€ãœã
ããã«ãã³ãŒã³ïŒïŒïŒïŒâãã¹âïŒïŒâã¡ãã«â
ïŒâããããã·ããšãã«ïŒâãããã³ïŒïŒïŒïŒâ
ãã¹âïŒïŒâã¯ããâïŒâããããã·ããšãã«ïŒâ
ãããã³ïŒãã¹âïŒïŒïŒïŒâãžã¡ãã«âïŒâãã
ããã·ããšãã«ïŒâã¡ã¿ã³ïŒïŒïŒïŒâãã¹âïŒïŒïŒ
ïŒâãžã¡ãã«âïŒâããããã·ããšãã«ïŒããã
ã³ïŒãã¹âïŒïŒâããããã·ããšãã«ïŒã¹ã«ã
ã³ïŒãã¹âïŒïŒïŒïŒâãžã¡ãã«âïŒâããããã·
ããšãã«ïŒã¹ã«ãã³ïŒïŒïŒïŒâãã¹âïŒïŒïŒïŒâ
ãžã¡ãã«âïŒâããããã·ããšãã«ïŒâïŒâã¡ã
ã«ãã¿ã³ïŒïŒïŒïŒâãã¹âïŒïŒïŒïŒâãžã¡ãã«â
ïŒâããããã·ããšãã«ïŒâã·ã¯ããããµã³ïŒ
αïŒÎ±â²âãã¹âïŒïŒïŒïŒâãžã¡ãã«âïŒâããã
ãã·ããšãã«ïŒâïœâãžã€ãœãããã«ãã³ãŒã³ïŒ
ïŒïŒïŒâãã¹âïŒïŒïŒïŒâãžã¯ããâïŒâããã
ãã·ããšãã«ïŒâãããã³ããã³ïŒïŒïŒâãã¹â
ïŒïŒïŒïŒâãžããã¢âïŒâããããã·ããšãã«ïŒâ
ãããã³ã§ããããšãã«å¥œãŸãããžããšããŒã«ã®
äŸã¯ïŒïŒïŒâãã¹âïŒïŒâããããã·ããšãã«ïŒâ
ãããã³ïŒïŒïŒïŒâãã¹âïŒïŒïŒïŒâãžã¡ãã«â
ïŒâããããã·ããšãã«ïŒâãããã³ïŒïŒïŒïŒâ
ãã¹âïŒïŒïŒïŒâãžã¯ããâïŒâããããã·ããš
ãã«ïŒâãããã³ïŒïŒïŒïŒâãã¹âïŒïŒïŒïŒâãžã
ãã¢âïŒâããããã·ããšãã«ïŒâãããã³ãã
ã³ïŒïŒïŒâãã¹âïŒïŒâããããã·ããšãã«ïŒâã·
ã¯ããããµã³ã§ããã
ããããžããšããŒã«ã¯åç¬ã§çšããã®ã¿ã§ãªã
æ··åç©ã®åœ¢ã§çšããããšãã§ããã
æ¬çºæã®æ¹æ³ã«çšããããªã«ãŒãããŒãã®æ¬äœ
ã¯ãäžè¿°ã®åŠãåçš®ãžãšããŒã«ååç©ãšãã¹ã²ã³
ãããã¯ãžããšãã«ã«ãŒãããŒãçãšã®åå¿ã«ã
ã€ãŠåŸãããããªã«ãŒãããŒãã§ããããããã«
ããªã«ãŒãããŒãã®åçš®å
±éåäœãäŸãã°ãžãªã
ã·ãžã¢ãªãŒã«ã¢ã«ã«ã³çžäºã®ã³ããªã«ãŒãããŒ
ãããžãªãã·ãžã¢ãªãŒã«ã¢ã«ã«ã³ãšãã以å€ã®è³
éŠæãžãªãã·ååç©ãšã®ã³ããªã«ãŒãããŒãããž
ãªãã·ãžã¢ãªãŒã«ã¢ã«ã«ã³ãšèèªæãžãªãã·åå
ç©ãšã®ã³ããªã«ãŒãããŒãããžãªãã·ãžã¢ãªãŒã«
ã¢ã«ã«ã³ä»¥å€ã®è³éŠæãžãªãã·ååç©çžäºã®ã³ã
ãªã«ãŒãããŒãããžãªãã·ãžã¢ãªãŒã«ã¢ã«ã«ã³ä»¥
å€ã®è³éŠæãžãªãã·ååç©ãšèèªæãžãªãã·åå
ç©ãšã®ã³ããªã«ãŒãããŒããªã©ã®ãã¢çµåå
±éå
äœãããã¯ãšã¹ãã«çµåãæããããªã«ãŒãããŒ
ãããŠã¬ã¿ã³çµåãæããããªã«ãŒãããŒããã
ã®ä»ã®ãããçµåå
±éåäœãªã©ããããããšãã§
ããã
æ¬çºæã®æ¹æ³ã§ã¯ãäžè¿°ã®åŠãããªã«ãŒãããŒ
ãã®æ«ç«¯äœãç¹ã«äž¡æ«ç«¯ã®äœçœ®ã«äžè¬åŒïŒïŒã§
è¡šããããå®èœåºã®çµåãããã®ãåå¿åæãšã
ãŠçšããããããã®æ«ç«¯ã«ç¹å®ã®å®çåºãæãã
ããªã«ãŒãããŒãã¯ãåçš®æ¹æ³ã«ãã補é ããã
ãšãã§ãããããšãã°ãçé¢éçž®åæ³ã§ã¯äžæŽ»æ§
ææ©æº¶å€ã®ååšäžãã¢ã«ã«ãªæ°Žæº¶æ¶²ã«æº¶è§£ãããž
ããšããŒã«é¡ãšãã¹ã²ã³ã®åå¿ã«ãããŠãåå¿
åãåå¿æãããã¯åå¿çµäºåŸã«ã
äžè¬åŒ
ãåŒäžãïŒR1ïŒR2ã¯åèšãšåããã
ã§è¡šãããã眮æããšããŒã«ãå ããããã«éå
