JPH0379626A - Copolycarbonate resin and production thereof - Google Patents
Copolycarbonate resin and production thereofInfo
- Publication number
- JPH0379626A JPH0379626A JP21406289A JP21406289A JPH0379626A JP H0379626 A JPH0379626 A JP H0379626A JP 21406289 A JP21406289 A JP 21406289A JP 21406289 A JP21406289 A JP 21406289A JP H0379626 A JPH0379626 A JP H0379626A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- formulas
- aryl
- copolycarbonate resin
- bis
- 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
- 229920005989 resin Polymers 0.000 title claims abstract description 18
- 239000011347 resin Substances 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 5
- 125000003118 aryl group Chemical class 0.000 claims abstract description 5
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 4
- 150000002367 halogens Chemical class 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 16
- 229920005668 polycarbonate resin Polymers 0.000 claims description 14
- 239000004431 polycarbonate resin Substances 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000001118 alkylidene group Chemical group 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 4
- 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 9
- 229920001296 polysiloxane Polymers 0.000 abstract description 7
- 125000001931 aliphatic group Chemical group 0.000 abstract description 5
- 150000002989 phenols Chemical class 0.000 abstract description 4
- 229930185605 Bisphenol Natural products 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 125000002947 alkylene group Chemical class 0.000 abstract 1
- 230000001588 bifunctional effect Effects 0.000 abstract 1
- 239000000470 constituent Substances 0.000 abstract 1
- 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
- 230000000052 comparative effect Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000006082 mold release agent Substances 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- -1 phenol compound Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 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 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
- 230000000694 effects Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 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
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-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
- 239000002253 acid Substances 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000006085 branching agent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000001294 propane Substances 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
- KFYLWBHJQAVNGU-UHFFFAOYSA-N (6-hydroxycyclohexa-2,4-dien-1-ylidene)methanone Chemical compound OC1C=CC=CC1=C=O KFYLWBHJQAVNGU-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- URFNSYWAGGETFK-UHFFFAOYSA-N 1,2-bis(4-hydroxyphenyl)ethane Natural products C1=CC(O)=CC=C1CCC1=CC=C(O)C=C1 URFNSYWAGGETFK-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- AOVWJWYVLYFRPC-UHFFFAOYSA-N 1,4-dichloroindole-2,3-dione Chemical compound C1=CC=C(Cl)C2=C1N(Cl)C(=O)C2=O AOVWJWYVLYFRPC-UHFFFAOYSA-N 0.000 description 1
- BSWWXRFVMJHFBN-UHFFFAOYSA-N 2,4,6-tribromophenol Chemical compound OC1=C(Br)C=C(Br)C=C1Br BSWWXRFVMJHFBN-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-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
- 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
- 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
- BATCUENAARTUKW-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)-diphenylmethyl]phenol Chemical compound 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
- 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
- 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
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 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
- NNDKZTBFZTWKLA-LUVWLHFXSA-N Neopine Natural products O(C)c1c2O[C@H]3[C@@H](O)CC=C4[C@H]5N(C)CC[C@]34c2c(cc1)C5 NNDKZTBFZTWKLA-LUVWLHFXSA-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
- 101100191375 Xenopus laevis prkra-b gene Proteins 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 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
- 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
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 150000002148 esters Chemical class 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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 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
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000010102 injection blow moulding Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- DIAIBWNEUYXDNL-UHFFFAOYSA-N n,n-dihexylhexan-1-amine Chemical compound CCCCCCN(CCCCCC)CCCCCC DIAIBWNEUYXDNL-UHFFFAOYSA-N 0.000 description 1
- NNDKZTBFZTWKLA-QISBLDNZSA-N neopine Chemical compound O[C@H]([C@@H]1O2)CC=C3[C@H]4CC5=CC=C(OC)C2=C5[C@@]13CCN4C NNDKZTBFZTWKLA-QISBLDNZSA-N 0.000 description 1
- 230000007935 neutral effect Effects 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
- 239000002244 precipitate Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000001175 rotational moulding Methods 0.000 description 1
- 238000003756 stirring Methods 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
- 239000008096 xylene Substances 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、新規なコーポリカーボネート樹脂およびその
製法であり、このコーポリカーボネート樹脂は、シリコ
ーン鎮、脂肪鎖を有するので離型性、流動性に優れてお
り、この特性を利用して種々の用途に好適に利用される
ものである。Detailed Description of the Invention [Industrial Field of Application] The present invention is a novel copolycarbonate resin and a method for producing the same. This copolycarbonate resin has a silicone base and a fatty chain, so it has good mold releasability and fluidity. This property makes it suitable for use in a variety of applications.
