JP5290584B2 - Polyarylate and method for producing the same - Google Patents
Polyarylate and method for producing the same Download PDFInfo
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- JP5290584B2 JP5290584B2 JP2008006870A JP2008006870A JP5290584B2 JP 5290584 B2 JP5290584 B2 JP 5290584B2 JP 2008006870 A JP2008006870 A JP 2008006870A JP 2008006870 A JP2008006870 A JP 2008006870A JP 5290584 B2 JP5290584 B2 JP 5290584B2
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- polyarylate
- bisphenol
- hydroxyphenyl
- bis
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- 229920001230 polyarylate Polymers 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229930185605 Bisphenol Natural products 0.000 claims abstract description 28
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims abstract description 11
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 claims abstract description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 9
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- 230000009477 glass transition Effects 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 3
- 239000002685 polymerization catalyst Substances 0.000 claims description 22
- 125000005843 halogen group Chemical group 0.000 claims description 11
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 10
- UMPGNGRIGSEMTC-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexyl]phenol Chemical compound C1C(C)CC(C)(C)CC1(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 UMPGNGRIGSEMTC-UHFFFAOYSA-N 0.000 claims description 7
- 238000012696 Interfacial polycondensation Methods 0.000 claims description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 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 claims description 3
- 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 claims 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 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 238000000576 coating method Methods 0.000 description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- -1 carboxylic acid halide Chemical class 0.000 description 10
- 239000008346 aqueous phase Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 239000012074 organic phase Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000012695 Interfacial polymerization Methods 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- 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 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VJGNLOIQCWLBJR-UHFFFAOYSA-M benzyl(tributyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 VJGNLOIQCWLBJR-UHFFFAOYSA-M 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 2
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N benzene-dicarboxylic acid Natural products OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N perisophthalic acid Natural products OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- BELBBZDIHDAJOR-UHFFFAOYSA-N Phenolsulfonephthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2S(=O)(=O)O1 BELBBZDIHDAJOR-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 1
- QSRFYFHZPSGRQX-UHFFFAOYSA-N benzyl(tributyl)azanium Chemical compound CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 QSRFYFHZPSGRQX-UHFFFAOYSA-N 0.000 description 1
- UDYGXWPMSJPFDG-UHFFFAOYSA-M benzyl(tributyl)azanium;bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 UDYGXWPMSJPFDG-UHFFFAOYSA-M 0.000 description 1
- ANHXKSXTBQIUAZ-UHFFFAOYSA-M benzyl(tributyl)azanium;hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 ANHXKSXTBQIUAZ-UHFFFAOYSA-M 0.000 description 1
- YOUGRGFIHBUKRS-UHFFFAOYSA-N benzyl(trimethyl)azanium Chemical compound C[N+](C)(C)CC1=CC=CC=C1 YOUGRGFIHBUKRS-UHFFFAOYSA-N 0.000 description 1
- UUZYBYIOAZTMGC-UHFFFAOYSA-M benzyl(trimethyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)CC1=CC=CC=C1 UUZYBYIOAZTMGC-UHFFFAOYSA-M 0.000 description 1
- YBQCZIKWFFYEEM-UHFFFAOYSA-M benzyl(trimethyl)azanium;hydrogen sulfate Chemical compound OS([O-])(=O)=O.C[N+](C)(C)CC1=CC=CC=C1 YBQCZIKWFFYEEM-UHFFFAOYSA-M 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 description 1
- DWTYPCUOWWOADE-UHFFFAOYSA-M hydron;tetramethylazanium;sulfate Chemical compound C[N+](C)(C)C.OS([O-])(=O)=O DWTYPCUOWWOADE-UHFFFAOYSA-M 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229960003531 phenolsulfonphthalein Drugs 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 1
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 1
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
Description
本発明は、耐熱性にすぐれ、さらに電気特性にも優れたポリアリレートを製造する方法に関する。 The present invention relates to a method for producing polyarylate having excellent heat resistance and excellent electrical characteristics.
シクロヘキサン環構造を有するビスフェノールと芳香族ジカルボン酸から構成されるポリアリレートは、その高い耐熱性により電気・電子材料分野を中心として使用されている。ポリアリレートの重合方法は種々が知られているが、分子量が高く、かつ着色が少なく、しかも、純度の高いポリマーが得られる界面重合が最適であるとされている。しかしながら、シクロヘキサン環単位を有するビスフェノールを一成分とするポリアリレートを界面重合で得ようとすると、その反応性の低さから、活性の低い重合触媒では十分に分子量が上昇しない問題があり、活性の高い重合触媒を使用する必要があった。一方、イソプロピリデンを骨格とするビスフェノールは、反応性が高く、活性の低い重合触媒でも十分に高分子量のポリアリレートが重合できる。 Polyarylate composed of bisphenol having a cyclohexane ring structure and an aromatic dicarboxylic acid is used mainly in the field of electric and electronic materials due to its high heat resistance. Various methods for polymerizing polyarylate are known, but interfacial polymerization that yields a polymer having a high molecular weight, little coloration, and high purity is considered to be optimal. However, when polyarylate containing bisphenol having a cyclohexane ring unit as a component is obtained by interfacial polymerization, there is a problem that the molecular weight does not increase sufficiently with a low activity polymerization catalyst due to its low reactivity. It was necessary to use a high polymerization catalyst. On the other hand, bisphenol having isopropylidene as a skeleton has high reactivity, and a sufficiently high molecular weight polyarylate can be polymerized even with a polymerization catalyst having low activity.