觊åªãšããŠç¬¬äžçŽã¢ãã³ã®ååšäžãéçž®ååå¿ã
ããããšã«ãã€ãŠåŸããããããã§äžè¬åŒïŒïŒ
ã§è¡šãããã眮æããšããŒã«ãšããŠã¯ãïœâã€ãœ
ãããã«ããšããŒã«ãïœâã€ãœãããã«ããšããŒ
ã«ãªã©ãããããã®éãäžèšäžè¬åŒïŒïŒã§è¡šã
ããã眮æããšããŒã«ã¯ããªã«ãŒãããŒãã®åå
é調ç¯å€ãšããŠäœçšããããšãšãªãããã®çµæã
æªç«¯ã«ç¹å®ã®å®èœåºãæãããšå
±ã«ææã®éå床
ã®ããªã«ãŒãããŒããããã¯ãã®ãªãªãŽããŒãåŸ
ããããããã§äŸãã°äžè¬åŒïŒïŒã§è¡šãããã
ãžããšããŒã«ååç©ãšãã¹ã²ã³ãã補é ããããª
ã«ãŒãããŒããããã¯ãã®ãªãªãŽããŒãçšããã
ããšäžè¬åŒïŒïŒã§è¡šãããã眮æããšããŒã«ã
åå¿ãããå Žåã«ã¯ãåŸãããç¹å®ã®æ«ç«¯åºãã
ã€ããªã«ãŒãããŒãã¯ãäžè¬åŒ
ã§è¡šãããããã®ãšãªããåŒäžãïŒR1ïŒR2ïŒ
Râ²ïŒY1ïŒY2ïŒïœïŒïœã¯åèšãšåããã®ã§ããã
ãŸãïœã¯éå床ã瀺ãããã®éå床ïœã¯ç¹ã«å¶é
ã¯ãªããæçµçã«åŸãããããªã«ãŒãããŒãå
±é
åäœã®äœ¿çšç®ççã«å¿ããŠé©å®éžå®ããã°ãã
ããäžè¬ã«ã¯ïœïŒïŒã100ã奜ãŸããã¯ïœïŒïŒã
60ã®ç¯å²ãšããã
次ã«ãäžèšã®ç¹å®æ«ç«¯åºãæããããªã«ãŒãã
ãŒããšåå¿ãããããªããšãã¬ã³ãªãã·ãã¯åçš®
ã®ãã®ãããããéåžžã¯
äžè¬åŒ
ãåŒäžãR3ïŒR4ïŒR5ããã³R6ã¯æ°ŽçŽ ãããã²
ã³ã眮æãããã¯é眮æçåæ°ŽçŽ åºã§ãããR3
ãR6ã¯åããã®ã§ãããç°ãªããã®ã§ãã€ãŠã
ããããå°ãªããšãïŒã€ã¯ã¡ãã«åºã§ãããã
ã§è¡šãããããã®ã§ããã
ãã®äžè¬åŒïŒïŒã§è¡šããããããªããšãã¬ã³
ãªãã·ãã¯äžèšã®äžè¬åŒ
ãåŒäžãR3ïŒR4ïŒR5ïŒR6ã¯åèšãšåããã
ã§è¡šããããããšããŒã«é¡ã®éåã«ãã€ãŠåŸãã
ãšãã§ãããã®ã§ããããã®ããšããŒã«é¡ã®äŸãš
ããŠã¯ïŒïŒïŒâãžã¡ãã«ããšããŒã«ãïŒâã¡ãã«
âïŒâãšãã«ããšããŒã«ãïŒïŒïŒâãžãšãã«ããš
ããŒã«ãïŒïŒïŒâãžããšãã«ããšããŒã«ãïŒâã¡
ãã«âïŒâããšãã«ããšããŒã«ãïŒâã¡ãã«âïŒ
âã¯ãã«ããšããŒã«ãïŒâãšãã«âïŒâïœâãã
ãã«ããšããŒã«ãïŒâã¡ãã«âïŒâããã¢ããšã
ãŒã«ãïŒâã¡ãã«âïŒâã€ãœãããã«ããšããŒ
ã«ãïŒâã¡ãã«âïŒâã¡ããã·ããšããŒã«ãïŒâ
ã¡ãã«âïŒâïœâããã«ããšããŒã«ãïŒâãšãã«
âïŒâã¯ãã«ããšããŒã«ãªã©ããããããããã
ãã®ããšããŒã«é¡ã®éåã¯é
žåéå觊åªãšããŠã®
第äžçŽã第äºçŽã第äžçŽã®ã¢ããåºãäžååäžã«
å°ãªããšãïŒã€æã€ã¢ããååç©ãšå¡©å第äžé
ãª
ã©ã®éå±å¡©ã®ååšäžãããšããŒã«é¡ãšé
žçŽ ãåå¿
ãããããšã«ããè¡ãªãããããã®å Žåã«è³éŠæ
ç³»ãŸãã¯èèªæç³»çåæ°ŽçŽ ãéååªäœãšããŠäœ¿çš
ããããšãã§ããã
æ¬çºæã®æ¹æ³ã«ãããŠã¯ããã®éåäœãããªã
ã¡äžè¬åŒïŒïŒã§è¡šããããããªããšãã¬ã³ãªã
ã·ããåå¿åæãšããŠããããšåè¿°ããç¹å®ã®æ«
端åºãæããããªã«ãŒãããŒããšãåå¿ãããã
ãšãšãªããããã§ãããªããšãã¬ã³ãªãã·ãã瀺
ãäžè¬åŒïŒïŒäžã®éå床ïœã¯ãäžè¬çã«ã¯ïœïŒ
ïŒã200ã§ããããã奜ãŸããã¯ïœïŒïŒã120ã§ã
ãã
æ¬çºæã®æ¹æ³ã§ã¯ãäžèšã®åŠãç¹å®æ«ç«¯åºãæ
