JPH01272631A - Production of polycarbonate resin - Google Patents
Production of polycarbonate resinInfo
- Publication number
- JPH01272631A JPH01272631A JP10138388A JP10138388A JPH01272631A JP H01272631 A JPH01272631 A JP H01272631A JP 10138388 A JP10138388 A JP 10138388A JP 10138388 A JP10138388 A JP 10138388A JP H01272631 A JPH01272631 A JP H01272631A
- Authority
- JP
- Japan
- Prior art keywords
- metal compound
- alkali metal
- catalyst
- earth metal
- bisphenol
- 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 description 14
- 239000004431 polycarbonate resin Substances 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 150000001339 alkali metal compounds Chemical class 0.000 claims abstract description 19
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims abstract description 14
- -1 diaryl carbonate Chemical compound 0.000 claims abstract description 12
- 238000005809 transesterification reaction Methods 0.000 claims description 9
- 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 abstract description 24
- 238000006243 chemical reaction Methods 0.000 abstract description 21
- 229930185605 Bisphenol Natural products 0.000 abstract description 8
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract 2
- 229920005989 resin Polymers 0.000 abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 1
- 238000004040 coloring Methods 0.000 description 17
- 229920000642 polymer Polymers 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 150000002989 phenols Chemical class 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 6
- 229920000515 polycarbonate Polymers 0.000 description 6
- 239000004417 polycarbonate Substances 0.000 description 6
- 238000002835 absorbance Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 4
- 239000000347 magnesium hydroxide Substances 0.000 description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 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 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 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
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- ZKZKMLKTQUCSNX-UHFFFAOYSA-N 2,6-dibromo-4-(3,5-dibromo-4-hydroxyphenyl)sulfinylphenol Chemical compound C1=C(Br)C(O)=C(Br)C=C1S(=O)C1=CC(Br)=C(O)C(Br)=C1 ZKZKMLKTQUCSNX-UHFFFAOYSA-N 0.000 description 1
- TXYQFJWVHVYIHB-UHFFFAOYSA-N 2,6-dichloro-4-(3,5-dichloro-4-hydroxyphenoxy)phenol Chemical compound C1=C(Cl)C(O)=C(Cl)C=C1OC1=CC(Cl)=C(O)C(Cl)=C1 TXYQFJWVHVYIHB-UHFFFAOYSA-N 0.000 description 1
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-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
- 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
- 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 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
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920001651 Cyanoacrylate Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000005036 alkoxyphenyl group Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical class [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 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
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- NLCKLZIHJQEMCU-UHFFFAOYSA-N cyano prop-2-enoate Chemical class C=CC(=O)OC#N NLCKLZIHJQEMCU-UHFFFAOYSA-N 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 150000005205 dihydroxybenzenes Chemical class 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 125000005429 oxyalkyl group Chemical group 0.000 description 1
- 150000008379 phenol ethers Chemical class 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はエステル交換法によりポリカーボネートを製造
する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing polycarbonate by a transesterification method.
更に詳しくは、二価フェノールとジアリールカーボネー
トのエステル交換反応において、アルカリ金属化合物及
びアルカリ土類金属化合物からなる触媒を使用すること
を特徴とするポリカーボネート樹脂の製法に関するもの
である。More specifically, the present invention relates to a method for producing a polycarbonate resin characterized by using a catalyst comprising an alkali metal compound and an alkaline earth metal compound in the transesterification reaction of dihydric phenol and diaryl carbonate.
（従来技術とその課題）
一般に二価フェノールとジアリールカーボネートのエス
テル交換反応によるポリカーボネートの製造は、アルカ
リ金属化合物触媒の存在下、窒素の如き不活性ガス中で
行われる。まず、二価フェノールとジアリールカーボネ
ートの混合物を加熱溶融し、触媒を添加する。そして、
温度２００〜２３０°Ｃ９圧力１０〜３０ｍｍＨｇの条
件で撹はん下に反応させると、大部分のフェノールが留
去される。(Prior Art and its Problems) Generally, the production of polycarbonate by transesterification of dihydric phenol and diaryl carbonate is carried out in the presence of an alkali metal compound catalyst in an inert gas such as nitrogen. First, a mixture of dihydric phenol and diaryl carbonate is heated and melted, and a catalyst is added. and,
When the reaction is carried out with stirring at a temperature of 200 to 230°C and a pressure of 10 to 30 mmHg, most of the phenol is distilled off.