従来、ポリカーボネート樹脂は耐熱性、耐衝撃性等に優
れたものであるが、離型性、流動性が劣ることが欠点の
一つである。Conventionally, polycarbonate resins have excellent heat resistance, impact resistance, etc., but one of their drawbacks is that they have poor mold releasability and fluidity.
離型性を改良する方法としては、主にポリカーボネート
樹脂中に離型剤を添加してなる組成物を用いる方法が取
られている。しかし、離型剤として用いられている化合
物類は必ずしも熱的に安定ではなく、特にポリカーボネ
ート樹脂は高温で成形されるので、離型剤化合物が熱分
解し、ポリカーボネートの分子量を低下させたり、耐熱
性を低下させる不都合がある。また、流動性を改良する
方法としても種々の方法が提案され、可塑剤を配合する
方法、分子量調節剤愛は末端停止剤として可塑化効果を
有する長鎖アルキル基を持った化合物類を用いる方法、
その他種々の方法が知られている。しかし、可塑剤を用
いる方法は上記した離型剤の使用と同様の欠点が生じ、
また、末端に長鎖アルキル基を導入する方法は、末端基
の数が限定されることから流動性の改良効果に制限が生
じるものであった。The main method for improving mold release properties is to use a composition made by adding a mold release agent to a polycarbonate resin. However, the compounds used as mold release agents are not necessarily thermally stable. In particular, since polycarbonate resin is molded at high temperatures, the mold release agent compounds may thermally decompose, lowering the molecular weight of polycarbonate, or increasing the heat resistance. There is an inconvenience that reduces sex. Various methods have also been proposed to improve fluidity, such as adding a plasticizer, and using compounds with long-chain alkyl groups that have a plasticizing effect as end-stoppers. ,
Various other methods are known. However, the method using a plasticizer has the same drawbacks as the use of a mold release agent described above.
Furthermore, the method of introducing a long-chain alkyl group at the end has a limited number of end groups, which limits the fluidity improvement effect.
本発明は、ポリカーボネート樹脂の優れた熱安定性を維
持し、離型性、流動性を改良したポリカーボネート樹脂
を提供することによって、射出成形、射出吹き込み成形
、圧縮成形、回転成形などが容易で、かつ、金型、ダイ
ス、ロールなどに対して非粘着性を有するポリカーボネ
ート樹脂を提供することである。The present invention provides a polycarbonate resin that maintains the excellent thermal stability of polycarbonate resin and has improved mold releasability and fluidity, thereby facilitating injection molding, injection blow molding, compression molding, rotational molding, etc. Another object of the present invention is to provide a polycarbonate resin that is non-adhesive to molds, dies, rolls, and the like.
本発明者らは、上記の課題を解決する方法について鋭意
検討した結果、原料二価フェノールの一部としてシリコ
−゛ン鎖、脂肪鎖を含有する化合物を使用する方法を見
出し、本発明に到達した。As a result of intensive studies on methods to solve the above problems, the present inventors discovered a method of using a compound containing a silicone chain and aliphatic chain as part of the raw material dihydric phenol, and arrived at the present invention. did.
すなわち、本発明は、下記構造式（Ａ）及び（Ｂ）で表
される構成単位を有するコーポリカーボネート樹脂であ
って、該コーポリカーボネート樹脂中の構造式（Ａ）で
表される構成単位が０．１〜７０モル％の範囲であるこ
と、並びに界面重合法によるポリカーボネート樹脂の製
法において、二価フェノールとして下記−数式（１）お
よび（２）で表される化合物を使用することを特徴とす
る新規コーポリカーボネート樹脂の製法である。That is, the present invention provides a copolycarbonate resin having structural units represented by the following structural formulas (A) and (B), wherein the structural unit represented by the structural formula (A) in the copolycarbonate resin is 0. .1 to 70 mol%, and in the method for producing polycarbonate resin by interfacial polymerization, compounds represented by the following formulas (1) and (2) are used as dihydric phenols. This is a new method for producing copolycarbonate resin.
