JPS633023A - Production of vinyl-terminated polycarbonate resin - Google Patents
Production of vinyl-terminated polycarbonate resinInfo
- Publication number
- JPS633023A JPS633023A JP14600986A JP14600986A JPS633023A JP S633023 A JPS633023 A JP S633023A JP 14600986 A JP14600986 A JP 14600986A JP 14600986 A JP14600986 A JP 14600986A JP S633023 A JPS633023 A JP S633023A
- Authority
- JP
- Japan
- Prior art keywords
- polycarbonate resin
- vinyl
- hydroxyphenyl
- bis
- isopropenylphenol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920005668 polycarbonate resin Polymers 0.000 title claims abstract description 21
- 239000004431 polycarbonate resin Substances 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- WUQYBSRMWWRFQH-UHFFFAOYSA-N 2-prop-1-en-2-ylphenol Chemical compound CC(=C)C1=CC=CC=C1O WUQYBSRMWWRFQH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 7
- 239000011347 resin Substances 0.000 abstract description 7
- 239000003607 modifier Substances 0.000 abstract description 5
- 229920000515 polycarbonate Polymers 0.000 abstract description 5
- 239000004417 polycarbonate Substances 0.000 abstract description 5
- 229920001400 block copolymer Polymers 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 8
- -1 vinyl compound Chemical class 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 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 5
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical compound OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 2
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 238000012695 Interfacial polymerization Methods 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 239000006085 branching agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-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
- 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
- CKNCVRMXCLUOJI-UHFFFAOYSA-N 3,3'-dibromobisphenol A Chemical compound C=1C=C(O)C(Br)=CC=1C(C)(C)C1=CC=C(O)C(Br)=C1 CKNCVRMXCLUOJI-UHFFFAOYSA-N 0.000 description 1
- REWLXMVGEZMKSG-UHFFFAOYSA-N 3-prop-1-en-2-ylphenol Chemical compound CC(=C)C1=CC=CC(O)=C1 REWLXMVGEZMKSG-UHFFFAOYSA-N 0.000 description 1
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- RQCACQIALULDSK-UHFFFAOYSA-N 4-(4-hydroxyphenyl)sulfinylphenol Chemical compound C1=CC(O)=CC=C1S(=O)C1=CC=C(O)C=C1 RQCACQIALULDSK-UHFFFAOYSA-N 0.000 description 1
- BATCUENAARTUKW-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)-diphenylmethyl]phenol Chemical group C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BATCUENAARTUKW-UHFFFAOYSA-N 0.000 description 1
- RSSGMIIGVQRGDS-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)-phenylmethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C1=CC=CC=C1 RSSGMIIGVQRGDS-UHFFFAOYSA-N 0.000 description 1
- KJMVGAOYRRKQPY-UHFFFAOYSA-N 4-[2,4,6-tri(propan-2-yl)phenyl]phenol Chemical compound CC(C)C1=CC(C(C)C)=CC(C(C)C)=C1C1=CC=C(O)C=C1 KJMVGAOYRRKQPY-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
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- AYGGQJHJRFZDFH-UHFFFAOYSA-N 5,7-dichloro-1h-indole-2,3-dione Chemical compound ClC1=CC(Cl)=CC2=C1NC(=O)C2=O AYGGQJHJRFZDFH-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
- SJVGFKBLUYAEOK-SFHVURJKSA-N 6-[4-[(3S)-3-(3,5-difluorophenyl)-3,4-dihydropyrazole-2-carbonyl]piperidin-1-yl]pyrimidine-4-carbonitrile Chemical compound FC=1C=C(C=C(C=1)F)[C@@H]1CC=NN1C(=O)C1CCN(CC1)C1=CC(=NC=N1)C#N SJVGFKBLUYAEOK-SFHVURJKSA-N 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
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical class OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 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
- 239000012442 inert solvent Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- DIAIBWNEUYXDNL-UHFFFAOYSA-N n,n-dihexylhexan-1-amine Chemical compound CCCCCCN(CCCCCC)CCCCCC DIAIBWNEUYXDNL-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- XULSCZPZVQIMFM-IPZQJPLYSA-N odevixibat Chemical compound C12=CC(SC)=C(OCC(=O)N[C@@H](C(=O)N[C@@H](CC)C(O)=O)C=3C=CC(O)=CC=3)C=C2S(=O)(=O)NC(CCCC)(CCCC)CN1C1=CC=CC=C1 XULSCZPZVQIMFM-IPZQJPLYSA-N 0.000 description 1
- 239000012766 organic filler Substances 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
- 150000002989 phenols Chemical class 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- ABVVEAHYODGCLZ-UHFFFAOYSA-N tridecan-1-amine Chemical compound CCCCCCCCCCCCCN ABVVEAHYODGCLZ-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、末端にビニル基を有する新規なポリカーボネ
ート樹脂の製法であり、該製法によるポリカーボネート
は、末端のビニル基を利用して他樹脂とのブロックコポ
リマー製造用の原料、反応型の樹脂改質剤、或いはフィ
ルム材料など種々の用途に好適に使用さるものである。Detailed Description of the Invention [Industrial Application Field] The present invention is a method for producing a novel polycarbonate resin having a vinyl group at the end. It is suitably used for various purposes such as raw materials for producing block copolymers, reactive resin modifiers, and film materials.