更に温度を２７０〜３００°Ｃまで上昇させ、圧力もｌ
ｍｍＨｇ以下にすると、フェノールはほとんど除去され
て、高分子量ポリカーボネートが得られる。Furthermore, the temperature was increased to 270-300°C, and the pressure was also increased.
When the temperature is below mmHg, most of the phenol is removed and a high molecular weight polycarbonate is obtained.
しかしながら、こうして合成されたポリカーボネートは
、薄黄色に着色することが多く、着色のないポリカーボ
ネートを得ることは困難であった。（゛プラスチック材
料講座■ポリカーボネート樹脂”ｐ８３日刊工業新聞社
（１９７９） ）（課題を解決するための手段）
本発明者らは、エステル交換法によるポリカーボネート
樹脂の製造方法において、高活性で、かつ着色のない透
明性に優れたポリカーボネート樹脂を合成し得る触媒を
見出す為に鋭意研究を重ねた結果、アルカリ金属化合物
及びアルカリ土類金属化合物からなる触媒を用いて反応
せしめることによって、ポリカーボネート樹脂の着色を
抑制でき、且つまた高い触媒活性が得られることを見出
した。However, the polycarbonate synthesized in this way is often colored pale yellow, and it has been difficult to obtain a polycarbonate without coloring. (Plastic Materials Course - Polycarbonate Resin, p. 83, Nikkan Kogyo Shimbun, 1979) (Means for Solving the Problem) The present inventors have developed a method for producing polycarbonate resin using a transesterification method, which is highly active and colored. As a result of extensive research in order to find a catalyst that can synthesize polycarbonate resin with excellent transparency and no color, we have discovered that the coloring of polycarbonate resin can be reduced by reacting it with a catalyst consisting of an alkali metal compound and an alkaline earth metal compound. It has been found that the catalytic activity can be suppressed and high catalytic activity can be obtained.
即ち本発明は、二価フェノールとジアリールカーボネー
トからエステル交換反応によりポリカーボネート樹脂を
製造するにあたり、エステル交換触媒としてアルカリ金
属化合物とアルカリ土類金属化合物からなる触媒を添加
することを特徴とするポリカーボネート樹脂の製法であ
る。That is, the present invention provides a polycarbonate resin characterized in that a catalyst consisting of an alkali metal compound and an alkaline earth metal compound is added as a transesterification catalyst when producing a polycarbonate resin from a dihydric phenol and a diaryl carbonate by a transesterification reaction. It's the manufacturing method.
本発明の内容を以下に詳細に説明する。本発明の内容の
実施にあたって使用する二価フェノールは、反応性基が
二つのフェノール性ヒドロキシル基である既知のフェノ
ールである。これらのいくつかは、−数式
によって表される。式中Ａは、炭素原子１〜約１５を含
有する二価炭化水素基；炭素原子１〜約１５を含有する
置換二価炭化水素基及びハロゲンｊ Ｓ ｊ−８二
Ｓ−
の如き置換基であり、各Ｘは独立に、水素、ハロゲン、
炭素原子１〜約８のアルキル基の如き一何次素基、炭素
原子６〜１８のアリール基、炭素原子７〜約１４のアル
キル基、炭素原子１〜約８のオキシアルキル基、または
炭素原子６〜１８のオキシアリール基からなる群から選
択する、ｍはＯ又は１である。The content of the present invention will be explained in detail below. The dihydric phenols used in carrying out the subject matter of the present invention are the known phenols whose reactive groups are two phenolic hydroxyl groups. Some of these are represented by - formulas. where A is a divalent hydrocarbon group containing 1 to about 15 carbon atoms; a substituted divalent hydrocarbon group containing 1 to about 15 carbon atoms; and a substituent such as halogen j S j-82S- Yes, each X independently represents hydrogen, halogen,
A primary elementary group such as an alkyl group of 1 to about 8 carbon atoms, an aryl group of 6 to 18 carbon atoms, an alkyl group of 7 to about 14 carbon atoms, an oxyalkyl group of 1 to about 8 carbon atoms, or a carbon atom m is O or 1 selected from the group consisting of 6 to 18 oxyaryl groups.