（構造式（Ａ）及び−数式（１）において、ｎは１〜２
００の整数を示す。又、構造式（Ｂ）及び−数式（２）
において、Ｂは炭素数１〜１０の直鎮、分岐鎖酸いは環
状のアルキリデン基、アリール置換アルキレン基、アリ
ール基又は−ｏ−，−ｓ−、−ｃｏ−、−５ｏ２−を示
し、Ｒ１、Ｒ２、Ｒ３及びＲ４は水素、ハロゲン又は炭
素数１〜４のアルキル基を示す。）
以下、本発明の構成について説明する。(In structural formula (A) and -numerical formula (1), n is 1 to 2
Indicates an integer of 00. Also, structural formula (B) and -numerical formula (2)
, B represents a straight chain, branched chain acid or cyclic alkylidene group, aryl-substituted alkylene group, aryl group, or -o-, -s-, -co-, -5o2-, having 1 to 10 carbon atoms, and R1 , R2, R3 and R4 represent hydrogen, halogen or an alkyl group having 1 to 4 carbon atoms. ) Hereinafter, the configuration of the present invention will be explained.
本発明のコーポリカーボネート樹脂は、構成単位として
前記−数式（１）で表されるシリコーン鎮、脂肪鎖を有
するビスフェノールからなる前記構造式（Ａ）の構成単
位を有することにある。コーポリカーボネート中の構造
式（Ａ）で表される構成単位及び該コーポリカーボネー
ト樹脂の製造に使用する一般式（１）の化合物の使用量
は、用いる全て、の二価フェノール中の０．０１〜７０
モル％の範囲、好適には１〜？０モル％の範囲が、耐熱
性を活かし、流動性、離型性を改良する観点から好まし
い。The copolycarbonate resin of the present invention has, as a structural unit, a silicone base represented by the above-mentioned formula (1) and a structural unit of the structural formula (A) consisting of a bisphenol having an aliphatic chain. The amount of the structural unit represented by structural formula (A) in the copolycarbonate and the compound of general formula (1) used in the production of the copolycarbonate resin is from 0.01 to 0.01 to 70
Mol% range, preferably 1 to ? A range of 0 mol % is preferable from the viewpoint of taking advantage of heat resistance and improving fluidity and mold releasability.
このコーポリカーボネート樹脂を製造するのに使用する
前記−数式（２）の二価フェノール系化合物としては、
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）フロパン、２．２−ビス（
４−ヒドロキシフェニル）メタン、１．ｌ−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−ジクロロフ
ェニル）プロパン、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。これらの中で２，２−ビス（
４−ヒドロキシフェニル）プロパン、１．１−ビス（４
−ヒドロキシフェニル）シクロヘキサンが得られるコー
ポリカーボネート樹脂の熱安定性の面から好ましい。The dihydric phenol compound of formula (2) used to produce this copolycarbonate resin is as follows:
Bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxy) phenyl)ketone, 1.1-
Bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)furopane, 2,2-bis(
4-hydroxyphenyl)methane, 1. l-bis(4-
hydroxyphenyl)cyclohexane, 2,2-bis(
4-hydroxy-3,5-dibromophenyl)propane, 2.2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 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-hydroxy) Examples include phenyl〉-1-phenylethane and bis(4-hydroxyphenyl)diphenylmethane. Among these, 2,2-bis(
4-hydroxyphenyl)propane, 1,1-bis(4
-hydroxyphenyl)cyclohexane is preferred from the viewpoint of thermal stability of the copolycarbonate resin.
本発明のコーポリカーボネート樹脂の製法は、従来の芳
香族ポリカーボネート樹脂の製法において、前記−数式
（１）のシリコーン鎖、脂肪鎖を持った二価フェノール
を一部に使用することを除き従来の界面重合法と同様の
方法が適用される。The method for producing a copolycarbonate resin of the present invention is similar to the conventional method for producing an aromatic polycarbonate resin, except that a dihydric phenol having a silicone chain and an aliphatic chain of formula (1) is used in part. A method similar to the polymerization method is applied.
すなわち、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、前記−数式（１）、（２）の
二価フェノール系化合物及び適宜分子量調節剤（末端停
止剤）を用い、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、界面重合を行うことによってポリカーボネート樹脂
を得る。反応に際しては上記−数式（１）および（２）
で示される二価フェノールは同時に反応させる以外に、
場合によっては、−数式（１）か−数式（２）の二価フ
ェノールとホスゲンとをまず反応させ、ついで−数式（
２）か−数式（１）の二価フェノールを反応させる方法
を採用することもできる。さらに、末端停止剤の添加も
ホスゲン化時から重合反応開始時までの間であれば特に
限定されない。In other words, in the interfacial polymerization method, an organic solvent inert to the reaction,
In the presence of an alkaline aqueous solution, the dihydric phenol compound of formulas (1) and (2) above and an appropriate molecular weight regulator (terminal capper) are reacted with phosgene, and then tertiary amine or quaternary A polycarbonate resin is obtained by adding a polymerization catalyst such as a grade ammonium salt and performing interfacial polymerization. For the reaction, the above formulas (1) and (2)
In addition to reacting the dihydric phenols shown at the same time,
In some cases, the dihydric phenol of formula (1) or formula (2) is first reacted with phosgene, and then -
2) A method of reacting dihydric phenol of formula (1) can also be adopted. Furthermore, the addition of the terminal terminator is not particularly limited as long as it is between the time of phosgenation and the start of the polymerization reaction.