そのため、シクロヘキサン環構造を有するビスフェノールとイソプロピリデンを骨格とするビスフェノールを共重合しようとした場合、前記問題から、シクロヘキサン環構造を有するビスフェノールを考慮して、活性の高い重合触媒で重合することになる。しかしながら、イソプロピリデンを骨格とするビスフェノールに関しては、反応性が極端に早くなるため、逆に、副反応である加水分解反応が律速となるため、カルボキシル価が増大し、電気特性が悪化する問題があった（例えば、特許文献１等）。
本発明は、耐熱性にすぐれ、さらに電気特性にも優れたポリアリレートを提供することを目的とする。 An object of the present invention is to provide a polyarylate having excellent heat resistance and excellent electrical characteristics.
本発明者は、このような課題を解決するために鋭意研究を重ねた結果、活性の低い重合触媒と活性の高い重合触媒を特定の比率で混合して使用することで前記課題が解決することを見出し、本発明に到達した。 As a result of intensive studies to solve such problems, the present inventor can solve the above problems by mixing a polymerization catalyst having a low activity and a polymerization catalyst having a high activity at a specific ratio. And reached the present invention.
すなわち、本発明の要旨は下記の通りである。 That is, the gist of the present invention is as follows.
（Ａ）シクロヘキサン環構造を有するビスフェノールおよび（Ｂ）イソプロピリデン骨格を有するビスフェノール、（Ｃ）芳香族ジカルボン酸から構成されるポリアリレートであって、前記（Ａ）および（Ｂ）が、それぞれ下記から選ばれるものであり、下記式（１）の化学構造を有し、下記式（２）、（３）で示される重合触媒をビスフェノールに対し総量で０．５〜１．０モル％となる範囲で混合して用い、界面重縮合をして得られるものであり、インヘレント粘度（ηｉｎｈ）が０．４５〜１．００ｄｌ／ｇであり、カルボキシル価が３０ｍｏｌ／ｔ以下であり、さらにガラス転移点が２００℃以上であるポリアリレート。
（Ａ）：１，１−ビス（４−ヒドロキシフェニル）シクロヘキサン（ＢＰＺ）、または１，１−ビス（４−ヒドロキシフェニル）−３，３，５−トリメチルシクロヘキサン（ＢＰＴＭＣ）
（Ｂ）：２，２−ビス（４−ヒドロキシフェニル）プロパン（ＢＰＡ）、２，２−ビス（３−メチルー４−ヒドロキシフェニル）プロパン（ＢＰＣ）、または２，２−ビス（３，５−ジメチル−４−ヒドロキシフェニル）プロパン（ＴＭＢＰＡ）
(A) A polyarylate composed of a bisphenol having a cyclohexane ring structure and (B) a bisphenol having an isopropylidene skeleton, and (C) an aromatic dicarboxylic acid, wherein (A) and (B) are as follows: The selected range has a chemical structure of the following formula (1), and the total amount of the polymerization catalyst represented by the following formulas (2) and (3) is 0.5 to 1.0 mol% with respect to bisphenol. And obtained by interfacial polycondensation, having an inherent viscosity (ηinh) of 0.45 to 1.00 dl / g, a carboxyl value of 30 mol / t or less, and a glass transition point. Polyarylate having a temperature of 200 ° C. or higher.
(A): 1,1-bis (4-hydroxyphenyl) cyclohexane (BPZ) or 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (BPTMC)
(B): 2,2-bis (4-hydroxyphenyl) propane (BPA), 2,2-bis (3-methyl-4-hydroxyphenyl) propane (BPC), or 2,2-bis (3,5- Dimethyl-4-hydroxyphenyl) propane (TMBPA)
〜９０／１０である。）
またはＯＨ、ＨＳＯ ４ を表す。）
またはＯＨ、ＨＳＯ ４ を表す。）
（ＩＩ）（Ｉ）のポリアリレートの製造方法であって、下記式（２）の重合触媒および
下記式（３）の重合触媒を混合し、界面重縮合で製造することを特徴とするポリアリレー
トの製造方法。
~ 90/10. )
Or represents OH, the HSO 4. )
Or represents OH, the HSO 4. )
(II) A method for producing a polyarylate of (I), comprising mixing a polymerization catalyst of the following formula (2) and a polymerization catalyst of the following formula (3), and producing the polyarylate by interfacial polycondensation Manufacturing method.