ããããªã«ãŒãããŒããšããªããšãã¬ã³ãªãã·ã
ãšãéé¢åºçºçæ段ã®ä»åšäžã§åå¿ãããããšã
å¿
èŠã§ããã
ããã§éé¢åºçºçæ段ãšããŠã¯ãæ§ã
ãªãã®ã
ããããéåžžã¯åå¿ç³»ã«éé¢åºéå§å€ãååšãã
ãããšããªãŸã³ãé
žçŽ ã«ããåŠçãŸãã¯é»é¢æ§æŸ
å°ç·ãç
§å°ããããšãªã©ã§ãããéé¢åºéå§å€ãš
ããŠã¯ãäŸãã°ãã³ãŸã€ã«ããŒãªãã·ããã©ãŠãª
ã«ããŒãªãã·ããã¢ãŸãã¹ã€ãœããããããªã«ã
ãžã¯ãã«ããŒãªãã·ããïœâããã«ãããããŒãª
ãã·ããªã©ã奜é©ã«çšããããããŸãé»é¢æ§æŸå°
ç·ãšããŠã¯Î±ç·ãβç·ãγç·ã玫å€ç·ãç·ãªã©
ãèããããããããç
§å°ãããšåå¿ç³»ã«éé¢åº
ãçããã©ãžã«ã«åå¿ãé²è¡ããã
åå¿ã«ããã€ãŠã¯ãç¹å®ã®æ«ç«¯åºãæããããª
ã«ãŒãããŒããšããªããšãã¬ã³ãªãã·ããªãã³ã«
éé
žåç©çã®éé¢åºéå§å€ãåå¿ç³»ã«å ãããã
é
žçŽ ãããã¯ãªãŸã³åŠçãããããŸãã¯çŽ«å€ç·ç
ãç
§å°ããªãããããã溶åªäžãããã¯ç¡æº¶åªäž
ã«ãŠå ç±ããã°ãããããã§åå¿ç³»ã«å ããåå¿
åæã®æ·»å å²åã¯ç¹ã«å¶éã¯ãªãããéåžžã¯ç¹å®
æ«ç«¯åºãæããããªã«ãŒãããŒããšããªããšãã¬
ã³ãªãã·ããåè
ïŒåŸè
ïŒïŒã95ïŒ95ãïŒïŒéé
æ¯ïŒã奜ãŸããã¯10ã90ïŒ90ã10ïŒééæ¯ïŒãš
ããããã«éé¢åºéå§å€ãçšããå Žåã«ã¯åèšã®
äž¡åå¿åæ100éééšã«å¯ŸããŠ0.001éééšä»¥äžã
奜ãŸããã¯0.01ãïŒéééšã®å²åã§å ããã¹ãã§
ããã
åå¿ã¯æº¶æ¶²æ³ãããã¯æº¶åªæ³ãªã©æ§ã
ãªæ
æ§ã§
è¡ãªãããšãã§ããäŸãã°æº¶æ¶²æ³ã«ããå Žåã«ã¯
70ã200âã«ãŠïŒåãïŒæéåå¿ãããã°ããã
äžæ¹ã溶èæ³ã«ããå Žåã«ã¯180ã300âã®æž©åºŠã«
ãŠåå¿ãé²è¡ãããã°ããã
äžè¿°ã®æ¡ä»¶çã«ãŠåå¿ãè¡ãªãã°ãããªã«ãŒã
ããŒãã®æ«ç«¯ã«ååšããäžè¬åŒïŒïŒã§è¡šããã
ãå®èœåºã®
The present invention relates to a method for producing a polycarbonate copolymer, and more specifically, the present invention relates to a method for producing a polycarbonate copolymer, and more specifically, by reacting a polycarbonate having a specific terminal group with polyphenylene oxide in the presence of a free radical generating means, the polycarbonate copolymer has heat resistance,
The present invention relates to a method for efficiently producing a polycarbonate copolymer having excellent chemical resistance, film formability, moldability, etc., at a desired copolymerization ratio. Traditionally, polycarbonate resin has been well known as an engineering resin due to its excellent mechanical, thermal, and electrical properties, especially its impact resistance.