従来、ポリカーボネート樹脂の末端停止剤若しくは分子
量調節剤としては、ｐ−ターシャリ−ブチルフェノール
、フェノールなどの１価のフェノール類が使用され、又
、流動性の改良の為に長鎖アルキルフェノール類（特公
昭５２−５００７８号）を使用することが知られている
。Conventionally, monohydric phenols such as p-tert-butylphenol and phenol have been used as end-stoppers or molecular weight regulators for polycarbonate resins, and long-chain alkylphenols (Japanese Patent Publication No. 52 -50078) is known to be used.
これらの従来法の分子量調節剤により、製造されたポリ
カーボネート樹脂は、分子鎖末端が閉鎖さているので、
木質的にポリマー末端は不活性である。このため、他樹
脂その他の充填剤との組成物とする場合などの改質に際
しては、単純混合型であるために、相手樹脂が限定され
るという欠点があった。Polycarbonate resins produced using these conventional molecular weight regulators have their molecular chain ends closed;
Polymer ends are inactive in terms of wood quality. For this reason, when modifying the composition to form a composition with other resins or other fillers, there is a drawback that the partner resin is limited because it is of a simple mixing type.
また、末端不飽和のポリカーボネート樹脂を得、ビニル
化合物を付加重合してなるポリカーボネートブロック共
重合体が特公昭４８−２５０７６号公報に開示され、従
って、末端不飽和のポリカーボネート樹脂も公知である
。しかしながら、この発明において導入される不飽和基
は、脂肪族系の化合物であり、耐熱性などに問題点があ
った。更に、ビニルフェノールの例も開示されているが
、この化合物はビニル基の反応性が極めて高いために、
反応中などにゲル化などするという欠点があり、安定性
の優れた末端不飽和のポリカーボネートを得ることは困
難であった。Further, a polycarbonate block copolymer obtained by obtaining a terminally unsaturated polycarbonate resin and addition-polymerizing it with a vinyl compound is disclosed in Japanese Patent Publication No. 48-25076, and therefore, terminally unsaturated polycarbonate resins are also known. However, the unsaturated group introduced in this invention is an aliphatic compound, which has problems such as heat resistance. Furthermore, an example of vinylphenol is also disclosed, but this compound has extremely high reactivity of the vinyl group, so
It has the disadvantage of gelation during the reaction, and it has been difficult to obtain terminally unsaturated polycarbonate with excellent stability.
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、イソプロペニルフェノールが、従来のポ
リカーボネート樹脂の末端停止剤と同様にして使用でき
、かつ安定性に優れ、ビニル化合物などとの反応も容易
に行うことが可能であることを見出し、本発明に到達し
た。The present inventors have conducted intensive studies on methods to improve the above-mentioned drawbacks, and have found that isopropenylphenol can be used in the same manner as conventional end-stopping agents for polycarbonate resins, has excellent stability, and is compatible with vinyl compounds, etc. The present invention was achieved by discovering that the reaction can be easily carried out.
すなわち、本発明は、溶液法によるポリカーボネート樹
脂の製法において、分子量調節剤として、下記一般式（
１）で表されるイソプロペニルフェノールを使用するこ
とを特徴とするビニル末端ポリカーボネート樹脂の製法
である。That is, the present invention uses the following general formula (
This is a method for producing a vinyl-terminated polycarbonate resin characterized by using isopropenylphenol represented by 1).
（式中のｘｌは、Ｆ、 ＣＩ 、 Ｂｒ又は低級アルキ
ル基若しくはアルキロキシ基を示し、ｎはＯ〜４の整数
を示す。）
以下、本発明の構成について説明する。(xl in the formula represents F, CI, Br, or a lower alkyl group or alkyloxy group, and n represents an integer of O to 4.) Hereinafter, the structure of the present invention will be described.
