JPH0368627A - Production of aromatic polycarbonate - Google Patents
Production of aromatic polycarbonateInfo
- Publication number
- JPH0368627A JPH0368627A JP17108489A JP17108489A JPH0368627A JP H0368627 A JPH0368627 A JP H0368627A JP 17108489 A JP17108489 A JP 17108489A JP 17108489 A JP17108489 A JP 17108489A JP H0368627 A JPH0368627 A JP H0368627A
- Authority
- JP
- Japan
- Prior art keywords
- prepolymer
- groups
- polymerization
- polycarbonate
- number average
- 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.)
- Granted
Links
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 35
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 35
- 125000003118 aryl group Chemical group 0.000 title claims description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 10
- 239000011261 inert gas Substances 0.000 claims abstract description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 41
- 239000007790 solid phase Substances 0.000 claims description 19
- 125000005587 carbonate group Chemical group 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 abstract description 5
- 238000002425 crystallisation Methods 0.000 abstract description 5
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- JKJWYKGYGWOAHT-UHFFFAOYSA-N bis(prop-2-enyl) carbonate Chemical group C=CCOC(=O)OCC=C JKJWYKGYGWOAHT-UHFFFAOYSA-N 0.000 abstract 3
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 30
- 239000002904 solvent Substances 0.000 description 15
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- -1 aryl carbonate Chemical compound 0.000 description 8
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 150000001805 chlorine compounds Chemical class 0.000 description 4
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000005809 transesterification reaction Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000012696 Interfacial polycondensation Methods 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、エンジニアリングプラスチックである芳香族
ポリカーボネートの製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing aromatic polycarbonate, which is an engineering plastic.
芳香族ポリカーボネートは、２，２−ビス（４−ヒドロ
キシフェニル）プロパン（以下ビスフェノールＡという
）とホスゲンとの界面重縮合法で工業化されている。こ
の方法は有毒なホスゲンを用いなければならないこと、
副生、塩化水素や塩化ナトリウムが腐食性であり、また
、ポリマーに残留した場合、物性に悪影響を及ぼすとい
う欠点がある。又多量の塩化メチレンを溶媒として使用
することも欠点で、ポリマーとの分離が難しく、また残
留塩化メチレンも、物性に悪影響を及ぼす。Aromatic polycarbonates have been industrialized by interfacial polycondensation of 2,2-bis(4-hydroxyphenyl)propane (hereinafter referred to as bisphenol A) and phosgene. This method requires the use of toxic phosgene;
By-products such as hydrogen chloride and sodium chloride are corrosive, and if they remain in the polymer, they have the disadvantage of adversely affecting physical properties. Another drawback is that a large amount of methylene chloride is used as a solvent, making it difficult to separate it from the polymer, and residual methylene chloride also has a negative effect on physical properties.
ビスフェノールＡとジフェニルカーボネートを溶融重合
するエステル交換法も知られているが、高温で触媒を用
いて重合するため、カラーが悪く、分岐しやすく、また
高分子量がつくりにくいという欠点を有している−０
また、ビスフェノールＡのジメチルカーボネート縮金物
の自己縮合法が特開昭６４−４６１７号公報に記載され
ている。特開昭６４−４６１７号公報の方法には、溶融
重合後、固相重合する方法が記載されている。A transesterification method in which bisphenol A and diphenyl carbonate are melt-polymerized is also known, but because the polymerization is carried out using a catalyst at high temperatures, it has the drawbacks of poor color, easy branching, and difficulty in producing high molecular weight. -0 Furthermore, a self-condensation method of dimethyl carbonate condensate of bisphenol A is described in JP-A-64-4617. JP-A-64-4617 describes a method in which melt polymerization is followed by solid phase polymerization.