ここに、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、１，１．１−）リクロロエ
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、二） ＩＪ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使用
してもよい。Here, examples of solvents inert to the reaction include dichloromethane, 1,2-dichloroethane, 1.1.2.2-tetrachloroethane, chloroform, 1,1.1-)lichloroethane, carbon tetrachloride, monochlorobenzene, Examples include chlorinated hydrocarbons such as dichlorobenzene; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; and ether compounds such as diethyl ether; two or more of these organic solvents can be used in combination. You can also do that. In addition, if desired, solvents that have affinity with water such as ethers, ketones, esters, and IJs other than those mentioned above may be used within the limit that the mixed solvent system is not completely miscible with water. .
末端停止剤或いは分子量調節剤としては一価のフェノー
ル性水酸基を有する化合物が挙げられ、通常のフェノー
ル、ｐ−第三ブチルフェノール、トリブロモフェノール
などの他に、長鎖アル牛ルフェノール、脂肪族カルボン
酸クロライド、脂肪族カルボン酸、ヒドロキシ安息香酸
アルキルエステル、ヒドロキシ・フェニル酸アルキルエ
ステル、アルキルエーテルフェノールなどが例示される
。Examples of the terminal capping agent or molecular weight regulator include compounds having a monovalent phenolic hydroxyl group, including ordinary phenol, p-tert-butylphenol, tribromophenol, etc., as well as long-chain alkylphenol, aliphatic carbonylphenol, etc. Examples include acid chloride, aliphatic carboxylic acid, hydroxybenzoic acid alkyl ester, hydroxy phenyl acid alkyl ester, and alkyl ether phenol.
その使用量は用いる全ての二価フェノール系化合物１０
０モルに対して４ １００−０．５モル、好ましくは５
０〜２モルの範囲であり、二種以上の化合物を併用する
ことも当然に可能である。The amount used is 10% of all dihydric phenol compounds used.
4 100-0.5 mol to 0 mol, preferably 5
The amount is in the range of 0 to 2 moles, and it is naturally possible to use two or more kinds of compounds in combination.
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類；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。As a polymerization catalyst, tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, trihexylamine, tridecylamine, N,N-dimethylcyclohexylamine, pyridine, quinoline, and dimethylaniline; trimethylbenzylammonium chloride , tetramethylammonium chlorand, triethylbenzylammonium chloride, and other quaternary ammonium salts.
また、分岐化剤を上記の二価フェノール系化合物に対し
て、ｏ、ｏｉ〜３ミル３モルに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とすることもで
きる。分岐化剤としては、フロログリシン、２．６−シ
メチルー２．４．６− ）リ （４−ヒドロキシフェニ
ル）へブテン−３，４，６−シメチルー２．４．６−）
ＩＪ（４−ヒドロキシフェニル）へブテン−２，１，３
゜５−）ＩＪ（２−ヒドロキシフェニル）ペンゾール、
１゜１、１− ）リ （４−ヒドロキシフェニル）エタ
ン、２．６−ビス（２−ヒドロキシ−５−メチルベンジ
ル）−４−メチルフッエノール、α、α′ α′−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。A branched polycarbonate can also be obtained by using a branching agent in a range of 0.1 to 1.0 mol % in 3 mol of o, oi to 3 mil to the above dihydric phenol compound. As a branching agent, phloroglycin, 2,6-dimethyl-2.4.6-)li(4-hydroxyphenyl)hebutene-3,4,6-dimethyl-2.4.6-)
IJ(4-hydroxyphenyl)hebutene-2,1,3
゜5-) IJ (2-hydroxyphenyl)penzole,
1゜1,1-)li(4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylfuenol, α,α′ α′-tri(4-hydroxy polyhydroxy compounds exemplified by phenyl)-1,3,5-triisopropylbenzene, and 3,3-bis(4-hydroxyaryl)oxindole (=isatin bisphenol), 5-chloroisatin, 5,7- Examples include dichloroisatin and 5-bromiisatin.