本発明のポリカーボネート樹脂の製法は、従来のポリカ
ーボネート樹脂の製法と比較して、分子量調節剤若しく
は末端停止剤として、上記一般式（１）のイソプロペニ
ルフェノールを使用することを除き従来のポリカーボネ
ート樹脂の製法と同様の製法でよい。The method for producing a polycarbonate resin of the present invention is different from the conventional method for producing a polycarbonate resin, except that isopropenylphenol of the above general formula (1) is used as a molecular weight regulator or terminal stopper. A manufacturing method similar to the manufacturing method may be used.
即ち、界面重合法では、反応に不活性な有機溶媒、アル
カリ水溶液の存在下、二価フェノール系化合物及び前記
分子量調節剤とホスゲンとを反応させた後、第三級アミ
ン若しくは第四級アンモニウム塩などの重合触媒を添加
し重合する方法、ピリジン法では、二価フェノール系化
合物及び前記分子量調節剤をピリジン又はピリジン及び
不活性溶媒の混合溶液に溶解し、ホスゲンを吹き込んで
直接ポリカーボネート樹脂を得る方法である。なお、界
面重合法においては、ホスゲン化反応後の重合時に前記
分子量調節剤を添加する方法でおこなってもよい。That is, in the interfacial polymerization method, a dihydric phenol compound and the molecular weight regulator are reacted with phosgene in the presence of an organic solvent inert to the reaction and an aqueous alkali solution, and then a tertiary amine or quaternary ammonium salt is added. In the pyridine method, a dihydric phenol compound and the molecular weight regulator are dissolved in pyridine or a mixed solution of pyridine and an inert solvent, and phosgene is blown into the solution to directly obtain polycarbonate resin. It is. In the interfacial polymerization method, the molecular weight regulator may be added during the polymerization after the phosgenation reaction.
本発明の二価フェノール系化合物として好ましいものは
、具体的には、ビス（４−ヒドロキシフェニル）メタン
、ビス（４−ヒドロキシフェニル）エーテル、ビス（４
−ヒドロキシフェニル）スルホン、ビス（４−ヒドロキ
シフェニル）スルホキシド、ビス（４−ヒドロキシフェ
ニル）スルフィド、ビス（４−ヒドロキシフェニル）ケ
トン、１，１−ビス（４−ヒドロキシフェニル）エタン
、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、１．
１−ビス（４−ヒドロキシフェニル）シクロヘキサン、
２，２−ビス（４−ヒドロキシ−３，５−ジブロモフェ
ニル）プロパン、２．２−ビス（４−ヒドロキシ−３，
５−’、；クロロフェニル）フロパン、２．２−ビス（
４−ヒドロキシ−３−ブロモフェニル）プロパン、２，
２−ビス（４−ヒドロキシ−３−クロロフェニル）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）−１−フェニルエタン、ビス（４−ヒドロキ
シフェニル）ジフェニルメタンが例示される。Preferred dihydric phenol compounds of the present invention include bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)ether, and bis(4-hydroxyphenyl)methane.
-hydroxyphenyl) sulfone, bis(4-hydroxyphenyl) sulfoxide, bis(4-hydroxyphenyl) sulfide, bis(4-hydroxyphenyl)ketone, 1,1-bis(4-hydroxyphenyl)ethane, 2.2- bis(4-hydroxyphenyl)propane,
2.2-bis(4-hydroxyphenyl)butane, 1.
1-bis(4-hydroxyphenyl)cyclohexane,
2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-hydroxy-3,
5-', ;chlorophenyl)furopane, 2,2-bis(
4-hydroxy-3-bromophenyl)propane, 2,
2-bis(4-hydroxy-3-chlorophenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, An example is bis(4-hydroxyphenyl)diphenylmethane.
上記一般式（１）で示される分子量調節剤として用いる
イソプロペニルフェノールとしては、メタ−又はパラ−
イソプロペニルフェノールが好適であり、その使用量は
二価フェノール系化合物に対して １０〜０．５モル％
、好ましくは ７〜２モル％の範囲であり、本発明にお
いては、上記−般弐（１１の化合物と共に従来公知の分
子量調節剤を併用することも可能である。The isopropenylphenol used as the molecular weight regulator represented by the above general formula (1) is meta- or para-
Isopropenylphenol is preferred, and the amount used is 10 to 0.5 mol% based on the dihydric phenol compound.