本発明によれば、高分子量でかつ残留触媒の残存量が著しく少なく、耐熱性に優れると同時に、電気的特性、特に絶縁特性に優れたポリアリレートを生産性よく、簡便に製造することができる。また、本発明によって製造されるポリアリレートは、溶媒に容易に溶解し易いので、溶媒に溶解させて塗工液を調製し、容易にフィルム化や表面被膜化することができる。したがって本発明によって製造されるポリアリレートは、例えばフィルムとして、電気機器、モーター、発電機、層間絶縁膜等の絶縁材料、変圧器、コンデンサなどの誘電体フィルム、液晶の表示板や各種基板などへの応用、また表面被膜として、電線の被膜、絶縁被膜材などへの応用が可能であり、産業上の利用価値は極めて高い。 According to the present invention, polyarylate having a high molecular weight and a residual amount of residual catalyst is remarkably small and excellent in heat resistance, and at the same time excellent in electrical characteristics, particularly in insulating characteristics, can be easily produced with high productivity. . Moreover, since the polyarylate produced by the present invention is easily dissolved in a solvent, it can be dissolved in a solvent to prepare a coating solution, and can be easily formed into a film or a surface film. Therefore, the polyarylate produced according to the present invention is used as, for example, a film as an insulating material such as an electric device, a motor, a generator, an interlayer insulating film, a dielectric film such as a transformer or a capacitor, a liquid crystal display plate or various substrates. In addition, as a surface coating, it can be applied to a coating of an electric wire, an insulating coating material, etc., and its industrial utility value is extremely high.
本発明のポリアリレートについて説明する。ポリアリレートは、２価フェノール残基と芳香族２価カルボン酸残基とから構成されているポリエステルであるが、本発明では、界面重合によって合成される。すなわち、アルカリ水溶液に溶解させた２価フェノール（以下「ビスフェノール」）（水相）と、水に溶解しない有機溶剤に溶解させた２価カルボン酸ハライド（有機相）とを混合することによって行われ（Ｗ．Ｍ．ＥＡＲＥＣＫＳＯＮＪ．Ｐｏｌｙ．Ｓｃｉ．ＸＬ３９９ １９５９年、特公昭４０−１９５９号公報）、溶液重合と比較して反応が速く、そのため酸ハライドの加水分解を最小限に抑えることが可能である。本発明のような高分子量のポリアリレートを得る場合には有利な合成法である。 The polyarylate of the present invention will be described. Polyarylate is a polyester composed of a dihydric phenol residue and an aromatic divalent carboxylic acid residue. In the present invention, polyarylate is synthesized by interfacial polymerization. That is, it is carried out by mixing a dihydric phenol (hereinafter referred to as “bisphenol”) (aqueous phase) dissolved in an alkaline aqueous solution and a divalent carboxylic acid halide (organic phase) dissolved in an organic solvent that is not soluble in water. (W.M.EARECCKSONJ.Poly.Sci.XL399 1959, Japanese Patent Publication No. 40-1959), the reaction is faster than solution polymerization, and therefore it is possible to minimize hydrolysis of the acid halide. . This is an advantageous synthesis method for obtaining a high molecular weight polyarylate as in the present invention.
本発明に用いることのできる２価の芳香族カルボン酸ハライドとしては、テレフタル酸ハライド、イソフタル酸ハライド、フタル酸ハライド、ジフェン酸ハライド、１，４−ナフタレンジカルボン酸ハライド、あるいは、芳香核にアルキル基やハロゲン基が置換した混合物が挙げられる。好適には、テレフタル酸ハライド１０〜９０モル％とイソフタル酸ハライド９０〜１０モル％の混合物が用いられ、特に好ましくは両者の等量混合物である。 Examples of the divalent aromatic carboxylic acid halide that can be used in the present invention include terephthalic acid halide, isophthalic acid halide, phthalic acid halide, diphenic acid halide, 1,4-naphthalenedicarboxylic acid halide, or an alkyl group in the aromatic nucleus. And a mixture substituted with a halogen group. Preferably, a mixture of 10 to 90 mol% of terephthalic acid halide and 90 to 10 mol% of isophthalic acid halide is used, and an equivalent mixture of both is particularly preferable.