It is often used for mechanical parts, electrical parts, etc. However, polycarbonate resin has the inherent disadvantage that it whitens and crazes when it comes into contact with acetone, heptane, carbon tetrachloride, etc., and also cracks under stress.
Although this resin has excellent properties, its use and application fields have been severely limited. Furthermore, this polycarbonate resin has disadvantages such as insufficient compatibility when blended with other thermoplastic resins such as polystyrene resins. In order to eliminate these drawbacks, a method of mechanically mixing polyphenylene oxide with polycarbonate resin or a method of mixing it as a solution has been proposed (Japanese Patent Publication No. 15782/1982). However, this method involves mere physical mixing, and there are problems in that compatibility is insufficient and the resulting composition is opaque and has poor uniformity. In order to overcome these drawbacks of the prior art, the present inventors have already succeeded in developing a block copolymer consisting of polycarbonate and polyphenylene oxide and a method for producing the same (Japanese Patent Application No. 56-66556).
No. Specification). The present inventors have conducted extensive research in order to develop a method that can more efficiently produce a copolymer of polycarbonate and polyphenylene oxide at a desired copolymerization ratio. As a result, they discovered that the object could be achieved by using polycarbonate having a specific functional group at the end and reacting it with polyphenylene oxide, leading to the completion of the present invention. That is, the present invention has the general formula [In the formula, R represents hydrogen or a desired substituent,
R 1 and R 2 each represent an alkyl group or an aryl group. ] A method for producing a polycarbonate copolymer is provided, which comprises reacting a polycarbonate having a terminal group represented by the following with polyphenylene oxide through the intervention of a free radical generating means. As mentioned above, the polycarbonate used in the method of the present invention must have a functional group represented by the general formula () at its terminal end. In the formula, R is not particularly limited and may be a hydrogen atom or a desired substituent, but is usually appropriately selected from a hydrogen atom, a halogen atom, or an alkyl group. In addition, R 1 and R 2 are each an alkyl group such as a methyl group, an ethyl group, a propyl group, or an aryl group, but especially R 1 ,
Most commonly, both R 2 are methyl groups. Various types of polycarbonate bodies having terminal groups as described above can be considered, and those obtained by reacting various diphenol compounds with phosgene or diphenyl carbonate are used. Here, the diphenol compound usually has the general formula Or general formula [In the formula, R' is a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms, -O-, -S-, -SO2- , or -CO-, and Y1 and Y2 are hydrogen or halogen atoms, a and b are integers of 1-4. ] We can list the following expressions. Examples of the diphenol compounds represented by the above general formula () or () include 4,4'-dihydroxydiphenyl; 2,2-bis-(4-hydroxyphenyl)-propane (bisphenol A); , 4-bis-(4-hydroxyphenyl)-2-methylbutane; 1,1-bis-(4-hydroxyphenyl)-cyclohexane; α, αâ²-
Bis-(4-hydroxyphenyl)-p-diisopropylbenzene; 2,2-bis-(3-methyl-
4-hydroxyphenyl)-propane; 2,2-
Bis-(3-chloro-4-hydroxyphenyl)-
Propane; bis-(3,5-dimethyl-4-hydroxyphenyl)-methane; 2,2-bis-(3,
5-dimethyl-4-hydroxyphenyl)propane; bis-(4-hydroxyphenyl)sulfone; bis-(3,5-dimethyl-4-hydroxyphenyl)sulfone; 2,4-bis-(3,5 â
dimethyl-4-hydroxyphenyl)-2-methylbutane; 1,1-bis-(3,5-dimethyl-
4-hydroxyphenyl)-cyclohexane;
α,αâ²-bis-(3,5-dimethyl-4-hydroxyphenyl)-p-diisopropylbenzene;
2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane and 2,2-bis-
(3,5-dibromo-4-hydroxyphenyl)-
It's propane. A particularly preferred example of diphenol is 2,2-bis-(4-hydroxyphenyl)-
Propane; 2,2-bis-(3,5-dimethyl-
4-hydroxyphenyl)-propane; 2,2-
Bis-(3,5-dichloro-4-hydroxyphenyl)-propane; 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane and 1,1-bis-(4-hydroxy phenyl)-cyclohexane. These diphenols can be used not only alone but also in the form of a mixture. The main body of the polycarbonate used in the method of the present invention is polycarbonate obtained by the reaction of various dienol compounds as described above with phosgene or diphenyl carbonate, etc., but also various copolymers of polycarbonate, such as dioxydiaryl alkane. Mutual copolycarbonates, copolycarbonates of dioxydiarylalkane and other aromatic dioxy compounds, copolycarbonates of dioxydiarylalkane and aliphatic dioxy compounds, copolycarbonates of aromatic dioxy compounds other than dioxydiarylalkane , homobond copolymers such as copolycarbonates of aromatic dioxy compounds other than dioxydiarylalkane and aliphatic dioxy compounds, polycarbonates with ester bonds, polycarbonates with urethane bonds, and other heterobond copolymers. be able to. In the method of the present invention, a polycarbonate having a functional group represented by the general formula () bonded to the terminal position, particularly at both terminal positions, is used as a reaction raw material. This polycarbonate having a specific functional group at its terminal can be produced by various methods. For example, in the interfacial polycondensation method, in the reaction of diphenols dissolved in an alkaline aqueous solution and phosgene in the presence of an inert organic solvent, the general formula [In the formula, R, R 1 and R 2 are the same as above. ] It can be obtained by adding a substituted phenol represented by the following and further carrying out a polycondensation reaction in the presence of a tertiary amine as a polymerization catalyst. Here the general formula ()
Examples of substituted phenols represented by include p-isopropylphenol and m-isopropylphenol. At this time, the substituted phenol represented by the above general formula () acts as a molecular weight regulator for polycarbonate, and as a result,
A polycarbonate or an oligomer thereof having a specific functional group at the end and a desired degree of polymerization can be obtained. Here, for example, if a diphenol compound represented by the general formula () and a polycarbonate or its oligomer made from phosgene are used, and this is reacted with a substituted phenol represented by the general formula (), the resulting specific terminal group is Polycarbonate has the general formula It will be expressed as. In the formula, R, R 1 , R 2 ,
Râ², Y 1 , Y 2 , a, b are the same as above,
Further, m indicates the degree of polymerization. The degree of polymerization m is not particularly limited and may be appropriately selected depending on the purpose of use of the polycarbonate copolymer finally obtained, but generally m = 2 to 100, preferably m = 4 to 100.
