JPH05408B2 - - Google Patents
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- Publication number
- JPH05408B2 JPH05408B2 JP63032527A JP3252788A JPH05408B2 JP H05408 B2 JPH05408 B2 JP H05408B2 JP 63032527 A JP63032527 A JP 63032527A JP 3252788 A JP3252788 A JP 3252788A JP H05408 B2 JPH05408 B2 JP H05408B2
- Authority
- JP
- Japan
- Prior art keywords
- aromatic polyether
- producing
- phenol
- reaction
- amount
- 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.)
- Expired - Lifetime
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- Polyethers (AREA)
Description
〔産業上の利用分野〕
本発明は、芳香族ポリエーテルの製造方法に関
し、さらに詳細には狭い分子量分布をもつ芳香族
ポリエーテルの製造方法に関する。
〔従来の技術〕
近年、高性能樹脂であるエンジニアリングプラ
スチツクスの開発が盛んに行われている。熱可塑
性の芳香族ポリエーテル、とりわけポリスルホ
ン、ポリエーテルスルホンおよびポリエーテルケ
トンは耐熱性、機械物性及び耐薬品性に優れてい
るため、電気・電子、食品工業、医療機器、自動
車部品、精密工業等の広汎な分野で使用されてい
る。
このような芳香族ポリエーテルを製造する方法
としては、ビスフエノールとジハロゲノベンゼノ
イド化合物とをジメチルスルホキシドやスルホラ
ンなどの有機高極性スルホキシドもしくはスルホ
ン溶媒中でアルカリ金属の炭酸塩の存在下に重縮
合させる方法（特公昭46−21458号公報）や、ビ
スフエノールとジハロベンゼノイド化合物とを有
機高極性スルホキシドもしくはスルホン溶媒中で
アルカリ金属の炭酸塩の存在下に重縮合させる際
に、共沸溶媒を用いないで溶媒の煮沸下に水を蒸
留除去する方法（特公昭55−23574号公報）が知
られている。
〔発明が解決しようとする課題〕
しかしながら、前者の方法は得られるポリマー
は分子量分布が広いという重大な欠点があつた。
さらに前者の製造方法は、重縮合反応中の生成水
を除去するために共沸溶媒等を使用しなければな
らず、溶媒回収の必要もあることから製造工程が
複雑化しコスト高になるという問題もあつた。
さらに有機高極性スルホキシドもしくはスルホ
ン溶媒は常圧下では沸点が安定しないことから減
圧蒸留を必要とし製造工程が煩雑化するという問
題もあつた。
そこで、本発明の目的は、工程が煩雑化せず分
子量分布の狭い芳香族ポリエーテルを製造する方
法を提供することにある。
〔課題を解決するための手段〕
本発明者らは、上記課題を解決すべく鋭意検討
した結果、反応溶媒として不活性有機高極性アミ
ド溶媒であるＮ，Ｎ−ジメチルアセトアミドを使
用することで分子量分布の狭い所定の高分子量の
芳香族ポリエーテルを、工程を煩雑化することな
く製造することに成功した。
即ち、本発明は、二価フエノールと、該二価フ
エノールと実質的に等モル量のジハロゲノベンゼ
ノイド化合物とを、フエノール基一つに対し実質
的に一つ以上のアルカリ金属原子を有する量のア
ルカリ金属炭酸塩の存在下で反応させる芳香族ポ
リエーテルの製造方法であつて、反応溶媒にＮ，
Ｎ−ジメチルアセトアミドを使用し、反応により
生成した水を共沸溶媒の不存在下に蒸留除去する
ことを特徴とする芳香族ポリエーテルの製造方法
を提供するものである。
本発明において用いられる二価フエノールとし
ては、１分子内にフエノール性水酸基を２個有す
るものであれば、特に制限はないが、例えば、以
下のようなものが挙げられる。
[Industrial Application Field] The present invention relates to a method for producing an aromatic polyether, and more particularly to a method for producing an aromatic polyether having a narrow molecular weight distribution. [Prior Art] In recent years, engineering plastics, which are high-performance resins, have been actively developed. Thermoplastic aromatic polyethers, especially polysulfone, polyethersulfone, and polyetherketone, have excellent heat resistance, mechanical properties, and chemical resistance, so they are used in electrical and electronic industries, food industries, medical equipment, automobile parts, precision industries, etc. It is used in a wide range of fields. A method for producing such an aromatic polyether is to polycondense bisphenol and a dihalogenobenzenoid compound in an organic highly polar sulfoxide or sulfone solvent such as dimethyl sulfoxide or sulfolane in the presence of an alkali metal carbonate. (Japanese Patent Publication No. 46-21458), or when polycondensing bisphenol and a dihalobenzenoid compound in an organic highly polar sulfoxide or sulfone solvent in the presence of an alkali metal carbonate, an azeotropic solvent is used. A method (Japanese Patent Publication No. 55-23574) is known in which water is removed by distillation while boiling a solvent without using. [Problems to be Solved by the Invention] However, the former method has a serious drawback in that the resulting polymer has a wide molecular weight distribution.