また、本発明に用いられるシクロヘキサン環構造を有するビスフェノールとしては、１，１−ビス（４−ヒドロキシフェニル）シクロヘキサン（以下、ＢＰＺ）または１，１−ビス（４−ヒドロキシフェニル）−３，３，５−トリメチルシクロヘキサン（以下、ＢＰＴＭＣ）が挙げられる。
The bisphenol having a cyclohexane ring structure used in the present invention is 1,1-bis (4-hydroxyphenyl) cyclohexane (hereinafter referred to as BPZ) or 1,1-bis (4-hydroxyphenyl) -3,3. 5-trimethylcyclohexane (hereinafter referred to as BPTMC).
また、このビフェノール誘導体に共重合するビスフェノール類としては、イソプロピリ
デン基を骨格の中心に持つビスフェノール類である。具体的には２，２−ビス（４−ヒド
ロキシフェニル）プロパン（以下、ＢＰＡ）、２，２−ビス（３−メチルー４−ヒドロキ
シフェニル）プロパン（以下、ＢＰＣ）、２，２−ビス（３，５−ジメチル−４−ヒドロ
キシフェニル）プロパン（以下、ＴＭＢＰＡ）が挙げられる。
The bisphenols copolymerized with this biphenol derivative are bisphenols having an isopropylidene group at the center of the skeleton. Specifically, 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as BPA), 2,2-bis (3-methyl-4-hydroxyphenyl) propane (hereinafter referred to as BPC), 2,2-bis (3 , 5-dimethyl-4-hydroxyphenyl) propane (hereinafter referred to as TMBPA).
式（１）に示す共重合の比率（ｍ／ｎ比）としてはビスフェノール成分を１００モル％とした場合に、ｍ／ｎ＝１０／９０〜９０／１０モル％であり、好適にはｍ／ｎ＝１５／８５〜８５／１５モル％の範囲である。最適にはｍ／ｎ＝２０／８０〜８０／２０モル％である。ｍが１０モル％未満の場合、シクロヘキサン環構造を有するビスフェノール成分を共重合することによる効果、すなわち、高い耐熱性が得られない。一方、ｍが８０モル％を超える場合、生成したアリレートの溶剤溶解性が低下するため分子量が上昇しない。 The copolymerization ratio (m / n ratio) represented by the formula (1) is m / n = 10/90 to 90/10 mol% when the bisphenol component is 100 mol%, preferably m / n. n = 15/85 to 85/15 mol%. Optimally, m / n = 20/80 to 80/20 mol%. When m is less than 10 mol%, the effect of copolymerizing a bisphenol component having a cyclohexane ring structure, that is, high heat resistance cannot be obtained. On the other hand, when m exceeds 80 mol%, the solvent solubility of the produced arylate is lowered, so the molecular weight does not increase.
本発明の重合触媒としては、（２）式および（３）式で示される、第４級アンモニウム塩を該ビスフェノールのモル数に対して総量で0.5〜1.0モル％することが必須である。0.5モル％より少ないと十分な触媒作用が働かないため高い分子量が得られない。また、1.0モル％より多いと主反応だけでなく副反応である加水分解反応も活性になるため、カルボキシル価が増大する。 As the polymerization catalyst of the present invention, it is essential that the quaternary ammonium salt represented by the formulas (2) and (3) is 0.5 to 1.0 mol% in total with respect to the number of moles of the bisphenol. If the amount is less than 0.5 mol%, a sufficient molecular weight cannot be obtained because sufficient catalytic action does not work. On the other hand, if it exceeds 1.0 mol%, not only the main reaction but also the hydrolysis reaction, which is a side reaction, becomes active, so that the carboxyl number increases.
前記（２）式の具体的な物質としては、トリメチルベンジルアンモニウムクロライド、トリメチルベンジルアンモニウムブロマイド、トリメチルベンジルアンモニウムヒドロキシサイト、トリメチルベンジルアンモニウムハイドロジェンサルフェート、テトラメチルアンモニウムクロライド、テトラメチルアンモニウムブロマイド、テトラメチルアンモニウムヒドロキシサイト、テトラメチルアンモニウムハイドロジェンサルフェートなどが挙げられる。その中でも。トリメチルベンジルアンモニウムクロライドが好適である。 Specific substances of the formula (2) include trimethylbenzylammonium chloride, trimethylbenzylammonium bromide, trimethylbenzylammonium hydroxysite, trimethylbenzylammonium hydrogen sulfate, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium hydroxy Site, tetramethylammonium hydrogen sulfate, and the like. Among them. Trimethylbenzylammonium chloride is preferred.