本発明の実施に当たって使用しうる二価フェノールのい
くつかの代表例には、ビスフェノール例えばビス（４−
ヒドロキシフェニル）メタン、２，２−ビス（４−ヒド
ロキシフェニル）プロパン（ビスフェノールＡとしても
知られている）、２，２−ビス（４−ヒドロキシ−３−
メチルフェニル）プロパン、４，４．ビス（４−ヒドロ
キシフェニル）へブタン、２，２−ビス（４−ヒドロキ
シ−３，５−ジクロロフェニル）プロパン、２，２−ビ
ス（４−ヒドロキシ−３，５−ジブロモフェニル）プロ
パン等；二価フェノールエーテル例えばビス（４−ヒド
ロキシフェニル）エーテル、ビス（３，５−ジクロロ−
４−ヒドロキシフェニル）エーテル等；ジヒドロキシジ
フェニル例えば、Ｐ、Ｐ−ジヒドロキシジフェニル、３
，３−ジクロロ−４，４−ジヒドロキシジフェニル等；
ジヒドロキシアリールスルホン例えば、ビス（４−ヒド
ロキシフェニルスルホン、ビス（３，５−ジメチル、４
．ヒドロキシフェニル）スルホン等；ジヒドロキシベン
ゼン、ハロゲン及びアルキル置換ジヒドロキシベンゼン
例えば・、１，４−ジヒドロキシ−２，５，ジクロロベ
ンゼン、１．４−ジヒドロキシ−３−メチルベンゼン等
；及びジヒドロキシジフェニルスルフィド及びスルホキ
サイド例えばビス（４−ヒドロキシフェニル）サルファ
イド及びビス（４−ヒドロキシフェニル）スルホキサイ
ド、ビス（３，５−ジブロモ−４−ヒドロキシフェニル
）スルホキサイド等がある。Some representative examples of dihydric phenols that may be used in the practice of this invention include bisphenols such as bis(4-
hydroxyphenyl)methane, 2,2-bis(4-hydroxyphenyl)propane (also known as bisphenol A), 2,2-bis(4-hydroxy-3-
methylphenyl)propane, 4,4. Bis(4-hydroxyphenyl)hebutane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, etc.; divalent Phenol ethers such as bis(4-hydroxyphenyl)ether, bis(3,5-dichloro-
4-hydroxyphenyl) ether, etc.; dihydroxydiphenyl e.g. P, P-dihydroxydiphenyl, 3
, 3-dichloro-4,4-dihydroxydiphenyl, etc.;
Dihydroxyarylsulfones such as bis(4-hydroxyphenylsulfone, bis(3,5-dimethyl, 4
．． hydroxyphenyl) sulfone, etc.; dihydroxybenzene, halogen- and alkyl-substituted dihydroxybenzene, e.g., 1,4-dihydroxy-2,5, dichlorobenzene, 1,4-dihydroxy-3-methylbenzene, etc.; and dihydroxydiphenyl sulfide and sulfoxide, e.g. Examples include bis(4-hydroxyphenyl) sulfide, bis(4-hydroxyphenyl) sulfoxide, and bis(3,5-dibromo-4-hydroxyphenyl) sulfoxide.
別の二価フェノール、例えば米国特許第２９９９８３５
号、第３０２８３６５号及び第３１５３００８号に記載
されている二価フェノールも利用できる。二種類以上の
異なる二価フェノール又は二価フェノールとグリコール
の組合せも使用しうろことは勿論である。ここでグリコ
ールとは炭素数２〜２０の脂肪族の二価アルコールであ
る。Another dihydric phenol, such as U.S. Pat. No. 2,999,835
Dihydric phenols described in US Pat. No. 3,028,365 and No. 3,153,008 can also be used. Of course, two or more different dihydric phenols or a combination of dihydric phenols and glycols may also be used. Here, glycol is an aliphatic dihydric alcohol having 2 to 20 carbon atoms.
本発明の実施に当たって使用する炭酸ジアリールとして
は、次の一般式で示されるものが用いられる。As the diaryl carbonate used in carrying out the present invention, those represented by the following general formula are used.