なお、本発明のポリカーボネート樹脂には、その使用目
的に応じて、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, depending on the purpose of use, the polycarbonate resin of the present invention may contain antioxidants, light stabilizers, colorants, inorganic or organic fillers, reinforcing agents such as carbon fibers and glass fibers,
A lubricant, an antistatic agent, etc. may be used in combination as appropriate.
以下、実施例および比較例によって本発明を具体的に説
明する。Hereinafter, the present invention will be specifically explained with reference to Examples and Comparative Examples.
比較例 １
水酸化ナトリウム３．７ｋｇを水４２１に溶解し、２０
℃に保ちながら、２．２−ビス（４−ヒドロキシフェニ
ル）プロパン（以下ｒＢＰＡ Ｊと記す） ７．３ｋ
ｇ、ハイドロサルファイド８ｇを溶解じた。Comparative Example 1 3.7 kg of sodium hydroxide was dissolved in 421 kg of water,
2.2-bis(4-hydroxyphenyl)propane (hereinafter referred to as rBPA J) 7.3k while keeping at ℃
g, 8 g of hydrosulfide was dissolved.
これにメチレンクロライド（以下ｒＭｃＪと記す）２８
１を加えて撹拌しつつ、ｐ−ｔ−ブチルフェノール（以
下ｒＰＴＢＰ」と記す） １４８ｇを加え、ついでホス
ゲン３．５ｋｇを６０分で吹き込んだ。To this, methylene chloride (hereinafter referred to as rMcJ) 28
1 was added and while stirring, 148 g of pt-butylphenol (hereinafter referred to as "rPTBP") was added, and then 3.5 kg of phosgene was blown in over 60 minutes.
ホスゲン吹き込み終了後、激しく撹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
撹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３５１加えて、重合物を沈澱
させた。沈澱物を濾過し、その後乾燥する事により、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 washing with water until the pH of the washing solution became neutral, 351% of isopropanol was added to the polymerization solution. was precipitated. The precipitate was filtered and then dried to obtain a white powdery polycarbonate resin.
このポリカーボネート樹脂をベント付き４０ｍｍ押出機
で２６０〜２８０℃の温度で押出してベレットとし、粘
度、流れ値を測定した。This polycarbonate resin was extruded using a vented 40 mm extruder at a temperature of 260 to 280°C to form a pellet, and the viscosity and flow value were measured.
また、このベレットを熱風乾燥機中で１２０℃にて８時
間以上乾燥した後、住友ネオマツ） Ｎ３５０／１２０
５ＹＣＡＰにて成形温度２８０℃、金型温度１００℃で
、肉厚２．５ｍｍ、高さ６０閣、縦横共に７０ｍｍの箱
型成形品を成形し、その時の金型内圧と離型抵抗をセン
サー（テクノプラスＣ−ＢＨ）にて測定した。In addition, after drying this pellet in a hot air dryer at 120°C for 8 hours or more, the pellet was dried (Sumitomo neopine) N350/120.
At 5YCAP, a box-shaped molded product with a wall thickness of 2.5 mm, a height of 60 mm, and both length and width of 70 mm was formed at a molding temperature of 280°C and a mold temperature of 100°C, and a sensor ( Measured using Technoplus C-BH).
これらの結果を第１表に示した。These results are shown in Table 1.
比較例 ２
比較例１において、ＢＰＡを１．１−ビス（４−ヒドロ
キシフェニル）シクロヘキサン（以下ｒＢＰＺ Ｊと記
す）８．６ｋｇに、ＰＴＢＰを１８０ｇにそれぞれ変更
する他は同様とした。結果を第１表に示した。Comparative Example 2 Comparative Example 1 was carried out in the same manner as in Comparative Example 1 except that BPA was changed to 8.6 kg of 1,1-bis(4-hydroxyphenyl)cyclohexane (hereinafter referred to as rBPZ J) and PTBP was changed to 180 g. The results are shown in Table 1.
実施例 １
比較例１において、水酸化ナトリウムを３．８ｋｇに、
水を４５１に、ＢＰＡをＢＰＡ ７．２ｋｇと一般式
（１）の化合物としてシリコーン鎮の平均繰り返し数ｎ
＝５０のもの（以下ｒ １６５ＢＪと記す。下記に構造
式を示した） １．３ｋｇに、ＭＣを３２１に、ＰＴ
ＢＰを１５８ｇにそれぞれ変更する他は同様とした。Example 1 In Comparative Example 1, sodium hydroxide was changed to 3.8 kg,
The average number of repetitions n of the silicone compound is as follows: water is 451, BPA is 7.2 kg, and the compound of general formula (1) is used.