Furthermore, the former manufacturing method requires the use of an azeotropic solvent to remove the water produced during the polycondensation reaction, which also requires solvent recovery, which complicates the manufacturing process and increases costs. It was hot too. Furthermore, since the boiling point of organic highly polar sulfoxide or sulfone solvents is not stable under normal pressure, vacuum distillation is required, complicating the manufacturing process. Therefore, an object of the present invention is to provide a method for producing an aromatic polyether having a narrow molecular weight distribution without complicating the process. [Means for Solving the Problems] As a result of intensive studies to solve the above problems, the present inventors have found that by using N,N-dimethylacetamide, which is an inert organic highly polar amide solvent, as a reaction solvent, the molecular weight can be reduced. We succeeded in producing an aromatic polyether with a narrow distribution and a predetermined high molecular weight without complicating the process. That is, the present invention provides divalent phenol and a dihalogenobenzenoid compound in a substantially equimolar amount to the divalent phenol in an amount having substantially one or more alkali metal atoms per one phenol group. A method for producing an aromatic polyether in which the reaction is carried out in the presence of an alkali metal carbonate, the method comprising: N,
The present invention provides a method for producing an aromatic polyether, which uses N-dimethylacetamide and removes water produced by the reaction by distillation in the absence of an azeotropic solvent. The divalent phenol used in the present invention is not particularly limited as long as it has two phenolic hydroxyl groups in one molecule, but examples include the following.
以下、本発明を実施例により具体的に説明する
が、本発明はこれらに何等限定されない。
実施例 １
攪拌機、窒素導入管、温度計及び先端に受器を
付した凝縮器とを備えた１フラスコ内に、２，
２−ビス−（４−ヒドロキシフエニル）プロパン
45.66ｇ（0.2モル）、４，4′−ジクロロジフエニル
スルホン57.42ｇ（0.2モル）、無水炭酸カリウム
55.28ｇ（0.4モル）及びＮ，Ｎ−ジメチルアセト
アミド300ｇを仕込み、30分間、窒素ガスを導入
し、系内を窒素置換した。温度を反応液の沸点ま
で上昇させ、２時間かけて約60ｇのＮ，Ｎ−ジメ
チルアセトアミドを留出させた。この際、約3.6
ｇのH2Oが同時に留出した。その後還流状態で
４時間反応させたのち、100℃まで降温し、Ｎ，
Ｎ−ジメチルアセトアミド120ｇを添加し、反応
粗液の粘度を下げて、塩化メチルガスを300dl／
minで30分吹き込んだ。温度を室温まで戻し、析
出した塩及び過剰の炭酸カリウムを濾別し、濾液
を大量のメタノール中に注いで、生成ポリマーを
沈澱させた。生成ポリマーを単離し、数回メタノ
ールで洗浄したのち150℃で３時間減圧で乾燥さ
せた。
得られたポリマーの収率は97％であり、0.5％
wt／volのクロロホルム溶液中の25℃における還
元粘度は1.34dl／ｇであつた。また、GPC（ゲル
パーメーシヨンクロマトグラフイー）測定による
分子量分布の分散度ｗ／ｎ＝2.01であつた。
実施例 ２
４，4′−ジクロロジフエニルスルホンの量を
58.57ｇ（0.204モル）にした以外は、実施例１と