式中Ａｒ、とＡｒ２が同じでも異なるものであってもよ
い。Ａｒｌ ＊ Ａｒ２はフェニル又はメチル、エチル
、プロピル基等の置換基を有するアルキルフェニル、メ
トキシやエトキシ、プロポキシ基等の置換基を有するア
ルコキシフェニル、フェノキシ基を持つフェノキシフェ
ニル、アリール基を置換基に持つアリールフェニル、塩
素や臭素の置換基を持つハロゲン化フェニルヲ表ス。In the formula, Ar and Ar2 may be the same or different. Arl * Ar2 is phenyl or alkylphenyl having a substituent such as methyl, ethyl, or propyl group, alkoxyphenyl having a substituent such as methoxy, ethoxy, or propoxy group, phenoxyphenyl having a phenoxy group, or having an aryl group as a substituent Aryl phenyl, halogenated phenyl with chlorine or bromine substituents.
本発明の実施に当たって使用するアルカリ金属化合物は
、リチウム、ナトリウム、カリウム。The alkali metal compounds used in carrying out the present invention are lithium, sodium, and potassium.
ルビジウム、セシウムの水酸化物、塩化物、酸化物、リ
ン酸塩、酢酸塩、硫酸塩、硝酸塩等が例示され、アルカ
リ土類金属化合物には、ベリリウム、マグネシウム、カ
ルシウム、ストロンチウム。Examples include hydroxides, chlorides, oxides, phosphates, acetates, sulfates, and nitrates of rubidium and cesium, and alkaline earth metal compounds include beryllium, magnesium, calcium, and strontium.
バリウムの水酸化物、塩化物、酸化物、リン酸塩、酢酸
塩、硫酸塩、硝酸塩等が例示される。これらのアルカリ
金属化合物及び、アルカリ土類金属化合物のうち、水酸
化物、酸化物、酢酸塩が好ましい。Examples include barium hydroxide, chloride, oxide, phosphate, acetate, sulfate, and nitrate. Among these alkali metal compounds and alkaline earth metal compounds, hydroxides, oxides, and acetates are preferred.
これらの触媒は、合計で通常のエステル交換反応の有効
量のビスフェノール基準で約１０−６〜１０−１モル％
、好ましくは１０−４〜１０−２モル％が使用される。These catalysts are present in a total amount of about 10-6 to 10-1 mole percent based on bisphenol, an effective amount for conventional transesterification reactions.
, preferably 10-4 to 10-2 mol%.
あまりに少量では触媒効果は十分でなく、あまりに多量
に用いると着色防止効果は減少する。また、アルカリ金
属化合物とアルカリ土類金属化合物との比率は、モル比
で１：０．１〜０．１ ： １、好ましくは１ ：０．
３〜０．３ ： １である。If the amount is too small, the catalytic effect will not be sufficient, and if the amount is too large, the coloring prevention effect will be reduced. The molar ratio of the alkali metal compound to the alkaline earth metal compound is 1:0.1 to 0.1:1, preferably 1:0.
3-0.3:1.
本発明で得られるポリカーボネート樹脂に、使用目的に
合わせて任意の添加剤を混合してもよい。このような添
加剤としては、例えば酸化防止剤、加水分解安定剤、例
えばエポキシド類、リン系（１，合物類、フェノール系
化合物等紫外線吸収剤、例えばベンゾフェノン類、ベン
ゾトリアゾール類、シアノアクリレート類等、衝撃改質
剤、充填剤２着色安定剤、難燃剤等である。Any additives may be mixed into the polycarbonate resin obtained in the present invention depending on the purpose of use. Such additives include, for example, antioxidants, hydrolysis stabilizers, epoxides, phosphorus compounds, phenolic compounds, etc. Ultraviolet absorbers, such as benzophenones, benzotriazoles, cyanoacrylates, etc. etc., impact modifiers, fillers, color stabilizers, flame retardants, etc.
以下、具体的に実施例により発明の詳細な説明する。Hereinafter, the invention will be specifically explained in detail with reference to Examples.
本発明により得られたポリカーボネートの評価に用いた
項目の測定方法は、次の通りである。The methods for measuring the items used to evaluate the polycarbonate obtained according to the present invention are as follows.
（１）粘度平均分子量の評価方法： ２０’Ｃにおける
塩化メチレン溶液の固有粘度［ｒｌ］ （ｄｌ／ ｇ）
をウベローデ粘度管を用いて測定し、次式を用いて粘度
平均分子量Ｍｖを計算した。(1) Evaluation method of viscosity average molecular weight: Intrinsic viscosity of methylene chloride solution at 20'C [rl] (dl/g)
was measured using an Ubbelohde viscosity tube, and the viscosity average molecular weight Mv was calculated using the following formula.