=50 (hereinafter referred to as r 165BJ.The structural formula is shown below) 1.3 kg, MC to 321, PT
The procedure was the same except that the BP was changed to 158g.
結果を第１表に示した。The results are shown in Table 1.
実施例 ２
実施例１において、ＢＰＡを７．０ｋｇに、１６５Ｂを
６．５ｋｇに、ＰＴＢＰを１９４ｇにそれぞれ変更する
他は同様とした。結果を第１表に示した。Example 2 The procedure of Example 1 was repeated except that BPA was changed to 7.0 kg, 165B was changed to 6.5 kg, and PTBP was changed to 194 g. The results are shown in Table 1.
実施例 ３
実施例１において、ＢＰＡを７．３ｋｇに、１６５Ｂを
シリコーン鎮の平均繰り返し数ｎ＝７１のもの（以下ｒ
１６５ＣＪと記す。下記に構造式を示した） ０．
９ｋｇに、ＰＴＢＰを１６５ｇにそれぞれ変更する他は
同様とした。結果を第１表に示した。Example 3 In Example 1, BPA was changed to 7.3 kg and 165B was applied to silicone with an average number of repetitions n = 71 (hereinafter r
It is written as 165CJ. The structural formula is shown below) 0.
The procedure was the same except that the weight was changed to 9 kg and the PTBP was changed to 165 g. The results are shown in Table 1.
実施例 ４
実施例１において、水を１００１に、ＢＰＡを１．１＝
ビス（４−ヒドロキシフェニル）シクロヘキサン（以下
ｒＢＰＺ Ｊと記す）７．７ｋｇに、１６５Ｂを１２．
８ｋｇに、ＭＣを８０１に、ＰＴＢＰを２４０ｇにそれ
ぞれ変更した他は同様としてポリカーボネート樹脂粉末
を得ること、この粉末を温度２８０〜３００℃に変更し
てペレットとし、射出成形温度を３００℃にそれぞれ変
更した。結果を第１表に示した。Example 4 In Example 1, water was set to 1001 and BPA was set to 1.1.
Add 165B to 7.7 kg of bis(4-hydroxyphenyl)cyclohexane (hereinafter referred to as rBPZ J) for 12.
Polycarbonate resin powder was obtained in the same manner except that the weight was changed to 8 kg, MC to 801, and PTBP to 240 g. This powder was made into pellets by changing the temperature from 280 to 300°C, and the injection molding temperature was changed to 300°C. did. The results are shown in Table 1.
実施例 ５
実施例４において、ＢＰＺを８ｋｇに、１６５Ｂを１６
５ＣＩ２．６ｋｇに、ＰＴ１３Ｐを２２５ｇにそれぞれ
変更した他は同様とした。結果を第１表に示した。Example 5 In Example 4, BPZ was 8 kg and 165B was 16 kg.
The procedure was the same except that 5CI was changed to 2.6 kg and PT13P was changed to 225 g. The results are shown in Table 1.
第１表−１
第１表−２
〔発明の作用および効果〕
本発明のコーポリカーボネート樹脂は、従来の熱安定性
を維持し、離型性、流動性が著しく向上したものである
。Table 1-1 Table 1-2 [Operations and Effects of the Invention] The copolycarbonate resin of the present invention maintains the conventional thermal stability and has significantly improved mold releasability and fluidity.
従って、従来困難とされていた成形が容易であり、一般
の成形品は無論のこと、精密成形品としても好適な成形
材料であり、また、フィルム、シート咎の材料としても
有用なものであることが理解されるものである。Therefore, it is easy to mold, which was previously considered difficult, and is a suitable molding material not only for general molded products but also for precision molded products, and is also useful as a material for films and sheets. This is understood.