前記（３）式の具体的な物質としては、トリ−ｎ−ブチルベンジルアンモニウムクロライド、トリ−ｎ−ブチルベンジルアンモニウムブロマイド、トリ−ｎ−ブチルベンジルアンモニウムヒドロキサイト、トリ−ｎ−ブチルベンジルアンモニウムハイドロジェンサルフェート、テトラ−ｎ−ブチルアンモニウムクロライド、テトラ−ｎ−ブチルアンモニウムブロマイド、テトラ−ｎ−ブチルアンモニウムヒドロキサイト、テトラ−ｎ−ブチルアンモニウムハイドロジェンサルフェートなどが挙げられる。その中でも、トリ−ｎ−ブチルベンジルアンモニウムクロライドが好適である。 Specific examples of the substance represented by the formula (3) include tri-n-butylbenzylammonium chloride, tri-n-butylbenzylammonium bromide, tri-n-butylbenzylammonium hydroxide, tri-n-butylbenzylammonium hydrogen. Examples thereof include sulfate, tetra-n-butylammonium chloride, tetra-n-butylammonium bromide, tetra-n-butylammonium hydroxide, tetra-n-butylammonium hydrogensulfate and the like. Of these, tri-n-butylbenzylammonium chloride is preferred.
本発明の必須の構成要件としては、前記（２）および（３）の重合触媒を混合して使用することである。その場合、混合比率は構成モノマーの比に応じて決定することになる。例えば、シクロヘキサン環構造を有するビスフェノールモノマーとイソプロピリデンを骨格に有するビスフェノールモノマーが１：１の等量であれば、該２価フェノールのモル数に対して、総量で0.5〜1.0モル％の範囲で、重合触媒に関しても等量を添加することで本発明を達成することができる。 An essential constituent requirement of the present invention is that the polymerization catalysts (2) and (3) are mixed and used. In that case, the mixing ratio is determined according to the ratio of the constituent monomers. For example, if the bisphenol monomer having a cyclohexane ring structure and the bisphenol monomer having isopropylidene in the skeleton have an equivalent amount of 1: 1, the total amount is in the range of 0.5 to 1.0 mol% with respect to the number of moles of the dihydric phenol. The present invention can be achieved by adding an equal amount of the polymerization catalyst.
ポリアリレートのガラス転移点は200℃以上であることが好ましい。200℃を下回ると、所望の耐熱性が得られない。 The glass transition point of polyarylate is preferably 200 ° C. or higher. Below 200 ° C, the desired heat resistance cannot be obtained.
また、分子量調整剤として、重合時に１官能の化合物、具体的にはフェノール、クレゾール、ｐ−tert−ブチルフェノール等を添加してもよい。 As the molecular weight modifier, a monofunctional compound, specifically phenol, cresol, p-tert-butylphenol, or the like may be added during polymerization.
次に有機相として、水と相溶せず、かつ、ポリアリレートを溶解するような溶媒、具体的には塩化メチレン、１，２−ジクロロエタン、クロロホルム、四塩化炭素、クロロベンゼン、１，１，２，２−テトラクロロエタン、１，１，１−トリクロロエタン、ｏ−ジクロロベンゼン、ｍ−ジクロロベンゼン、ｐ−ジクロロベンゼンなどの塩素系溶媒、トルエン、ベンゼン、キシレンなどの芳香族系炭化水素、もしくはテトラヒドロフランなどに、二価の芳香族カルボン酸ハライドを溶解させる。この有機相の溶液を前述の水相の溶液に混合し、２５℃以下の温度で１時間〜５時間攪拌しながら界面重縮合反応をおこなうことによって、高分子量のポリアリレートが得られる。 Next, as an organic phase, a solvent which is incompatible with water and dissolves polyarylate, specifically methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride, chlorobenzene, 1,1,2 , 2-tetrachloroethane, 1,1,1-trichloroethane, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene and other chlorinated solvents, toluene, benzene, xylene and other aromatic hydrocarbons, tetrahydrofuran, etc. In addition, a divalent aromatic carboxylic acid halide is dissolved. A high molecular weight polyarylate is obtained by mixing this organic phase solution with the aforementioned aqueous phase solution and conducting an interfacial polycondensation reaction with stirring at a temperature of 25 ° C. or lower for 1 to 5 hours.
本発明のポリアリレートの分子量範囲は、インヘレント粘度（ηinh）は0.45〜1.00dl/gであり、最適には0.50〜0.80dl/gである。インヘレント粘度が0.45dl/g未満であるとポリアリレートの機械特性が不十分な場合や、溶媒に溶解させた塗工液を調製して被膜を形成させる際に、塗工液の溶液粘度が低すぎて塗工できない場合があるので好ましくない。一方1.00dl/gを超えると、塗工する際に曳糸性が生じたり、塗工液の粘度が上昇して取扱が困難になる場合があるので好ましくない。インヘレント粘度（分子量）は前記した重合触媒および分子量調整剤の添加量で制御できる。具体的には前記重合触媒量の適度な添加量で高分子量化が可能となり、微調整を分子量調整剤でおこなうことができる。 The molecular weight range of the polyarylate of the present invention is that the inherent viscosity (ηinh) is 0.45 to 1.00 dl / g, optimally 0.50 to 0.80 dl / g. If the inherent viscosity is less than 0.45 dl / g, the solution viscosity of the coating solution is low when the mechanical properties of polyarylate are insufficient or when a coating solution is prepared by dissolving the coating solution in a solvent. Since it may be too much to coat, it is not preferable. On the other hand, if it exceeds 1.00 dl / g, spinnability may occur during coating, or the viscosity of the coating solution may increase, making handling difficult. The inherent viscosity (molecular weight) can be controlled by adding the polymerization catalyst and the molecular weight modifier. Specifically, high molecular weight can be achieved with an appropriate addition amount of the polymerization catalyst, and fine adjustment can be performed with a molecular weight adjusting agent.