, preferably in the range of 7 to 2 mol %, and in the present invention, it is also possible to use a conventionally known molecular weight modifier together with the above compound (11).
反応に不活性な溶媒としては、ジクロロメタン、１，２
−ジクロロエタン、１，１，２．２−テトラクロロエタ
ン、クロロホルム、ＬＬ、１−１−ジクロロエタン、四
塩化炭素、モノクロロベンゼン、ジクロロベンゼン等の
塩素化炭化水素類；ベンゼン、トルエン、キシレン、エ
チルベンゼン等の芳香族炭化水素；ジエチルエーテル等
のエーテル系化合物を挙げることが出来、これらの有機
溶媒は二種以上を混合して使用することも出来る。また
、所望により前記以外のエーテル類、ケトン類、エステ
ル類、ニトリル類などの水と親和性のある溶媒を混合溶
媒系が水と完全に相溶しない限度内で混合したものでも
よい。Examples of solvents inert to the reaction include dichloromethane, 1,2
- Chlorinated hydrocarbons such as dichloroethane, 1,1,2,2-tetrachloroethane, chloroform, LL, 1-1-dichloroethane, carbon tetrachloride, monochlorobenzene, dichlorobenzene; benzene, toluene, xylene, ethylbenzene, etc. Aromatic hydrocarbons include ether compounds such as diethyl ether, and two or more of these organic solvents may be used in combination. Further, if desired, a solvent having an affinity for water such as ethers, ketones, esters, and nitriles other than those mentioned above may be mixed within the limit that the mixed solvent system is not completely miscible with water.
また、重合触媒としては、トリメチルアミン、トリエチ
ルアミン、トリブチルアミン、トリプロピルアミン、ト
リヘキシルアミン、トリデシルアミン、Ｎ、Ｎ−ジメチ
ルシクロヘキシルアミン、ピリジン、キノリン、ジメチ
ルアニリンなどの第三級アミン頚ニトリメチルベンジル
アンモニウムクロライド、テトラメチルアンモニウムク
ロランド、トリエチルベンジルアンモニウムクロライド
などの第四級アンモニウム塩などが挙げられる。In addition, as a polymerization catalyst, tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, trihexylamine, tridecylamine, N,N-dimethylcyclohexylamine, pyridine, quinoline, dimethylaniline, etc. Examples include quaternary ammonium salts such as ammonium chloride, tetramethylammonium chlorand, and triethylbenzylammonium chloride.
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
．１〜１．０モル％の範囲で併用して分岐化ポリカーボ
ネートどすることもできる。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 1.0 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− トリ （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
、Ｌ３，５− ） ＩＪ （２−ヒドロキシフェニル
）ペンゾール、１，１．１− ）す（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−メチルフッエノール、α、α９
．αパ−トリ （４−ヒドロキシフェニル） −１，３
，５−トリ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−ブロムイサチンなどが例示される。Such branching agents include phloroglycin, 2.6
-Simethyl-2.4.6- Tri(4-hydroxyphenyl)hebutene-3,4,6-cymethyl-2.4.6
- tri(4-hydroxyphenyl)hebutene-2
, L3,5-) IJ (2-hydroxyphenyl)penzole, 1,1.1-)su(4-hydroxyphenyl)ethane, 2,6:bis(2-hydroxy-5-
methylbenzyl)-4-methylfuenol, α, α9
．． α-partri (4-hydroxyphenyl) -1,3
, 5-triisopropylbenzene, etc., and 3,3-bis(4-hydroxyaryl)oxindole (= isatin bisphenol), 5-chloroisatin, 5,7-dichloroisatin, 5-bromiisatin, etc. is exemplified.
本発明の製法によるポリカーボネート樹脂は、末端が活
性であるので、共重合用の原料として、またこのビニル
基と容易に゛反応する他のポリマーとの溶融混合等によ
り、従来のポリカーボネートとは容易に相溶せず、有用
な組成物とされなかった樹脂類との組成物の製造などに
好適に使用されるものであり、単独でもしくは通常のポ
リカーボネート樹脂と併用して用いられる。Since the polycarbonate resin produced by the production method of the present invention has active terminals, it can be easily used as a raw material for copolymerization, or by melt-mixing with other polymers that easily react with this vinyl group. It is suitably used in the production of compositions with resins that are not compatible and cannot be used as useful compositions, and can be used alone or in combination with ordinary polycarbonate resins.