固相重合法は溶融重合法に比べ、重合温度が低く、その
分重合時のポリマーの劣化が少ないことが特徴であるが
、重合速度が遅いのが欠点である。Compared to the melt polymerization method, the solid phase polymerization method is characterized by a lower polymerization temperature and therefore less deterioration of the polymer during polymerization, but the disadvantage is that the polymerization rate is slow.
従来の方法では重合速度が十分でなく、重合時間が長時
間にわたり、また重合時間を短縮しようとして触媒を使
用するとポリマーの品質が低下するという問題をかかえ
ていた。Conventional methods have had the problem that the polymerization rate is not sufficient, the polymerization time is long, and the quality of the polymer deteriorates when a catalyst is used to shorten the polymerization time.
本発明は、従来のホスゲン法や熔融法が有している種々
の欠点を克服し、塩素化合物を含まない商品質の芳香族
ポリカーボネートを製造する方法であり、しかも重合速
度が速く工業的に有利な固相重合プロセスを提供するこ
とにある。The present invention overcomes the various drawbacks of the conventional phosgene method and melting method, and is a method for producing commercial quality aromatic polycarbonate that does not contain chlorine compounds.Moreover, it has a fast polymerization rate and is industrially advantageous. The objective is to provide a solid phase polymerization process.
〔課題を解決するための手段］
本発明者らは、固相重合法による芳香族ポリカーボネー
トの製造方法について鋭意研究した結果、数平均分子量
が１ 、５００以上で、末端基がヒドロキシル基とアリ
ールカーボネート基からなる結晶性ポリカーボネートプ
レポリマーを、該プレポリマ１ｇ当り０．１〜７ ＮＩ
２／Ｈｒの不活性ガス気流中、１５０〜２６０℃の温度
で固相重合することにより、上記課題を解決することを
見出し、この知見に基づいて本発明を完成するに至った
。[Means for Solving the Problems] As a result of intensive research into a method for producing aromatic polycarbonate using a solid phase polymerization method, the present inventors found that a polycarbonate having a number average molecular weight of 1,500 or more and having a terminal group of a hydroxyl group and an aryl carbonate. A crystalline polycarbonate prepolymer consisting of 0.1 to 7 NI per 1 g of the prepolymer
It has been discovered that the above problem can be solved by solid phase polymerization at a temperature of 150 to 260° C. in an inert gas flow of 2/Hr, and the present invention has been completed based on this knowledge.
即ち、本発明は、数平均分子量が、１，５００以上で、
末＃Ａ基がヒドロキシル基とアリールカーボネート基か
らなる結晶性ポリカーボネートプレポリマーを、該プレ
ポリマー１ｇ当り０，１〜７Ｎ１／Ｈｒの不活性ガス気
流中、１５０〜２６０℃の温度で固相重合することを特
徴とする芳香族ポリカーボネートの製造方法である。That is, the present invention has a number average molecular weight of 1,500 or more,
A crystalline polycarbonate prepolymer whose terminal #A group is a hydroxyl group and an aryl carbonate group is solid-phase polymerized at a temperature of 150 to 260°C in an inert gas flow of 0.1 to 7 N1/Hr per gram of the prepolymer. This is a method for producing aromatic polycarbonate characterized by the following.
本発明に用いる結晶性ポリカーボネートプレポリマーの
数平均分子量は、ｌ 、 ５００以上、好ましくは２．
０００〜２０．０００である。数平均分子量が１ 、５
００以下では、固相重合時間が長くなりすぎるし、又固
相重合時の融着が生じやすく、好ましくない。The number average molecular weight of the crystalline polycarbonate prepolymer used in the present invention is l, 500 or more, preferably 2.
000 to 20.000. Number average molecular weight is 1,5
If it is less than 00, the solid phase polymerization time becomes too long and fusion tends to occur during the solid phase polymerization, which is not preferable.
また、結晶性プレポリマーの末端基はヒドロキシル基と
アリールカーボネート基からなっている。Furthermore, the terminal groups of the crystalline prepolymer consist of hydroxyl groups and aryl carbonate groups.