本発明におけるポリアリレートのカルボキシル価の範囲は、30mol/t以下であることが好ましい。30mol/tを超えると、塗膜にした場合に電気特性が著しく悪くなる。 The range of the carboxyl value of the polyarylate in the present invention is preferably 30 mol / t or less. When it exceeds 30 mol / t, the electrical properties are remarkably deteriorated when a coating film is formed.
本発明によって製造されるポリアリレートは、汎用溶媒に対して良好な溶解性を有しているので、溶媒に溶解させて容易に塗工液を調製し、被膜形成用樹脂として用いることができる。そのような溶媒の具体例としては、塩化メチレン、１，２−ジクロロエタン、クロロホルム、四塩化炭素、クロロベンゼン、１，１，２，２−テトラクロロエタン、１，１，１−トリクロロエタン、ｏ−ジクロロベンゼン、ｍ−ジクロロベンゼン、ｐ−ジクロロベンゼンなどの塩素系溶媒、トルエン、ベンゼン、キシレンなどの芳香族系炭化水素、もしくはテトラヒドロフランなどが挙げられる。塗工液とする際には、適宜選択される１種類もしくは２種類以上を混合した溶媒に、ポリアリレートを好ましくは１０重量％以上の濃度になるように完溶させればよい。塗工液には必要に応じて各種添加物を含有させ、基材上に塗工した後に溶媒を除去して被膜を形成させ、被膜物して、あるいは、これを剥離してフィルムとして用いることができる。 Since the polyarylate produced according to the present invention has good solubility in general-purpose solvents, it can be easily dissolved in a solvent to prepare a coating solution and used as a film-forming resin. Specific examples of such solvents include methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride, chlorobenzene, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, o-dichlorobenzene. Chlorinated solvents such as m-dichlorobenzene and p-dichlorobenzene, aromatic hydrocarbons such as toluene, benzene and xylene, or tetrahydrofuran. When the coating liquid is used, the polyarylate is preferably completely dissolved in a solvent in which one kind or two or more kinds are appropriately selected so that the concentration is preferably 10% by weight or more. The coating solution contains various additives as necessary, and after coating on the substrate, the solvent is removed to form a film, and the film is coated or peeled off and used as a film. Can do.
発明によって製造されるポリアリレートは、バインダー樹脂やフィルム用樹脂として好適に用いられ、前記のような塗工液として流延法により、あるいは、溶融押出法またはカレンダー法により、耐磨耗性および電気特性に優れた被膜物やフィルムを製造することができ、特に電子材料分野へ応用することができる。 The polyarylate produced according to the invention is suitably used as a binder resin or a resin for a film. As a coating liquid as described above, the polyarylate is produced by a casting method, or a melt extrusion method or a calendering method. It is possible to produce coatings and films having excellent characteristics, and in particular, they can be applied to the electronic material field.