［ｒｌ］＝１．１１Ｘ１０−’ （Ｍｖ）０−８２（２
）着色の評価方法：塩化メチレン中に１００ｇ／ｌの濃
度でポリカーボネート樹脂を溶解させた溶液を光路長１
００ｍｍのセルに入れ分光光度計を使用して３５０部ｍ
〜６００ｎｍの波長に対する吸光度を測定し、３８０部
ｍの吸光度の値から５８０部ｍの吸光度の値を引いた値
で着色を評価した。数字は小さい程着色が少ないことを
意味する。[rl]=1.11X10-' (Mv)0-82(2
) Coloring evaluation method: A solution of polycarbonate resin dissolved in methylene chloride at a concentration of 100 g/l was
00mm cell and use a spectrophotometer to measure 350 parts.
The absorbance at a wavelength of ~600 nm was measured, and the coloration was evaluated based on the value obtained by subtracting the absorbance value at 580 parts m from the absorbance value at 380 parts m. The smaller the number, the less coloring.
以下、部は重量基準を示す。Hereinafter, parts are based on weight.
（実施例）
実施例１
窒素置換した撹はん機付反応器にビスフェノールＡ１８
３部とジフェニルカーボネート１７６部を入れ、１６０
０Ｃで溶融した後、触媒として水酸化マグネシウムと水
酸化リチウムをそれぞれビスフェノールＡに対して５×
１０°４モル％加え、反応を開始する。３時間かけて徐
々に２７０°Ｃまで昇温し、反応系圧力も１０ｍｍＨｇ
まで減圧し、生成するフェノールを留去する。引続き２
７０°Ｃで１時間３０分０．１５〜０．１０ｍｍＨｇで
反応させ、ポリマーを得た。(Example) Example 1 Bisphenol A18 was added to a reactor equipped with a stirrer and replaced with nitrogen.
3 parts and 176 parts of diphenyl carbonate, and 160 parts
After melting at 0C, magnesium hydroxide and lithium hydroxide were used as catalysts, respectively, at 5x for bisphenol A.
10° 4 mol% was added to start the reaction. The temperature was gradually raised to 270°C over 3 hours, and the reaction system pressure was 10 mmHg.
The pressure is reduced to 100%, and the phenol produced is distilled off. Continued 2
The reaction was carried out at 70°C for 1 hour and 30 minutes at 0.15 to 0.10 mmHg to obtain a polymer.
得られたポリマーは着色がなく透明性に優れ、粘度平均
分子量が２１，０００であった。The obtained polymer was free from coloration, had excellent transparency, and had a viscosity average molecular weight of 21,000.
得られたポリマーの着色の評価の結果は、第１表及び第
１図に示した。The results of evaluating the coloring of the obtained polymers are shown in Table 1 and Figure 1.
実施例２
窒素置換した撹はん機付反応器にビスフェノ−フルＡ１
８３部とジフェニルカーボネート１７６部を入れ、１６
０°Ｃで溶融した後、触媒として水酸化マグネシウムと
水酸化リチウムをそれぞれビスフェノールＡに対してＩ
Ｘ １０’モル％加え、反応を開始する。３時間かけ
て徐々に２７０°Ｃまで昇温し、反応系圧力も１０ｍｍ
Ｈｇまで減圧し、生成するフェノールを留去する。引続
き２７０°Ｃで２時間０．１５〜０．１０ｍｍＨｇで反
応させ、ポリマーを得た。得られたポリマーは着色がな
く透明性に優れ、粘度平均分子量が２９，８００であっ
た。Example 2 Bisphenoflu A1 was added to a reactor equipped with a stirrer and replaced with nitrogen.
Add 83 parts and 176 parts of diphenyl carbonate,
After melting at 0 °C, magnesium hydroxide and lithium hydroxide were used as catalysts for bisphenol A, respectively.
Add 10'mol% of X to start the reaction. The temperature was gradually raised to 270°C over 3 hours, and the reaction system pressure was also 10 mm.
The pressure is reduced to Hg and the formed phenol is distilled off. Subsequently, the reaction was carried out at 270°C for 2 hours at 0.15 to 0.10 mmHg to obtain a polymer. The obtained polymer was free from coloration, had excellent transparency, and had a viscosity average molecular weight of 29,800.
得られたポリマーの着色の評価の結果は、第１表及び第
１図に示した。The results of evaluating the coloring of the obtained polymers are shown in Table 1 and Figure 1.