ヒドロキシル基とアリールカーボネート基の比率に特に
制限はないが重合速度の点から１０ ： ９０〜９０
： １０ 、特に２０ ： ８０〜８０ ： ２０の範
囲が好ましい。There is no particular restriction on the ratio of hydroxyl group to aryl carbonate group, but from the viewpoint of polymerization rate it is 10:90-90.
:10, particularly preferably in the range of 20:80 to 80:20.
本発明で用いられる結晶性ポリカーボネートプレポリマ
ーは、下記の一般式で表わされる。The crystalline polycarbonate prepolymer used in the present invention is represented by the following general formula.
でＲは、水素又はアルキル基、Ａｒは芳香族残基を表わ
す。）
Ｒの具体例としては、−Ｈ，−ＣＨ３゜のジアリールア
ルカン残基、
等が挙げられる。結晶性ポリカーボネートプレポリマー
においては、Ａｒは一種又は二種以上が組合わされても
良いが、通常ジアリールアルカン残基がＡｒ中の５０
ｍｏ １２％以上のものが好ましく、さらには８０ ｍ
ｏ １％以上含むものが特に好ましい。where R represents hydrogen or an alkyl group, and Ar represents an aromatic residue. ) Specific examples of R include -H, -CH3° diarylalkane residues, and the like. In the crystalline polycarbonate prepolymer, Ar may be used alone or in combination, but usually the diarylalkane residue is 50% in Ar.
mo 12% or more is preferable, more preferably 80 m
o Those containing 1% or more are particularly preferred.
又、本発明の結晶性プレポリマーの結晶化度については
特に制限はないが、結晶化度は通常５〜５５％の範囲（
Ｘ線回折法）である。結晶化度が低いと融着しやすく、
高すぎると重合速度が遅くなる。Further, there is no particular restriction on the degree of crystallinity of the crystalline prepolymer of the present invention, but the degree of crystallinity is usually in the range of 5 to 55% (
X-ray diffraction method). When the degree of crystallinity is low, it is easy to fuse,
If it is too high, the polymerization rate will be slow.
本発明に用いる結晶性プレポリマーの形状には特に制限
はなく、パウダー状、ペレジト状、繊維状、フィルム状
のいずれでも可能である。There is no particular restriction on the shape of the crystalline prepolymer used in the present invention, and it may be in the form of powder, pellet, fiber, or film.
本発明において、固相重合は結晶性ポリカーボネートフ
゛レボリマ−１ｇ当り０．１〜７ Ｎｌ／Ｈｒ、好まし
くは０．２〜５ Ｎｌ／Ｈｒの不活性ガス気流中で行な
われる。不活性ガスの流量が０．１ Ｎｊ！／Ｈｒより
低い場合には固相重合速度が遅くなり、また、７ Ｎｌ
／Ｈｒより流量が高い場合には、縮合副生成物であるフ
ェノール等の芳香族モノヒドロキシ化合物あるいはジア
リールカーボネートと不活性ガスを分離するための設備
が大きくなり、工業的に好ましくない。In the present invention, the solid phase polymerization is carried out in an inert gas flow of 0.1 to 7 Nl/Hr, preferably 0.2 to 5 Nl/Hr per gram of crystalline polycarbonate polymer. The flow rate of inert gas is 0.1 Nj! /Hr, the solid phase polymerization rate becomes slow, and 7 Nl
If the flow rate is higher than /Hr, the equipment for separating the inert gas from the condensation by-products, such as aromatic monohydroxy compounds such as phenol or diaryl carbonate, becomes large, which is industrially undesirable.
本発明で用いられる不活性ガスとしては、窒素、ネオン
、アルゴン、ＣＯ２等が挙げられる。入手の容易さとい
う点で特に窒素が好ましい。Examples of the inert gas used in the present invention include nitrogen, neon, argon, CO2, and the like. Nitrogen is particularly preferred from the viewpoint of easy availability.