以下、本発明を実施例によりさらに詳細に説明する。各種物性値の測定は、以下の方法
により実施した。
（インヘレント粘度（ηｉｎｈ））
１，１，２，２−テトラクロロエタンを測定溶媒として、濃度１ｇ／ｄｌ、温度２５℃の条件で測定した。
（カルボキシル価）
試料０．３ｇを２０ｍｌの塩化メチレンに三角フラスコ内で溶解した後、指示薬（フェノールレッド）を加え、０．１Ｎ ＫＯＨ溶液で適定した。
（ガラス転移点）
示差熱分析計（Ｐｅｒｋｉｎ−Ｅｌｍｅｒ社製、ＤＳＣ−７）を用いて、２０℃／分の昇温速度で求めた。
〔実施例１〕
攪拌装置を備えた反応容器中に、２価フェノールとして、ＢＰＡを４０５９ｇ（１７．
７８モル）とＢＰＴＭＣを２３６６ｇ（７．６２モル）、末端停止剤であるp-tert-ブチ
ルフェノールを１９０．８ｇ（１．２７モル）、水酸化ナトリウムを２１８７ｇ（５４．
６８モル）、重合触媒を全ビスフェノールのモル数に対して総量として０．７０モル％仕
込む。その内訳としては、ＢＰＡに対して、トリメチルベンジルアンモニウムクロライド
（以下、ＴＭＢＡＣ）を２３．１ｇ（０．４９モル％）、ＢＰＴＭＣに対して、トリ−ｎ−ブチルベンジルアンモニウムクロライド（以下、ＴＢＢＡＣ）１６．６ｇ（０．２１モル％）とし、水相１１７Ｌに溶解した（水相）。これとは別に塩化メチレン６９Ｌにテレフタル／イソフタル酸クロライド＝１／１混合物（以下、ＭＰＣ）５２８６ｇを溶解した（有機相）。この有機相を先に調整した水相中に強攪拌下で添加し、１５℃で２時間界面重縮合反応を行った。重合停止（攪拌停止）後、水相と有機相をデカンテーションして分離させた。水相を抜取った後、等量のイオン交換水を投入して攪拌しながら、ｐＨが中性になるまで酢酸を添加した。さらに、２０分間攪拌した後２０分間デカンテーションして水相を抜いて新たなイオン交換水に交換する作業を５回繰り返した。洗浄後の有機相であるポリマー溶液を、ホモミキサーを装着した容器に入った５０℃の温水中に投入して塩化メチレンを蒸発させ粉末状ポリマーを得た。この粉末状ポリマーを脱水した後、少量の水を含んだ含水粉末状ポリマーを真空乾燥機で、減圧下１２０℃で２４時間乾燥してポリアリレート樹脂を得た。
〔実施例２〜８、比較例１〜７〕
実施例１の重合触媒の混合比率、添加量、ビスフェノールモノマーの組成を変更した以
外は実施例１と同じ方法でポリアリレートを製造した。
Hereinafter, the present invention will be described in more detail with reference to examples. Various physical property values were measured by the following methods.
(Inherent viscosity (ηinh))
1,1,2,2-Tetrachloroethane was used as a measurement solvent, and measurement was performed under the conditions of a concentration of 1 g / dl and a temperature of 25 ° C.
(Carboxyl value)
After 0.3 g of a sample was dissolved in 20 ml of methylene chloride in an Erlenmeyer flask, an indicator (phenol red) was added, and it was appropriately determined with a 0.1 N KOH solution.
(Glass transition point)
It calculated | required by the temperature increase rate of 20 degree-C / min using the differential thermal analyzer (The Perkin-Elmer company make, DSC-7).
[Example 1]
In a reaction vessel equipped with a stirrer, 4059 g (17.
78 mol), 2366 g (7.62 mol) of BPTMC, 190.8 g (1.27 mol) of p-tert-butylphenol as a terminal terminator, and 2187 g (54.54 mol) of sodium hydroxide.
68 mol), the polymerization catalyst is charged in a total amount of 0.70 mol% with respect to the total number of moles of bisphenol. As the breakdown for BPA, trimethylbenzylammonium chloride (hereinafter, TMBAC) and 23.1 g (0.49 mol%), relative to BPTMC, tri - n-butyl benzyl ammonium chloride (hereinafter, TBBAC) 16 0.6 g (0.21 mol%) and dissolved in 117 L of aqueous phase (aqueous phase). Separately, 5286 g of a terephthalic / isophthalic acid chloride = 1/1 mixture (hereinafter MPC) was dissolved in 69 L of methylene chloride (organic phase). This organic phase was added to the previously prepared aqueous phase under strong stirring, and an interfacial polycondensation reaction was performed at 15 ° C. for 2 hours. After the polymerization was stopped (stirring was stopped), the aqueous phase and the organic phase were decanted and separated. After removing the aqueous phase, acetic acid was added until the pH became neutral while stirring the same amount of ion-exchanged water. Further, the operation of stirring for 20 minutes and then decanting for 20 minutes to remove the aqueous phase and replace with new ion-exchanged water was repeated 5 times. The polymer solution, which is an organic phase after washing, was poured into 50 ° C. warm water contained in a container equipped with a homomixer to evaporate methylene chloride to obtain a powdery polymer. After dehydrating the powder polymer, the water-containing powder polymer containing a small amount of water was dried with a vacuum dryer at 120 ° C. for 24 hours under reduced pressure to obtain a polyarylate resin.
[Examples 2-8, Comparative Examples 1-7]
A polyarylate was produced in the same manner as in Example 1, except that the mixing ratio, addition amount, and composition of the bisphenol monomer of Example 1 were changed.
表１から明らかなように、実施例では耐熱性とカルボキシル価の低いポリアリレートが作製できた。 As is clear from Table 1, polyarylate having low heat resistance and low carboxyl value could be produced in the examples.