The range is 60. Next, there are various types of polyphenylene oxide to be reacted with the polycarbonate having the above-mentioned specific end groups, but usually it has the general formula [In the formula, R 3 , R 4 , R 5 and R 6 are hydrogen, halogen, substituted or unsubstituted hydrocarbon group, and R 3
~R 6 may be the same or different, but at least one is a methyl group. ] It is expressed as. The polyphenylene oxide represented by this general formula () has the following general formula [In the formula, R 3 , R 4 , R 5 , and R 6 are the same as above. ] It can be obtained by polymerization of phenols represented by the following. Examples of these phenols include 2,6-dimethylphenol, 2-methyl-6-ethylphenol, 2,6-diethylphenol, 2,6-diphenylphenol, 2-methyl-6-phenylphenol, 2- Methyl-6
-Chlorphenol, 2-ethyl-6-n-propylphenol, 2-methyl-6-bromophenol, 2-methyl-6-isopropylphenol, 2-methyl-6-methoxyphenol, 2-
Examples include methyl-6-n-butylphenol and 2-ethyl-6-chlorophenol. The polymerization of these phenols is carried out in the presence of an amino compound having at least one primary, secondary, or tertiary amino group in one molecule and a metal salt such as cuprous chloride as an oxidative polymerization catalyst. This is done by reacting phenols with oxygen. Aromatic or aliphatic hydrocarbons can be used as polymerization medium in this case. In the method of the present invention, this polymer, that is, polyphenylene oxide represented by the general formula (), is used as a reaction raw material and is reacted with the polycarbonate having the above-mentioned specific terminal group. Here, the degree of polymerization n in the general formula () representing polyphenylene oxide is generally n=
Although n=2 to 200, more preferably n=4 to 120. In the method of the present invention, it is necessary to react a polycarbonate having a specific terminal group as described above with polyphenylene oxide in the presence of a free radical generating means. There are various ways to generate free radicals, but usually include the presence of a free radical initiator in the reaction system, treatment with ozone or oxygen, or irradiation with ionizing radiation. Free radical initiators include, for example, benzoyl peroxide, lauryl peroxide, azobisisobutyronitrile,
Dicumyl peroxide, t-butyl hydroperoxide and the like are preferably used. Ionizing radiation may include α rays, β rays, γ rays, ultraviolet rays, X rays, etc. When irradiated with these, free radicals are generated in the reaction system and radical reactions proceed. For the reaction, add a polycarbonate with a specific end group, polyphenylene oxide, and a free radical initiator such as peroxide to the reaction system, or
This may be heated in a solvent or without a solvent while being treated with oxygen or ozone or irradiated with ultraviolet rays or the like. There is no particular restriction on the ratio of the reaction raw materials added to the reaction system, but usually polycarbonate having a specific end group and polyphenylene oxide are used, the former: the latter = 5 to 95: 95 to 5 (weight ratio), preferably 10-90:90-10 (weight ratio), and when using a free radical initiator, 0.001 part by weight or more per 100 parts by weight of both of the above reaction materials,
It should preferably be added in a proportion of 0.01 to 5 parts by weight. The reaction can be carried out in various ways such as a solution method or a solvent method. For example, when using a solution method,
It is sufficient to react at 70 to 200â for 1 minute to 2 hours.