本発明の製造方法は、結晶性ポリカーボネートプレポリ
マーのガラス転移温度以上、融点以下の温度で固相重合
により行われ、１５０℃〜２６０℃の範囲である。１５
０″Ｃ以下では重合速度が遅く、２６０℃以上では固相
重合中に融着が激しくなり好ましくない。The production method of the present invention is carried out by solid phase polymerization at a temperature above the glass transition temperature and below the melting point of the crystalline polycarbonate prepolymer, and is in the range of 150°C to 260°C. 15
If it is below 0''C, the polymerization rate will be slow, and if it is above 260°C, fusion will become intense during solid phase polymerization, which is not preferable.
固相重合の圧力は特に制限はなく、減圧、常圧、加圧の
いずれでも実施できるが、特に常圧又は微加圧の状態で
も容易に重合が進行することが明らかになったので、安
価な設備で工業的に容易に実施できることも本発明の特
徴である。There is no particular restriction on the pressure for solid phase polymerization, and it can be carried out at reduced pressure, normal pressure, or increased pressure, but it has become clear that polymerization proceeds easily even under normal pressure or slightly increased pressure, so it is less expensive. Another feature of the present invention is that it can be easily implemented industrially using suitable equipment.
固相重合のプロセスとしては各種の方法が知られている
がいずれの方法も使用できる。Various methods are known as solid phase polymerization processes, and any of these methods can be used.
たとえば、タンブラ−型、キルン型、パドルドライヤー
型、スクリューコンベア型、振動型、流動床型、固定床
型、移動床型等が挙げられる。Examples include tumbler type, kiln type, paddle dryer type, screw conveyor type, vibrating type, fluidized bed type, fixed bed type, and moving bed type.
固相重合して得られる芳香族ポリカーボネートの数平均
分子量としては通常６．０００〜２００ 、０００であ
る。The number average molecular weight of the aromatic polycarbonate obtained by solid phase polymerization is usually 6.000 to 200,000.
なお、固相重合は、触媒の存在下もしくは不存在下のど
ちらも可能であるが、無触媒重合の方が得られるポリマ
ーのカラー、耐熱性、耐熱水性が格段に優れるので好ま
しい９重合触媒としてはポリカーボネートあるいはポリ
エステルに使われる公知の各種のエステル交換触媒等の
重合触媒が使用できる。例えば、ビスフェノールＡのア
ルカリ金属塩、スズ、鉛の化合物等が挙げられる。Although solid-phase polymerization can be carried out in the presence or absence of a catalyst, non-catalytic polymerization is the preferred polymerization catalyst because the resulting polymer has much better color, heat resistance, and hot water resistance. For this purpose, polymerization catalysts such as various known transesterification catalysts used for polycarbonate or polyester can be used. Examples include alkali metal salts of bisphenol A, compounds of tin, and lead.
本発明に用いる結晶性ポリカーボネートプレポリマーを
得る方法としては、通常まず非晶性ポリカーポネ〜トブ
レボリマーを合成し、次いでこの非晶性ポリカーボネー
トプレボリマーを結晶化する方法がとられる。The method for obtaining the crystalline polycarbonate prepolymer used in the present invention is usually to first synthesize an amorphous polycarbonate to Treble polymer, and then to crystallize the amorphous polycarbonate prepolymer.
非晶性プレポリマーの合成方法としては特に限定はなく
、下記の種々の方法で合成される。There are no particular limitations on the method of synthesizing the amorphous prepolymer, and the amorphous prepolymer can be synthesized by various methods described below.