比較例１
窒素置換した撹はん機付反応器にビスフェノールＡ１８
３部とジフェニルカーボネート１７６部を入れ、１６０
°Ｃで溶融した後、触媒として水酸化リチウムをビスフ
ェノールＡに対して１×１０°３モル％加え、反応を開
始する。３時間かけて徐々に２７００Ｃまで昇温し、反
応系圧力も１０ｍｍＨｇまで減圧し、生成するフェノー
ルを留去する。引続き２７００Ｃで２時間０．１５〜０
．１０ｍｍＨｇで反応させ、ポリマーを得た。Comparative Example 1 Bisphenol A18 was added to a reactor equipped with a stirrer and replaced with nitrogen.
3 parts and 176 parts of diphenyl carbonate, and 160 parts
After melting at °C, 1x10°3 mol% of lithium hydroxide is added to bisphenol A as a catalyst to start the reaction. The temperature was gradually raised to 2700C over 3 hours, the reaction system pressure was also reduced to 10 mmHg, and the produced phenol was distilled off. Continue at 2700C for 2 hours from 0.15 to 0.
．． The reaction was carried out at 10 mmHg to obtain a polymer.
得られたポリマーの着色の評価の結果は、第１表及び第
１図に示した。The results of evaluating the coloring of the obtained polymers are shown in Table 1 and Figure 1.
実施例３
窒素置換した撹はん機付反応器にビスフェノールＡ１８
３部とジフェニルカーボネート１７６部を入れ、１６０
°Ｃで溶融した後、触媒として水酸化マグネシウムと水
酸化セシウムをそれぞれビスフェノールＡに対して５
Ｘ １０’モル％加え、反応を開始する。３時間かけて
徐々に２７０°Ｃまで昇温し、反応系圧力も１０ｍｍＨ
ｇまで減圧し、生成するフェノールを留去する。引続き
２７０°Ｃで２時間０．１５〜０．１０ｍｍＨｇで反応
させ、ポリマーを得た。得られたポリマーは着色がなく
透明性に優れ、粘度平均分子量が２１，１００であった
。Example 3 Bisphenol A18 was added to a reactor equipped with a stirrer and replaced with nitrogen.
3 parts and 176 parts of diphenyl carbonate, and 160 parts
After melting at °C, magnesium hydroxide and cesium hydroxide were used as catalysts at 5% for bisphenol A, respectively.
Add 10'mol% of X to start the reaction. The temperature was gradually raised to 270°C over 3 hours, and the reaction system pressure was 10 mmH.
The pressure is reduced to 1.5 g, and the phenol produced is distilled off. Subsequently, the reaction was carried out at 270°C for 2 hours at 0.15 to 0.10 mmHg to obtain a polymer. The obtained polymer was free from coloration, had excellent transparency, and had a viscosity average molecular weight of 21,100.
得られたポリマーの着色の評価の結果は、第２表及び第
２図に示した。The results of evaluating the coloring of the obtained polymers are shown in Table 2 and Figure 2.
実施例４
窒素置換した撹はん機付反応器にビスフェノールＡ１８
３部とジフェニルカーボネート１７６部を入れ、１６０
°Ｃで溶融した後、触媒として水酸化マグネシウムと水
素化ホウ素カリウムをそれぞれビスフェノールＡに対し
て５ｘｉｏ−４モル％加え、反応を開始する。３時間３
０分かけて徐々に２７０°Ｃまで昇温し、反応系圧力も
１０ｍｍＨｇまで減圧し、生成するフェノールを留去す
る。引続き２７０°Ｃで１時間１０分０．１５〜０．１
０ｍｍＨｇで反応させ、ポリマーを得た。得られたポリ
マーは着色がなく透明性に優れ、粘度平均分子量が２０
，７００であった。Example 4 Bisphenol A18 was added to a reactor equipped with a stirrer and replaced with nitrogen.
3 parts and 176 parts of diphenyl carbonate, and 160 parts
After melting at °C, magnesium hydroxide and potassium borohydride are each added in an amount of 5xio-4 mol % based on bisphenol A as catalysts to start the reaction. 3 hours 3
The temperature was gradually raised to 270°C over 0 minutes, the reaction system pressure was also reduced to 10 mmHg, and the produced phenol was distilled off. Continue at 270°C for 1 hour and 10 minutes 0.15 to 0.1
The reaction was carried out at 0 mmHg to obtain a polymer. The obtained polymer has no coloration, excellent transparency, and a viscosity average molecular weight of 20.