Claims (1)
有するコーポリカーボネート樹脂。 構造式（Ａ）； ▲数式、化学式、表等があります▼ 構造式（Ｂ）；▲数式、化学式、表等があります▼ （構造式（Ａ）のｎは１〜２００の整数を示し、また、
構造式（Ｂ）のＢは炭素数１〜１０の直鎖、分岐鎖或い
は環状のアルキリデン基、 アリール置換アルキレン基、アリール基又 は−Ｏ−、−Ｓ−、−ＣＯ−、−ＳＯ＿２−を示し、Ｒ
＾１、Ｒ＾２、Ｒ＾３及びＲ＾４は水素、ハロゲン又は
炭素数１〜４のアルキル基を示す。） ２ 該構造式（Ａ）で表される構成単位が０．０１〜７
０モル％の範囲である請求項１記載のコーポリカーボネ
ート樹脂。 ３ 界面重合法によるポリカーボネート樹脂の製法にお
いて、二価フェノールとして、下記一般式（１）および
（２）で表される化合物を使用することを特徴とする新
規コー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▼ 一般式（２）；▲数式、化学式、表等があります▼ （一般式（１）のｎは１〜２００の整数を示し、また、
一般式（２）のＢは炭素数１〜１０の直鎖、分岐鎖或い
は環状のアルキリデン基、 アリール置換アルキレン基、アリール基又 は−Ｏ−、−Ｓ−、−ＣＯ、−ＳＯ＿２−を示し、Ｒ＾
１、Ｒ＾２、Ｒ＾３及びＲ＾４は水素、ハロゲン又は炭
素数１〜４のアルキル基を示す。）[Claims] 1. A copolycarbonate resin having structural units represented by the following structural formulas (A) and (B). Structural formula (A); ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Structural formula (B); ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (n in structural formula (A) indicates an integer from 1 to 200, and ,
B in structural formula (B) represents a linear, branched or cyclic alkylidene group having 1 to 10 carbon atoms, an aryl-substituted alkylene group, an aryl group, or -O-, -S-, -CO-, -SO_2-. ,R
^1, R^2, R^3 and R^4 represent hydrogen, halogen or an alkyl group having 1 to 4 carbon atoms. ) 2 The structural unit represented by the structural formula (A) is 0.01 to 7
The copolycarbonate resin according to claim 1, wherein the copolycarbonate resin is in the range of 0 mol%. 3. A method for producing a new copolycarbonate resin, which is characterized in that a compound represented by the following general formulas (1) and (2) is used as the dihydric phenol in the method for producing a polycarbonate resin by an interfacial polymerization method. General formula (1); ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula (2); ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (n in general formula (1) indicates an integer from 1 to 200, and ,
B in general formula (2) represents a linear, branched or cyclic alkylidene group having 1 to 10 carbon atoms, an aryl-substituted alkylene group, an aryl group, or -O-, -S-, -CO, -SO_2-, R^
1, R^2, R^3 and R^4 represent hydrogen, halogen or an alkyl group having 1 to 4 carbon atoms. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21406289A JPH0379626A (en) | 1989-08-22 | 1989-08-22 | Copolycarbonate resin and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21406289A JPH0379626A (en) | 1989-08-22 | 1989-08-22 | Copolycarbonate resin and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0379626A true JPH0379626A (en) | 1991-04-04 |
Family
ID=16649627
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21406289A Pending JPH0379626A (en) | 1989-08-22 | 1989-08-22 | Copolycarbonate resin and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0379626A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992012208A1 (en) * | 1990-12-27 | 1992-07-23 | Idemitsu Petrochemical Co., Ltd. | Polycarbonate resin composition |
| US5916980A (en) * | 1996-10-03 | 1999-06-29 | Mitsubishi Gas Chemical Company, Inc. | Polycarbonate resin composition |
| EP0933387A1 (en) * | 1998-01-30 | 1999-08-04 | Dow Corning Toray Silicone Company, Ltd. | Method for preparation of organofunctional pentasiloxane, organic resin modifier and organic resins |
| US6114487A (en) * | 1998-01-30 | 2000-09-05 | Dow Corning Toray Silicone Co., Ltd. | Hydroxyphenyl-containing silalkarylene compounds and silalkarylene-modified organic resins |
| US6762250B2 (en) | 2002-06-07 | 2004-07-13 | Mitsubishi Engineering-Plastics Corporation | Polycarbonate resin composition |
| JP2005535759A (en) * | 2002-08-16 | 2005-11-24 | ゼネラル・エレクトリック・カンパニイ | Siloxane bischloroformate |
| WO2011013846A1 (en) | 2009-07-29 | 2011-02-03 | 帝人化成株式会社 | Polycarbonate/polydiorganosiloxane copolymer |