即ち、エステル交換法により、ビスフェノールＡ等のビ
フェノールとジアリールカーボネートの溶融重合による
合成する方法、末端停止剤としてフェノールやターシャ
リ−ブチルフェノール等芳香族モノヒドロキシ化合物の
存在下にビフェノールとホスゲンを界面重縮合させて合
成する方法、ビフェノールとジアリールカーボネートの
モル比Ｉ：２の縮合物をあらかじめ合成しておき、これ
とビフェノールを溶融重合する方法、界面重縮合におい
てビフェノールに対して過剰のホスゲンとフェノールを
反応させて得られるフェニルカーボネート末端ポリカー
ボネートオリゴマーに新たにビフェノールを加えて溶融
重合する方法等が挙げられる。That is, a method of synthesizing by melt polymerization of biphenol such as bisphenol A and diaryl carbonate by transesterification method, and interfacial polycondensation of biphenol and phosgene in the presence of an aromatic monohydroxy compound such as phenol or tert-butylphenol as a terminal stopper. A method in which a condensate of biphenol and diaryl carbonate with a molar ratio of I:2 is synthesized in advance and this is melt-polymerized with biphenol.A method in which excess phosgene and phenol are reacted with respect to biphenol in interfacial polycondensation. Examples include a method in which biphenol is newly added to a phenyl carbonate-terminated polycarbonate oligomer obtained by melt polymerization.
本発明においては、実質的に塩素化合物を含まない芳香
族ポリカーボネートを得ることができる。In the present invention, an aromatic polycarbonate substantially free of chlorine compounds can be obtained.
例えば、エステル交換法により得た非品性ポリカーボネ
ートを用いる場合は、原料中に塩素化合物がないため、
全く塩素を含まない芳香族ポリカーボネートを製造でき
る。For example, when using non-grade polycarbonate obtained by transesterification, there are no chlorine compounds in the raw material, so
Aromatic polycarbonate containing no chlorine can be produced.
又、ホスゲン等を使用して非晶性ポリカーボネートプレ
ボリマーを製造した場合でも、低分子量の非晶性プレポ
リマーから塩素を除くことは容易であるため、本発明の
場合、実質的に塩素を含まない芳香族ポリカーボネート
を得ることができる。Furthermore, even when an amorphous polycarbonate prepolymer is produced using phosgene or the like, it is easy to remove chlorine from a low molecular weight amorphous prepolymer. aromatic polycarbonate can be obtained.
非品性ポリカーボネートプレポリマーを結晶化させる方
法は特に制限はないが通常、溶媒処理法及び加熱結晶化
法が好ましく用いられる。There are no particular limitations on the method for crystallizing the non-quality polycarbonate prepolymer, but usually, a solvent treatment method and a heating crystallization method are preferably used.
前者の溶媒処理法は、適当な溶媒を用いてプレポリマー
を結晶化させる方法であり、具体的には非晶性プレポリ
マーを溶媒に溶解させたのち、この溶液から結晶性のプ
レポリマーを析出させる方法や、プレポリマーに対する
溶解力の小さい溶媒を用いて、その溶媒が非晶性プレポ
リマー中に浸透して、非品性プレポリマーを結晶化させ
るのに必要な時間、該プレポリマーを液状の溶媒又は溶
媒蒸気に接触させる方法などが好ましく用いられる。The former solvent treatment method is a method in which a prepolymer is crystallized using an appropriate solvent. Specifically, an amorphous prepolymer is dissolved in a solvent, and then a crystalline prepolymer is precipitated from this solution. The prepolymer is kept in a liquid state for a period of time necessary for the solvent to permeate into the amorphous prepolymer and crystallize the non-quality prepolymer using a solvent with low dissolving power for the prepolymer. A method of contacting with a solvent or solvent vapor is preferably used.