なお、これらの組成物を製造する場合においては、必要
に応じて、酸化防止剤、光安定剤、着色剤、無機乃至有
機の充填剤類、炭素繊維、ガラス繊維などの補強剤、滑
剤、帯電防止剤などを適宜併用しても良いものである。In addition, when manufacturing these compositions, antioxidants, light stabilizers, colorants, inorganic or organic fillers, reinforcing agents such as carbon fibers and glass fibers, lubricants, and electrostatic charges may be added as necessary. An inhibitor or the like may be used in combination as appropriate.
以下、実施例および比較例によって具体的に説明する。 Hereinafter, a detailed explanation will be given using Examples and Comparative Examples.
実施例−１
水酸化ナトリウム３．４ｋｇを水４２１に溶解し、２０
°Ｃに保ちながら、２，２−ビス（４−ヒドロキシフェ
ニル）プロパン（−Ｂ Ｐ Ａ） ６．６ ｋｇ、ハイ
ドロサルファイド８ｇを溶解した。Example-1 3.4 kg of sodium hydroxide was dissolved in 421 parts of water, and 20 kg of sodium hydroxide was dissolved in 421 parts of water.
While maintaining the temperature at °C, 6.6 kg of 2,2-bis(4-hydroxyphenyl)propane (-BPA) and 8 g of hydrosulfide were dissolved.
これにメチレンクロライド２８１を加えて攪拌しつつｐ
−イソプロペニルフェノール２５０ｇを加え、ついでホ
スゲン３．３ｋｇを６０分で吹き込んだ。Add methylene chloride 281 to this, and while stirring, p
- 250 g of isopropenylphenol were added and then 3.3 kg of phosgene was bubbled in over 60 minutes.
ホスゲン吹き込み終了後、激しく攪拌して反応液を乳化
させ、乳化後、８ｇのトリエチルアミンを加え約１時間
攪拌を続は重合させた。After the phosgene injection was completed, the reaction solution was vigorously stirred to emulsify it. After emulsification, 8 g of triethylamine was added and the mixture was stirred for about 1 hour to allow polymerization.
重合液を、水相と有機相に分離し、有機相をリン酸で中
和した後、洗液のＰＨが中性となるまで水洗を繰り返し
た後、イソプロパツールを３５ｆｆ加えて、重合物を沈
澱させた。沈澱物を濾過し、その後真空乾燥する事によ
り、白色粉末状のポリカーボネート樹脂を得た。The polymerization solution was separated into an aqueous phase and an organic phase, and the organic phase was neutralized with phosphoric acid. After repeating water washing until the pH of the washing solution became neutral, 35ff of isopropanol was added to the polymerization solution. was precipitated. The precipitate was filtered and then vacuum dried to obtain a white powdery polycarbonate resin.
このポリカーボネートの粘度等を測定した結果を第１表
に示した。The results of measuring the viscosity, etc. of this polycarbonate are shown in Table 1.
実施例−２
実ｊｆｌｌｉ例−１において、ｐ−イソプロペニルフェ
ノールをｍ−イソプロペニルフェノール１２８ｇに変更
する他は同様とした。Example 2 The procedure of Example 1 was repeated except that p-isopropenylphenol was changed to 128 g of m-isopropenylphenol.
結果を第１表に示した。The results are shown in Table 1.
実施例−３
実施例−１において、ＢＰＡに代えてＢＰＺ （＝ Ｌ
１− ヒス（４−ヒドロキシフェニル）シクロヘキサ
ン） ７．７ｋｇに、ｐ−イソプロペニルフェノール
１４８ｇにそれぞれ変更した他は同様とした。Example-3 In Example-1, BPZ (= L
The procedure was the same except that 7.7 kg of 1-his(4-hydroxyphenyl)cyclohexane) and 148 g of p-isopropenylphenol were used.
結果を第１表に示した。The results are shown in Table 1.
実施例−４
実施例−１において、ＢＰＡに代えて、ＢＰＡｐ ＜＝
ビス（４−ヒドロキシフェニル）−フェニルメタン）
８．４ｋｇに、ｐ−イソプロペニルフェノール１９４
ｇにそれぞれ変更した他は同様とした。Example-4 In Example-1, instead of BPA, BPAp <=
bis(4-hydroxyphenyl)-phenylmethane)
8.4 kg, p-isopropenylphenol 194
The same procedure was used except for changing to g.
結果を第１表に示した。The results are shown in Table 1.