On the other hand, when using the melting method, the reaction may proceed at a temperature of 180 to 300°C. If the reaction is carried out under the above-mentioned conditions, the functional group represented by the general formula () present at the end of the polycarbonate will be
éªéæ¿ãæããïŒã®åå¿å®¹åšã«ãæ«ç«¯ã¯ãã
ããŒã¡ãŒãåºå«æããªã«ãŒãããŒããªãªãŽããŒ
100ïœãïœâã€ãœãããã«ããšããŒã«1.6ïœãå«ã
å¡©åã¡ãã¬ã³æº¶æ¶²450mlããã¹ããšããŒã«ïŒ¡ã®ïŒ
èŠå®èæ§ãœãŒã氎溶液150mlããã³ããªãšãã«ã¢
ãã³50mgãä»èŸŒã¿ãå転æ°500r.p.mã§æ¹æããª
ãã50åéåå¿ãè¡ãªã€ãã
åå¿çµäºåŸãåå¿æ··åç©ãå¡©åã¡ãã¬ã³ïŒã§
åžéããæ°Ž1.5ãå ããŠæ¹æããã次ãã§æ°Žçž
ãåé¢é€å»åŸãå¡©é
žãæ°Žãèæ§ãœãŒã氎溶液ãã
ã³æ°Žã®é åºã§æŽæµãè¡ãªã€ãããããåŸææ©çžã
åé¢ããå¡©åã¡ãã¬ã³ãçå»ããŠèªè²ç²æ«ç¶ã®ã€
ãœãããã«ããšããŒã«æ«ç«¯ããªã«ãŒãããŒããåŸ
ãããã®ãã®ã®éå
ç²åºŠïŒÎ·SPïŒïŒ£ïŒã¯0.59
ïŒ30âã¯ãããã«ã 0.5ïœïŒdlïŒã§ãã€ãã
åèäŸ ïŒ
ãããªããšãã¬ã³ãªãã·ã(ã€)ã®è£œé ã
10åå¿å®¹åšã«ïŒïŒïŒâãžã¡ãã«ããšããŒã«
1000ïœããã«ãšã³1700mlãã¡ã¿ããŒã«2500mlãå¡©
å第äžé
19ïœããã³ããªãžã³190mlãä»èŸŒã¿ãé
ž
çŽ ã¬ã¹ã1.5ïŒminã®å¹ããã¿ãªãã宀枩ã«ãŠ
ïŒæéåå¿ãè¡ãªã€ããåå¿åŸãçæããæ²æŸ±ç©
ãïŒå¥ããå°éã®å¡©é
žãå«ãã¡ã¿ããŒã«ã§æŽæ»ã
也ç¥ãããªããšãã«ãªãã·ã(ã€)ãåŸãããã®ããª
ããŒã®åç87ïŒ
ãæ°å¹³åååé4800ïŒ40éäœïŒã§
ãã€ãã
åèäŸ ïŒ
ãããªããšãã¬ã³ãªãã·ã(ã)ã®è£œé ã
ïŒïŒïŒâãžã¡ãã«ããšããŒã«500ïœããã«ãšã³
2000mlãã¡ã¿ããŒã«1000mlãå¡©å第äžé
30ïœãã
ã³ããªãžã³300mlãçšããŠåèäŸïŒã«æºããŠããª
ããšãã¬ã³ãªãã·ã(ã)ãåŸããããªããŒã®åç84
ïŒ
ãæ°å¹³åååé7700ïŒ64éäœïŒã§ãã€ãã
å®æœäŸ ïŒ
åèäŸïŒã§åŸãããã€ãœãããã«ããšããŒã«æ«
端ããªã«ãŒãããŒã15ïœãåèäŸïŒã§åŸãããã
ãªããšãã¬ã³ãªãã·ã(ã€)ïŒïœããžã¯ãã«ããŒãªã
ã·ã400mgããã³ãã«ãšã³200mlããªãŒãã¯ã¬ãŒã
ã«ä»èŸŒã¿135âã§45åéå ç±åå¿ãè¡ãªã€ããå
å¿çµäºåŸã¡ã¿ããŒã«äžã§æ²æŸ±ãããæ²æŸ±ç©ãå
ã也ç¥ãããªã«ãŒãããŒãå
±éåäœ15.5ïœãåŸ
ãããã®ãã®ã®éå
ç²åºŠïŒÎ·SPïŒïŒ£ïŒã¯0.69
ïŒ30âãã¯ãããã«ã 0.5ïœïŒdlïŒãããªããšãã¬
ã³ãªãã·ãå«é26.7ééïŒ
ïŒNMR枬å®ïŒã§ãã€
ãããªããçæéåäœïŒïœãå¡©åã¡ãã¬ã³30mlã«
溶解ãããïŒæéæŸçœ®ãããæ²æŸ±ç©ã¯ãªããçæ
éåäœäžã«ããªããšãã¬ã³ãªãã·ããã¢ããªããŒ
ããªãããšã確èªããã
å®æœäŸ ïŒ
åèäŸïŒã§åŸãããã€ãœãããã«ããšããŒã«æ«
端ããªã«ãŒãããŒã15ïœãåèäŸïŒã§åŸãããã
ãªããšãã¬ã³ãªãã·ã(ã)ïŒïœããžã¯ãã«ããŒãªã
ã·ã600mgãããã³ãã«ãšã³200mlããªãŒãã¯ã¬ãŒ
ãã«ä»èŸŒã¿140âã§20åéå ç±åå¿ãè¡ãªã€ãã
å®æœäŸïŒã«æºããŠããªã«ãŒãããŒãå
±éåäœ17.1
ïœãåŸãããã®ãã®ã®éå
ç²åºŠïŒÎ·SPïŒïŒ£ïŒã¯
0.70ïŒ30âãã¯ãããã«ã 0.5ïœïŒdlïŒãããªããš
ãã¬ã³ãªãã·ãå«é22ééïŒ
ïŒNMR枬å®ïŒã§ã
ã€ãããªããçæéåäœäžã«ã¯ããªããšãã¬ã³ãª
ãã·ããã¢ããªããŒã¯èªããããªãã€ãã
å®æœäŸ ïŒ
å®æœäŸïŒããã³ïŒã§åŸãããããªã«ãŒãããŒã
å
±éåäœãçšããŠãã¯ãããã«ã 溶液ãã300ÎŒ
ã®ãã€ã¹ãã³ã°ãã€ã«ã ã補é ããããã®ãã€ã«
ã ãæãæ²ã宀枩äžã¢ã»ãã³äžã«æµžæŒ¬ãããçœå
ã¯çãããïŒæéåŸã«ãããã«çœåãããä»æ¹ã
ãªã«ãŒãããŒããçšããŠåæ§ã«æµžæŒ¬ãããšããç¬
æã«äºè£ãçããã
A polycarbonate oligomer containing a terminal chloroformate group was placed in one reaction vessel having a baffle plate.