このような非晶性プレポリマーの溶媒処理のために使用
できる溶媒としては、例えば、クロロメタン、塩化メチ
レン、クロロホルム、四塩化炭素、クロロエタン、ジク
ロロエタン（各種）、トリクロロエタン（各種）、トリ
クロロエチレン、テトラクロロエタン（各種）などの脂
肪族ハロゲン化炭化、１ｍ；クロロベンゼン、ジクロロ
ベンゼンナトの芳香族ハロゲン化炭化水素類；テトラヒ
ドロフラン、ジオキサンなどのエーテル類；酢酸メチル
、酢酸エチルなどのエステル類；アセトン、メチルエチ
ルケトンなどのケトン類；ベンゼン、トルエン、キシレ
ンなどの芳香族炭化水素類などが挙げられる。高品質の
ポリマーを得るためには、ハロゲンを含まない溶媒が特
に好ましい。これらの溶媒は１種用いてもよいし、２種
以上を混合して用いてもよい。Solvents that can be used for solvent treatment of such amorphous prepolymers include, for example, chloromethane, methylene chloride, chloroform, carbon tetrachloride, chloroethane, dichloroethane (various types), trichloroethane (various types), trichloroethylene, tetrachloroethane. Aliphatic halogenated hydrocarbons such as (various), 1m; aromatic halogenated hydrocarbons such as chlorobenzene and dichlorobenzenato; ethers such as tetrahydrofuran and dioxane; esters such as methyl acetate and ethyl acetate; acetone and methyl ethyl ketone, etc. Ketones; aromatic hydrocarbons such as benzene, toluene, and xylene. Halogen-free solvents are particularly preferred in order to obtain high quality polymers. These solvents may be used alone or in combination of two or more.
一方、加熱結晶化法は、該プレポリマーを目的とする芳
香族ポリカーボネートのガラス転移温度以上で、かつ該
プレポリマーが溶融しはじめる温度未満の範囲の温度に
おいて加熱することによって、結晶化させる方法である
。この方法は、単にプレポリマーを加熱下で保持するの
みで、結晶化させることができるので、極めて容易に工
業的に実施しうる。On the other hand, the heating crystallization method is a method in which the prepolymer is crystallized by heating at a temperature that is above the glass transition temperature of the target aromatic polycarbonate and below the temperature at which the prepolymer begins to melt. be. This method can be carried out industrially very easily since the prepolymer can be crystallized simply by holding it under heat.
本発明は、従来のホスゲン法や溶融法が有している種々
の欠点を克服し、塩素化合物を含まない高品質の芳香族
ポリカーボネートを製造することができ、しかも重合速
度が速く工業的に有利な固相重合プロセスである。The present invention overcomes various drawbacks of the conventional phosgene method and melting method, and can produce high-quality aromatic polycarbonate that does not contain chlorine compounds.Moreover, the polymerization rate is fast and it is industrially advantageous. It is a solid phase polymerization process.
次に実施例により本発明をさらに詳細に説明するが本発
明はこれらの例によってなんら限定されるものではない
。EXAMPLES Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to these examples in any way.
なお、分子量はゲルバーミエーシゴンクロマトグラフィ
−（ｃｐｃ）で測定した数平均分子量である。In addition, the molecular weight is a number average molecular weight measured by gel vermicelligon chromatography (CPC).
プレポリマー中の末端基は、高速液体クロマトグラフィ
ーによる分析又はＮＭＲによる分析を使用した。The end groups in the prepolymer were analyzed by high performance liquid chromatography or NMR.
結晶化度は、粉末Ｘ線回折より特願昭６３−２４０７８
５号に記載の方法で求めた。Crystallinity was determined by powder X-ray diffraction according to patent application No. 63-24078.
It was determined by the method described in No. 5.
実施例１
ビスフェノールＡとジフェニルカーボネートを原料とし
、アセトンによる溶媒結晶化法で得られた、数平均分子
量４．ＩｏＯ１末端ヒドロキシル１５３５％、 末端フ
ェニルカーボネート基６５％、結晶化度 ２５％の結晶
性ポリカーボネートプレポリマーを用いて、内径１５１
ｍのガラス製ガス流通式反応器で固相重合を行なった。Example 1 Using bisphenol A and diphenyl carbonate as raw materials, a number average molecular weight of 4.0 was obtained by solvent crystallization using acetone. Using a crystalline polycarbonate prepolymer with 1535% IoO1 terminal hydroxyls, 65% terminal phenyl carbonate groups, and 25% crystallinity, the inner diameter was 151%.