| WO2011122767A3 (en) * | 2010-03-29 | 2012-01-12 | 주식회사 삼양사 | Hydroxy-terminated siloxane, polysiloxane-polycarbonate copolymer, and preparation method thereof |
| KR101332434B1 (en) * | 2010-08-26 | 2013-11-22 | 제일모직주식회사 | Bishydroxyarylsilxoane and preparation method thereof |
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| JP2019031687A (en) * | 2013-03-29 | 2019-02-28 | 出光興産株式会社 | Method of producing polycarbonate-polyorganosiloxane copolymer |
-
1989
- 1989-08-22 JP JP21406289A patent/JPH0379626A/en active Pending
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992012208A1 (en) * | 1990-12-27 | 1992-07-23 | Idemitsu Petrochemical Co., Ltd. | Polycarbonate resin composition |
| US5488086A (en) * | 1990-12-27 | 1996-01-30 | Idemitsu Petrochemical Co., Ltd. | Polycarbonate resin composition |
| US5916980A (en) * | 1996-10-03 | 1999-06-29 | Mitsubishi Gas Chemical Company, Inc. | Polycarbonate resin composition |
| DE19745591B4 (en) * | 1996-10-03 | 2016-12-22 | Mitsubishi Gas Chemical Co., Inc. | Polycarbonate resin composition and process for its preparation |
| EP0933387A1 (en) * | 1998-01-30 | 1999-08-04 | Dow Corning Toray Silicone Company, Ltd. | Method for preparation of organofunctional pentasiloxane, organic resin modifier and organic resins |
| US6114487A (en) * | 1998-01-30 | 2000-09-05 | Dow Corning Toray Silicone Co., Ltd. | Hydroxyphenyl-containing silalkarylene compounds and silalkarylene-modified organic resins |
| US6133394A (en) * | 1998-01-30 | 2000-10-17 | Dow Corning Toray Silicone Co., Ltd. | Method for the preparation of organofunctional organopentasiloxane, organic resin modifier and organic resins |
| US6762250B2 (en) | 2002-06-07 | 2004-07-13 | Mitsubishi Engineering-Plastics Corporation | Polycarbonate resin composition |
| JP4776923B2 (en) * | 2002-08-16 | 2011-09-21 | サビック・イノベーティブ・プラスチックス・アイピー・ベスローテン・フェンノートシャップ | Siloxane bischloroformate |
| JP2005535759A (en) * | 2002-08-16 | 2005-11-24 | ゼネラル・エレクトリック・カンパニイ | Siloxane bischloroformate |
| WO2011013846A1 (en) | 2009-07-29 | 2011-02-03 | 帝人化成株式会社 | Polycarbonate/polydiorganosiloxane copolymer |
| KR20120050968A (en) | 2009-07-29 | 2012-05-21 | 테이진 카세이 가부시키가이샤 | Polycarbonate/polydiorganosiloxane copolymer |
| US8962780B2 (en) | 2009-07-29 | 2015-02-24 | Teijin Chemicals, Ltd. | Polycarbonate-polydiorganosiloxane copolymer |
| WO2011122767A3 (en) * | 2010-03-29 | 2012-01-12 | 주식회사 삼양사 | Hydroxy-terminated siloxane, polysiloxane-polycarbonate copolymer, and preparation method thereof |
| US8802804B2 (en) | 2010-03-29 | 2014-08-12 | Samyang Corporation | Hydroxy-terminated siloxane, polysiloxane-polycarbonate copolymer, and preparation method thereof |
| KR101289201B1 (en) * | 2010-03-29 | 2013-07-29 | 주식회사 삼양사 | Ester linkage-containing hydroxy-terminated siloxane, polysiloxane-polycarbonate copolymer and method of manufacturing the same |
| KR101332434B1 (en) * | 2010-08-26 | 2013-11-22 | 제일모직주식회사 | Bishydroxyarylsilxoane and preparation method thereof |
| WO2014073605A1 (en) | 2012-11-07 | 2014-05-15 | 東レ・ダウコーニング株式会社 | Phenol-denatured polyorganosiloxane with reduced platinum content, method for producing same, and organic resin modifier containing same |
| US9512276B2 (en) | 2012-11-07 | 2016-12-06 | Dow Corning Toray Co., Ltd. | Phenol-modified polyorganosiloxane with reduced platinum content, method for preparing the same, and modifier for organic resin containing the same |
| KR20170116252A (en) | 2012-11-07 | 2017-10-18 | 다우 코닝 도레이 캄파니 리미티드 | Phenol-modified polyorganosiloxane with reduced platinum content, method for preparing the same, and modifier for organic resin containing the same |
| JP2019031687A (en) * | 2013-03-29 | 2019-02-28 | 出光興産株式会社 | Method of producing polycarbonate-polyorganosiloxane copolymer |
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