100 g, 450 ml of methylene chloride solution containing 1.6 g of p-isopropylphenol, 2 of bisphenol A
150 ml of a normal aqueous sodium hydroxide solution and 50 mg of triethylamine were charged, and the reaction was carried out for 50 minutes while stirring at a rotation speed of 500 rpm. After the reaction was completed, the reaction mixture was diluted with 1 part of methylene chloride, 1.5 parts of water was added, and the mixture was stirred. After separating and removing the aqueous phase, washing was performed in the order of hydrochloric acid, water, aqueous caustic soda solution, and water. Thereafter, the organic phase was separated and methylene chloride was distilled off to obtain a self-colored powdery isopropylphenol-terminated polycarbonate. The reduced viscosity (ηSP/C) of this product is 0.59
(Chloroform 0.5g/dl at 30°C). Reference example 2 [Manufacture of polyphenylene oxide (a)] 10 2,6-dimethylphenol in a reaction vessel
1000 g, toluene 1700 ml, methanol 2500 ml, cuprous chloride 19 g and pyridine 190 ml were charged, and the reaction was carried out at room temperature for 3 hours while blowing oxygen gas at 1.5/min. After the reaction, the generated precipitate was separated into three parts and washed with methanol containing a small amount of hydrochloric acid.
It was dried to obtain polyphenyl oxide (a). The yield of this polymer was 87% and the number average molecular weight was 4800 (40 mer). Reference example 3 [Production of polyphenylene oxide (b)] 2,6-dimethylphenol 500g, toluene
According to Reference Example 2, polyphenylene oxide (b) was obtained using 2,000 ml of methanol, 1,000 ml of methanol, 30 g of cuprous chloride, and 300 ml of pyridine. Polymer yield 84
%, and the number average molecular weight was 7700 (64-mer). Example 1 15 g of isopropylphenol-terminated polycarbonate obtained in Reference Example 1, 5 g of polyphenylene oxide (a) obtained in Reference Example 2, 400 mg of dicumyl peroxide, and 200 ml of toluene were placed in an autoclave and heated at 135°C for 45 minutes. The reaction was carried out. After the reaction was completed, the mixture was precipitated in methanol, and the precipitate was collected and dried to obtain 15.5 g of a polycarbonate copolymer. The reduced viscosity (ηSP/C) of this product is 0.69
(30°C, chloroform 0.5 g/dl), and the polyphenylene oxide content was 26.7% by weight (NMR measurement). Note that 2 g of the produced polymer was dissolved in 30 ml of methylene chloride and left to stand for 6 hours, but no precipitate was found, confirming that there was no polyphenylene oxide homopolymer in the produced polymer. Example 2 15 g of isopropylphenol-terminated polycarbonate obtained in Reference Example 1, 4 g of polyphenylene oxide (B) obtained in Reference Example 3, 600 mg of dicumyl peroxide, and 200 ml of toluene were charged into an autoclave and heated at 140°C for 20 minutes. A heating reaction was carried out.
Polycarbonate copolymer 17.1 according to Example 1
I got g. The reduced viscosity (ηSP/C) of this material is
0.70 (30°C, chloroform 0.5 g/dl), and the polyphenylene oxide content was 22% by weight (NMR measurement). Note that no polyphenylene oxide homopolymer was observed in the produced polymer. Example 3 Using the polycarbonate copolymers obtained in Examples 1 and 2, 300Ό
cast film was manufactured. This film was folded and immersed in acetone at room temperature, but no whitening occurred, and the film slightly whitened after 3 hours. On the other hand, when polycarbonate was similarly immersed, cracks appeared instantly.