Solid phase polymerization was carried out in a glass gas flow reactor.
重合条件は、仕込んだ結晶性ポリカーボネートプレポリ
マー２ｇに対し、窒素を２．５Ｎｊ２／Ｈｒで供給し、
常圧下２１０ ”Ｃで行なった。重合時間２時間で数平
均分子量１０．８００のポリマーが得られた。The polymerization conditions were to supply nitrogen at 2.5 Nj2/Hr to 2 g of the charged crystalline polycarbonate prepolymer,
The polymerization was carried out under normal pressure at 210"C. A polymer having a number average molecular weight of 10.800 was obtained in a polymerization time of 2 hours.
実施例２〜４及び比較例１〜２
窒素流量、重合時間及び温度を第１表に示す如く変化さ
せる以外は、実施例１と全く同様にしてポリマーを得た
。その結果を第１表に示す。Examples 2 to 4 and Comparative Examples 1 to 2 Polymers were obtained in exactly the same manner as in Example 1, except that the nitrogen flow rate, polymerization time, and temperature were changed as shown in Table 1. The results are shown in Table 1.
（以下余白）
第
１
表
（以下余白）
よる溶媒結晶化法で得られた数平均分子１３．４００末
端ヒドロキシル基４０％、末端フェニルカーボネート基
６０％、結晶化度２３％の結晶性プレポリマーを用いる
以外は、実施例Ｉと全く同様にしてポリマーを得た。重
合時間２時間後の数平均分子量は１０，９００であった
。(Hereinafter in the margin) Table 1 (Hereinafter in the margin) A crystalline prepolymer with a number average molecular weight of 13.400, 40% terminal hydroxyl groups, 60% terminal phenyl carbonate groups, and 23% crystallinity was obtained by the solvent crystallization method according to Table 1 (blank below). A polymer was obtained in exactly the same manner as in Example I except for using the following. The number average molecular weight after 2 hours of polymerization was 10,900.
Claims (1)
キシル基とアリールカーボネート基からなる結晶性ポリ
カーボネートプレポリマーを、該プレポリマー１ｇ当り
０．１〜７Ｎｌ／Ｈｒの不活性ガス気流中、１５０〜２
６０℃の温度で固相重合することを特徴とする芳香族ポ
リカーボネートの製造方法。1. A crystalline polycarbonate prepolymer having a number average molecular weight of 1,500 or more and having terminal groups of hydroxyl groups and aryl carbonate groups is heated to 150% in an inert gas flow of 0.1 to 7 Nl/Hr per 1 g of the prepolymer. ~2
A method for producing aromatic polycarbonate, which comprises performing solid phase polymerization at a temperature of 60°C.