一方、比較例１ではシクロヘキサン環系モノマーを配合しなかったため耐熱性が低かった。比較例２ではイソプロピリデン系モノマーを配合しなかったため分子量が大きくならずインヘレント粘度は低かった。比較例３ではＴＢＢＡＣの配合を行わなかったため分子量が大きくならずインヘレント粘度は低かった。比較例４ではＴＭＢＡＣの配合を行わなかったため分子量が大きくならずインヘレント粘度は低かった。比較例５では配合する２種の重合触媒の総量がビスフェノールのモル数に対して１．０モル％を超えたため、副反応である加水分解反応が活性になりカルボキシル価が増大した。比較例６では配合する２種の重合触媒の総量がビスフェノールのモル数に対して０．５モル％を下回ったため、分子量が上がらずインヘレント粘度は低かった。比較例７では２種の重合触媒の配合およびその総量が適正であったが、イソプロピリデン系モノマーとシクロヘキサン系モノマーの配合が本願発明の範囲でなかったため分子量が上がらずインヘレント粘度は低かった。また、比較例においてインヘレント粘度が０．４５を超えなかったものについてはカルボキシル価も高く、また電気特性も悪かった。
On the other hand, heat resistance was low in Comparative Example 1 because no cyclohexane ring monomer was blended. In Comparative Example 2, since the isopropylidene monomer was not blended, the molecular weight was not increased and the inherent viscosity was low. In Comparative Example 3, since TBBAC was not blended, the molecular weight was not increased and the inherent viscosity was low. In Comparative Example 4, since TMBAC was not blended, the molecular weight was not increased and the inherent viscosity was low. In Comparative Example 5, the total amount of the two polymerization catalysts to be blended exceeded 1.0 mol% with respect to the number of moles of bisphenol, so that the hydrolysis reaction as a side reaction became active and the carboxyl number increased. In Comparative Example 6, the total amount of the two polymerization catalysts to be blended was less than 0.5 mol% with respect to the number of moles of bisphenol, so the molecular weight did not increase and the inherent viscosity was low. In Comparative Example 7, the blending of the two kinds of polymerization catalysts and the total amount thereof were appropriate, but the blending of the isopropylidene monomer and the cyclohexane monomer was not within the scope of the present invention, so the molecular weight did not increase and the inherent viscosity was low. In the comparative examples, those having an inherent viscosity not exceeding 0.45 also had a high carboxyl number and poor electrical characteristics.
Claims (2)
（Ａ）：１，１−ビス（４−ヒドロキシフェニル）シクロヘキサン（ＢＰＺ）、または１，１−ビス（４−ヒドロキシフェニル）−３，３，５−トリメチルシクロヘキサン（ＢＰＴＭＣ）
（Ｂ）：２，２−ビス（４−ヒドロキシフェニル）プロパン（ＢＰＡ）、２，２−ビス（３−メチルー４−ヒドロキシフェニル）プロパン（ＢＰＣ）、または２，２−ビス（３，５−ジメチル−４−ヒドロキシフェニル）プロパン（ＴＭＢＰＡ）
〜９０／１０である。）
またはＯＨ、ＨＳＯ ４ を表す。）
またはＯＨ、ＨＳＯ ４ を表す。） (A) A polyarylate composed of a bisphenol having a cyclohexane ring structure and (B) a bisphenol having an isopropylidene skeleton, and (C) an aromatic dicarboxylic acid, wherein (A) and (B) are as follows: The selected range has a chemical structure of the following formula (1), and the total amount of the polymerization catalyst represented by the following formulas (2) and (3) is 0.5 to 1.0 mol% with respect to bisphenol. And obtained by interfacial polycondensation, having an inherent viscosity (ηinh) of 0.45 to 1.00 dl / g, a carboxyl value of 30 mol / t or less, and a glass transition point. Polyarylate having a temperature of 200 ° C. or higher.
(A): 1,1-bis (4-hydroxyphenyl) cyclohexane (BPZ) or 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (BPTMC)
(B): 2,2-bis (4-hydroxyphenyl) propane (BPA), 2,2-bis (3-methyl-4-hydroxyphenyl) propane (BPC), or 2,2-bis (3,5- Dimethyl-4-hydroxyphenyl) propane (TMBPA)
~ 90/10. )
Or represents OH, the HSO 4. )
Or represents OH, the HSO 4. )
下記式（３）の重合触媒を混合し、界面重縮合で製造することを特徴とするポリアリレー
トの製造方法。
またはＯＨ、ＨＳＯ４を表す。）
またはＯＨ、ＨＳＯ４を表す。）
A method for producing a polyarylate according to claim 1, wherein the polymerization catalyst of the following formula (2) and the polymerization catalyst of the following formula (3) are mixed and produced by interfacial polycondensation. Production method.
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