Claims (1)
R1ããã³R2ã¯ããããã¢ã«ãã«åºãããã¯ã¢ãª
ãŒã«åºã瀺ããã ã§è¡šããããæ«ç«¯åºãæããããªã«ãŒãããŒããš
ããªããšãã¬ã³ãªãã·ããéé¢åºçºçæ段ãä»åš
ãããŠåå¿ãããããšãç¹åŸŽãšããããªã«ãŒãã
ãŒãå ±éåäœã®è£œé æ³ã ïŒ ããªããšãã¬ã³ãªãã·ãã äžè¬åŒ ãåŒäžãR3ïŒR4ïŒR5ããã³R6ã¯æ°ŽçŽ ãããã²
ã³çœ®æãããã¯é眮æçåæ°ŽçŽ åºã§ãããR3ã
R6ã¯åããã®ã§ãããç°ãªããã®ã§ãã€ãŠãã
ãããå°ãªããšãïŒã€ã¯ã¡ãã«åºã§ãããã ã§è¡šãããããã®ã§ããç¹èš±è«æ±ã®ç¯å²ç¬¬ïŒé èš
èŒã®è£œé æ³ã ïŒ éé¢åºçºçæ段ããåå¿ç³»ã«éé¢åºéå§å€ã
ååšãããããšã§ããç¹èš±è«æ±ã®ç¯å²ç¬¬ïŒé èšèŒ
ã®æ¹æ³ã ïŒ éé¢åºçºçæ段ãããªãŸã³ãããã¯é žçŽ ãçš
ããããšã§ããç¹èš±è«æ±ã®ç¯å²ç¬¬ïŒé èšèŒã®æ¹
æ³ã ïŒ éé¢åºçºçæ段ããé»é¢æ§æŸå°ç·ãç §å°ãã
ããšã§ããç¹èš±è«æ±ã®ç¯å²ç¬¬ïŒé èšèŒã®æ¹æ³ã[Claims] 1. General formula [In the formula, R represents hydrogen or a desired substituent,
R 1 and R 2 each represent an alkyl group or an aryl group. ] A method for producing a polycarbonate copolymer, which comprises reacting a polycarbonate having a terminal group represented by the following with polyphenylene oxide through the intervention of a free radical generating means. 2 Polyphenylene oxide has the general formula [In the formula, R 3 , R 4 , R 5 and R 6 are hydrogen, a halogen-substituted or unsubstituted hydrocarbon group, and R 3 -
R 6 may be the same or different, but at least one is a methyl group. ] The manufacturing method according to claim 1, which is represented by: 3. The method according to claim 1, wherein the free radical generating means is the presence of a free radical initiator in the reaction system. 4. The method according to claim 1, wherein the free radical generating means uses ozone or oxygen. 5. The method according to claim 1, wherein the free radical generating means is irradiation with ionizing radiation.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP19844981A JPS58101111A (en) | 1981-12-11 | 1981-12-11 | Manufacture of polycarbonate copolymer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP19844981A JPS58101111A (en) | 1981-12-11 | 1981-12-11 | Manufacture of polycarbonate copolymer |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS58101111A JPS58101111A (en) | 1983-06-16 |
JPS6146007B2 true JPS6146007B2 (en) | 1986-10-11 |
Family
ID=16391278
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP19844981A Granted JPS58101111A (en) | 1981-12-11 | 1981-12-11 | Manufacture of polycarbonate copolymer |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS58101111A (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61264020A (en) * | 1985-05-17 | 1986-11-21 | Idemitsu Kosan Co Ltd | Aromatic polycarbonate and production thereof |
US4775739A (en) * | 1986-06-18 | 1988-10-04 | Mitsubishi Chemical Industries Limited | Process for producing polycarbonate resin with tertiary alryl phenol molecular weight modifier |
US4777221A (en) * | 1987-02-17 | 1988-10-11 | General Electric Company | Polyphenylene ether-polycarbonate copolymers and method of preparation |
US4902735A (en) * | 1987-06-03 | 1990-02-20 | Idemitsu Petrochemical Co., Ltd. | High impact resistant polycarbonate and process for producing said polycarbonate |
US4973628A (en) * | 1989-09-14 | 1990-11-27 | General Electric Company | Method for preparing block polyphenylene ether-polycarbonates |
-
1981
- 1981-12-11 JP JP19844981A patent/JPS58101111A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS58101111A (en) | 1983-06-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0633292B1 (en) | Compositions of siloxane polyestercarbonate block terpolymers and high heat polycarbonates | |
US5109076A (en) | Polydiorganosiloxane/polycarbonate block cocondensates based on certain dihydroxydiphenylcycloalkanes | |
US3879347A (en) | High molecular, statistical copolycarbonates | |
CN108473670B (en) | Polyester-polycarbonate copolymer and method for producing same | |
JP6860671B2 (en) | Polycarbonate resin composition having excellent heat resistance and fluidity and molded products containing it | |
US4374233A (en) | Block copolymers of polyphenylene oxides and non-sterically-hindered high molecular weight aromatic polycarbonates | |
JPH0391528A (en) | Polycarbonate based on substituted cyclohexylidene bisphenol | |
JP6765432B2 (en) | Polysiloxane-polycarbonate copolymer with improved transparency and flame retardancy and its production method | |
JPH0774268B2 (en) | Method for producing copolyester carbonate | |
JPH0749473B2 (en) | Polycarbonate-polyether block copolymer | |
JPS6248689B2 (en) | ||
JPS63152623A (en) | Aliphatic diol-bis-diphenolcarbonate | |
JPH0764924B2 (en) | Aromatic polycarbonate | |
JPH03119054A (en) | Thermoplastic material blend | |
JPH02245022A (en) | Hydroxy-terminated polycarbonate | |
JP3466787B2 (en) | Production of copolyestercarbonate by bischloroformate method. | |
JPS6146007B2 (en) | ||
JPH1077338A (en) | Polycarbonate resin and its production | |
EP0093914B2 (en) | Process for the production of polycarbonate | |
JPH0112773B2 (en) | ||
JPH02300258A (en) | Heat-resistant polycarbonate molding composition | |
EP0230608A1 (en) | Modified co-polyester-carbonate resins | |
US4377662A (en) | Block copolymers of polyphenylene oxides and sterically-hindered aromatic polycarbonates | |
JPH03215551A (en) | Thermoplastic composition containing polycarbonate based on n-alkyl-substituted cyclohexylidene bisphenol | |
JPH0114926B2 (en) |