Priority Applications (12)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1171084A JPH0757793B2 (en) | 1989-07-04 | 1989-07-04 | Method for producing aromatic polycarbonate |
| SG1996003754A SG52381A1 (en) | 1988-12-27 | 1989-09-29 | A porous crystallized aromatic polycarbonate prepolymer a porous crystallized aromatic polycarbonate and production method |
| DE68928567T DE68928567T2 (en) | 1988-12-27 | 1989-09-29 | POROUS CRYSTALLIZED AROMATIC POLYCARBONATE PREPOLYMER, A POROUS CRYSTALLIZED AROMATIC POLYCARBONATE AND METHOD FOR PRODUCING THE SAME |
| EP89910918A EP0403657B1 (en) | 1988-12-27 | 1989-09-29 | A porous, crystallized, aromatic polycarbonate prepolymer, a porous, crystallized aromatic polycarbonate, and production methods |
| PCT/JP1989/000994 WO1990007536A1 (en) | 1988-12-27 | 1989-09-29 | A porous, crystallized, aromatic polycarbonate prepolymer, a porous, crystallized aromatic polycarbonate, and production methods |
| AT89910918T ATE162832T1 (en) | 1988-12-27 | 1989-09-29 | POROUS CRYSTALIZED AROMATIC POLYCARBONATE PREPOLYMER, A POROUS CRYSTALIZED AROMATIC POLYCARBONATE AND METHOD FOR PRODUCING |
| US07/442,353 US5204377A (en) | 1988-12-27 | 1989-09-29 | Porous, crystallized, aromatic polycarbonate prepolymer, a porous, crystallized aromatic polycarbonate, and production methods |
| KR1019890702244A KR930003022B1 (en) | 1988-12-27 | 1989-09-29 | Porous, crystallized, aromatic polycarbonate prepolymer porous crystallized aromatic polycarbonate and production methods |
| CA002170019A CA2170019C (en) | 1988-12-27 | 1989-10-04 | A porous, crystallized, aromatic polycarbonate prepolymer, a porous crystallized aromatic polycarbonate, and production methods |
| CA002000163A CA2000163C (en) | 1988-12-27 | 1989-10-04 | Porous, crystallized, aromatic polycarbonate prepolymer, a porous, crystallized aromatic polycarbonate, and production methods |
| SU894742448A RU2040532C1 (en) | 1988-12-27 | 1989-11-29 | Method of preparing crystalline aromatic polycarbonate prepolymer and a method of preparing high-molecular crystalline aromatic polycarbonate |
| ES08904354A ES2054594A6 (en) | 1988-12-27 | 1989-12-26 | A porous, crystallized, aromatic polycarbonate prepolymer, a porous, crystallized aromatic polycarbonate, and production methods. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1171084A JPH0757793B2 (en) | 1989-07-04 | 1989-07-04 | Method for producing aromatic polycarbonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0368627A true JPH0368627A (en) | 1991-03-25 |
| JPH0757793B2 JPH0757793B2 (en) | 1995-06-21 |
Family
ID=15916708
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1171084A Expired - Fee Related JPH0757793B2 (en) | 1988-12-27 | 1989-07-04 | Method for producing aromatic polycarbonate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0757793B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100298637B1 (en) * | 1999-06-29 | 2001-09-22 | 김충섭 | Process for the preparation of polycarbonate |
| JP2002215068A (en) * | 2001-01-17 | 2002-07-31 | Toppan Printing Co Ltd | Display medium |
| US7671142B2 (en) | 2003-12-10 | 2010-03-02 | Asahi Kasei Chemicals Corporation | Thermoplastic resin having rigidity when heated |
| WO2011115253A1 (en) | 2010-03-19 | 2011-09-22 | 旭化成ケミカルズ株式会社 | Styrene-based resin composition, and resin molded article comprising same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS644617A (en) * | 1987-06-26 | 1989-01-09 | Asahi Chemical Ind | Preparation of aromatic polycarbonate |
-
1989
- 1989-07-04 JP JP1171084A patent/JPH0757793B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS644617A (en) * | 1987-06-26 | 1989-01-09 | Asahi Chemical Ind | Preparation of aromatic polycarbonate |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100298637B1 (en) * | 1999-06-29 | 2001-09-22 | 김충섭 | Process for the preparation of polycarbonate |
| JP2002215068A (en) * | 2001-01-17 | 2002-07-31 | Toppan Printing Co Ltd | Display medium |
| US7671142B2 (en) | 2003-12-10 | 2010-03-02 | Asahi Kasei Chemicals Corporation | Thermoplastic resin having rigidity when heated |
| WO2011115253A1 (en) | 2010-03-19 | 2011-09-22 | 旭化成ケミカルズ株式会社 | Styrene-based resin composition, and resin molded article comprising same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0757793B2 (en) | 1995-06-21 |
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