実施例−５
実施例−１において、ＢＰＡ ３．３ ｋｇＸＢＰＺ
３．９ ｋｇに変更した他は同様とした。Example-5 In Example-1, BPA 3.3 kgXBPZ
The same procedure was used except that the weight was changed to 3.9 kg.
結果を第１表に示した。The results are shown in Table 1.
実施例−６
実施例−１において、ＢＰＡ ３．３ ｋｇ、 ＢＰ
ＡＰ４．２ｋｇに、ｐ−イソプロペニルフェノール１２
８ｇに変更した他は同様とした。Example-6 In Example-1, BPA 3.3 kg, BP
AP4.2kg, p-isopropenylphenol 12
Same procedure except that it was changed to 8g.
結果を第１表に示した。The results are shown in Table 1.
なお、第１表中の記載は下記によった。Note that the description in Table 1 is as follows.
本発明の製造方法によれば、通常のポリカーボネート樹
脂の製法と同様にして末端ビニル基含有ポリカーボネー
ト樹脂が得られるものであり、工業化が極めて容易であ
る。又、製造した末端ビニル基含有ポリカーボネート樹
脂は、安定性に優れかつ、ビニル基の性質を利用して、
従来単純混合法によっては、相溶性不良等から有用な組
成物を得ることの出来なかった樹脂類とのブレンド素材
として、更に、ビニル基を利用してブロック−コポリマ
ーの原料とすることなど容易に可能なものであるという
特徴を有するものである。According to the production method of the present invention, a terminal vinyl group-containing polycarbonate resin can be obtained in the same manner as a normal polycarbonate resin production method, and industrialization is extremely easy. In addition, the produced polycarbonate resin containing terminal vinyl groups has excellent stability, and by utilizing the properties of vinyl groups,
It can be easily used as a blend material with resins, for which it was not possible to obtain useful compositions due to poor compatibility using conventional simple mixing methods, and it can also be easily used as a raw material for block copolymers using the vinyl group. It is characterized by being possible.
Claims (1)
子量調節剤として、下記一般式（１）で表されるイソプ
ロペニルフェノールを使用することを特徴とするとビニ
ル末端ポリカーボネート樹脂の製法。 一般式（１）： ▲数式、化学式、表等があります▼・・・・・（１） （式中のＸ＾１は、Ｆ、Ｃｌ、Ｂｒ又は低級アルキル基
若しくはアルキロキシ基を示し、ｎは０〜４の整数を示
す。）[Scope of Claim] A method for producing a vinyl-terminated polycarbonate resin by a solution method, characterized in that isopropenylphenol represented by the following general formula (1) is used as a molecular weight regulator. General formula (1): ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(1) (X^1 in the formula represents F, Cl, Br, or a lower alkyl group or an alkyloxy group, and n is (Indicates an integer from 0 to 4.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14600986A JPS633023A (en) | 1986-06-24 | 1986-06-24 | Production of vinyl-terminated polycarbonate resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14600986A JPS633023A (en) | 1986-06-24 | 1986-06-24 | Production of vinyl-terminated polycarbonate resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS633023A true JPS633023A (en) | 1988-01-08 |
Family
ID=15398026
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14600986A Pending JPS633023A (en) | 1986-06-24 | 1986-06-24 | Production of vinyl-terminated polycarbonate resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS633023A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5362838A (en) * | 1993-02-19 | 1994-11-08 | Virginia Polytechnic Institute And State University | Carbonate polymers containing ethenyl aryl moieties |
| US5508359A (en) * | 1993-11-22 | 1996-04-16 | The Dow Chemical Company | Blends of high MW branched polycarbonate with a lower MW polycarbonate |
| US5552224A (en) * | 1993-11-22 | 1996-09-03 | The Dow Chemical Company | Carbonate blend polymer compositions comprising a high molecular weight branched carbonate polymer component and methods for their preparation |
-
1986
- 1986-06-24 JP JP14600986A patent/JPS633023A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5362838A (en) * | 1993-02-19 | 1994-11-08 | Virginia Polytechnic Institute And State University | Carbonate polymers containing ethenyl aryl moieties |
| US5508359A (en) * | 1993-11-22 | 1996-04-16 | The Dow Chemical Company | Blends of high MW branched polycarbonate with a lower MW polycarbonate |
| US5552224A (en) * | 1993-11-22 | 1996-09-03 | The Dow Chemical Company | Carbonate blend polymer compositions comprising a high molecular weight branched carbonate polymer component and methods for their preparation |
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