,700.
得られたポリマーの着色の評価の結果は、第２表及び第
２図に示した。The results of evaluating the coloring of the obtained polymers are shown in Table 2 and Figure 2.
比較例２〜３
窒素置換した撹はん機付反応器にビスフェノールＡ１８
３部とジフエニ・ルカーボネート１７６部を入れ、１６
０°Ｃで溶融した後、触媒として第２表に示した化合物
をビスフェノールＡに対してＩ Ｘ １０”３モル％加
え、反応を開始する。３時間かけて徐々に２７０°Ｃま
で昇温し、反応系圧力も１０ｍｍＨｇまで減圧し、生成
するフェノールを留去する。引続き２７０°Ｃで２時間
０．１５〜０．１０ｍｍＨｇで反応させ、ポリマーを得
た。Comparative Examples 2-3 Bisphenol A18 was added to a reactor equipped with a stirrer and replaced with nitrogen.
3 parts and 176 parts of diphenilucarbonate, 16
After melting at 0°C, a compound shown in Table 2 was added as a catalyst in an amount of 3 mol% of IX10 based on bisphenol A, and the reaction was started.The temperature was gradually raised to 270°C over 3 hours. The pressure of the reaction system was also reduced to 10 mmHg to distill off the produced phenol.Subsequently, the reaction was carried out at 270°C for 2 hours at 0.15 to 0.10 mmHg to obtain a polymer.
得られたポリマーの着色の評価の結果は、第２表及び第
２図に示した。The results of evaluating the coloring of the obtained polymers are shown in Table 2 and Figure 2.
（発明の効果）
第１表より実施例１の着色度は比較例１の着色度より小
さいことがわかる。このことより、アルカリ金属化合物
とアルカリ土類金属化合物からなる触媒を用いて合成し
たポリカーボネート樹脂は、アルカリ金属化合物を単独
で使用して得たポリカーボネート樹脂よりも着色が少な
いことがわかる。(Effects of the Invention) Table 1 shows that the degree of coloring of Example 1 is smaller than that of Comparative Example 1. This shows that the polycarbonate resin synthesized using a catalyst consisting of an alkali metal compound and an alkaline earth metal compound has less coloring than the polycarbonate resin obtained by using an alkali metal compound alone.
また、実施例１は、総触媒量を比較例１の触媒量に合わ
せた例であるが、アルカリ金属化合物の量を比較例１の
アルカリ金属化合物量に合わせ、更に同量のアルカリ土
類金属化合物を加えた実施例２においても、比較例１よ
り着色が少ないことが第１表よりわかる。Further, in Example 1, the total amount of catalyst was adjusted to the amount of catalyst in Comparative Example 1, but the amount of alkali metal compound was adjusted to the amount of alkali metal compound in Comparative Example 1, and the same amount of alkaline earth metal was added. Table 1 shows that even in Example 2, in which the compound was added, there was less coloring than in Comparative Example 1.
以上より本発明の効果は十分に証明される。From the above, the effects of the present invention are fully proven.
更に実施例３〜４．比較例２〜３において、実施例１〜
２．比較例１で示したアルカリ金属化合物とアルカリ土
類金属化合物の組合せ以外のアルカリ金属化合物とアル
カリ土類金属化合物の組合せ例を示した。第２表及び第
２図より、実施例２．実施例３共にアルカリ金属化合物
を単独で触媒として使用した場合（比較例２〜３）より
、着色が少ないことがわかる。Furthermore, Examples 3-4. In Comparative Examples 2 to 3, Examples 1 to 3
2. Examples of combinations of alkali metal compounds and alkaline earth metal compounds other than the combination of alkali metal compounds and alkaline earth metal compounds shown in Comparative Example 1 are shown. From Table 2 and FIG. 2, Example 2. It can be seen that in both Example 3, there was less coloring than in the case where an alkali metal compound was used alone as a catalyst (Comparative Examples 2 to 3).
第１図は、実施例１〜２．比較例１の着色評価の試験に
おける３５０ｎｍ〜６００ｎｍの範囲の吸光度曲線を図
示したものである。
第２図は、実施例３〜４．比較例２〜３の着色評価の試
験における３５０ｎｍ〜６００ｎｍの範囲の吸光度曲線
を図示したものである。
（符号の説明）
ａ ・・・・・・ 実施例１
ｂ ・・・・・・ 実施例２
Ｃ・・・・・・ 比較例１
ｄ ・・・・・・ 実施例３
ｅ ・・・・・・ 比較例２
ｆ ・・・・・・ 比較例３
ｇ ・・・・・・ 実施例４
第１図
第２図FIG. 1 shows examples 1 to 2. 2 is a diagram illustrating an absorbance curve in the range of 350 nm to 600 nm in a coloring evaluation test of Comparative Example 1. FIG. 2 shows examples 3 to 4. 3 is a diagram illustrating absorbance curves in the range of 350 nm to 600 nm in coloring evaluation tests of Comparative Examples 2 and 3. (Explanation of symbols) a...Example 1 b...Example 2 C...Comparative example 1 d...Example 3 e... ... Comparative example 2 f ... Comparative example 3 g ... Example 4 Fig. 1 Fig. 2
Claims (1)
ル交換反応によりポリカーボネート樹脂を製造するにあ
たり、エステル交換触媒としてアルカリ金属化合物及び
アルカリ土類金属化合物からなる触媒を添加することを
特徴とするポリカーボネート樹脂の製法。A method for producing a polycarbonate resin, which comprises adding a catalyst consisting of an alkali metal compound and an alkaline earth metal compound as a transesterification catalyst when producing the polycarbonate resin from dihydric phenol and diaryl carbonate by transesterification reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10138388A JPH01272631A (en) | 1988-04-26 | 1988-04-26 | Production of polycarbonate resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10138388A JPH01272631A (en) | 1988-04-26 | 1988-04-26 | Production of polycarbonate resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01272631A true JPH01272631A (en) | 1989-10-31 |
Family
ID=14299247
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10138388A Pending JPH01272631A (en) | 1988-04-26 | 1988-04-26 | Production of polycarbonate resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01272631A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03203928A (en) * | 1989-12-28 | 1991-09-05 | Nippon G Ii Plast Kk | Production of polycarbonate |
| EP0520805A2 (en) * | 1991-06-28 | 1992-12-30 | Ge Plastics Japan Limited | Polycarbonate production method |
| EP0520804A2 (en) * | 1991-06-28 | 1992-12-30 | Ge Plastics Japan Limited | Copolymeric polycarbonate production method |
| WO1995002624A1 (en) * | 1993-07-14 | 1995-01-26 | Idemitsu Kosan Co., Ltd. | Process for producing polycarbonate |
| JP2004521177A (en) * | 2001-01-12 | 2004-07-15 | ゼネラル・エレクトリック・カンパニイ | Molten polycarbonate catalyst system |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55142025A (en) * | 1979-04-24 | 1980-11-06 | Mitsubishi Chem Ind Ltd | Process of production of polycarbonate |
-
1988
- 1988-04-26 JP JP10138388A patent/JPH01272631A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55142025A (en) * | 1979-04-24 | 1980-11-06 | Mitsubishi Chem Ind Ltd | Process of production of polycarbonate |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03203928A (en) * | 1989-12-28 | 1991-09-05 | Nippon G Ii Plast Kk | Production of polycarbonate |
| EP0520805A2 (en) * | 1991-06-28 | 1992-12-30 | Ge Plastics Japan Limited | Polycarbonate production method |
| EP0520804A2 (en) * | 1991-06-28 | 1992-12-30 | Ge Plastics Japan Limited | Copolymeric polycarbonate production method |
| US5324809A (en) * | 1991-06-28 | 1994-06-28 | Ge Plastics Japan, Ltd. | Melt catalytic preparation of copolymeric polycarbonate from hydroquinone |
| US5418315A (en) * | 1991-06-28 | 1995-05-23 | Ge Plastics Japan | Copolymeric polycarbonate production method |
| US5484875A (en) * | 1991-06-28 | 1996-01-16 | Ge Plastics Japan | Copolymeric polycarbonate production method |
| WO1995002624A1 (en) * | 1993-07-14 | 1995-01-26 | Idemitsu Kosan Co., Ltd. | Process for producing polycarbonate |
| JP2004521177A (en) * | 2001-01-12 | 2004-07-15 | ゼネラル・エレクトリック・カンパニイ | Molten polycarbonate catalyst system |
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