同様にして実験を行いポリマーを得た。得られた
ポリマーの収率は98％で、還元粘度は実施例１と
同じ条件で0.46dl／ｇであつた。GPC測定による
分子量分布の分散度ｗ／ｎ＝1.98であつた。
実施例 ３
４，4′−ジクロロジフエニルスルホンの量を
57.27ｇ（0.196モル）にした以外は、実施例１と
同様にして実験を行いポリマーを得た。得られた
ポリマーの収率は96％で、還元粘度は実施例１と
同じ条件で0.43dl／ｇであつた。GPC測定による
分子量分布の分散度ｗ／ｎ＝1.99であつた。
実施例 ４
40反応器を用いて、実施例２の処方をスケー
ルアツプし、実施例と同じ条件で還元粘度0.47
dl／ｇのポリマーを得た。GPC測定による分子
量分布の分散度ｗ／ｎ＝1.97であつた。
比較例 １
溶媒にジメチルスルホキシド300ｇを用いた以
外は実施例１と同じ原料を仕込み、230mmHgの減
圧下で２時間かけて約60ｇのジメチルスルホキシ
ドを留去させた後、160℃で減圧還流下で更に４
時間反応させた。反応終了後はジメチルスルホキ
シド120ｇを添加し、反応粗液の粘度を下げて、
塩化メチルガスを300ml／minで30分吹き込んだ。
その後、実施例１と同様の操作を行い生成ポリマ
ーを単離した。得られたポリマーの収率は95％で
あり、0.5％wt／volのクロロホルム溶液中での25
℃での還元粘度は0.79dl／ｇで、GPC測定による
分子量分布の分散度ｗ／ｎ＝2.13であつた。
〔発明の効果〕
以上説明してきたように本発明によつて得られ
た芳香族ポリエーテルは、分子量分布が狭いため
高品質の製品を提供することが可能となる。
さらに本発明の製造方法は、煩雑な工程を必要
とせず、簡略かつ経済的な方法である。
EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these in any way. Example 1 In a flask equipped with a stirrer, a nitrogen introduction tube, a thermometer, and a condenser with a receiver attached to the tip, 2,
2-bis-(4-hydroxyphenyl)propane
45.66g (0.2mol), 4,4'-dichlorodiphenylsulfone 57.42g (0.2mol), anhydrous potassium carbonate
55.28 g (0.4 mol) and 300 g of N,N-dimethylacetamide were charged, and nitrogen gas was introduced for 30 minutes to purge the system with nitrogen. The temperature was raised to the boiling point of the reaction solution, and about 60 g of N,N-dimethylacetamide was distilled out over a period of 2 hours. At this time, approximately 3.6
g of H 2 O were distilled off at the same time. After that, the reaction was carried out under reflux for 4 hours, and then the temperature was lowered to 100°C.
120g of N-dimethylacetamide was added to lower the viscosity of the reaction crude liquid, and methyl chloride gas was added to 300dl/
I blew it for 30 minutes at min. The temperature was returned to room temperature, the precipitated salt and excess potassium carbonate were filtered off, and the filtrate was poured into a large amount of methanol to precipitate the produced polymer. The resulting polymer was isolated, washed several times with methanol, and then dried under reduced pressure at 150°C for 3 hours. The yield of the obtained polymer is 97% and 0.5%
The reduced viscosity at 25° C. in wt/vol chloroform solution was 1.34 dl/g. Furthermore, the degree of dispersion w/n of the molecular weight distribution measured by GPC (gel permeation chromatography) was 2.01. Example 2 The amount of 4,4'-dichlorodiphenyl sulfone
A polymer was obtained by carrying out an experiment in the same manner as in Example 1, except that the amount was changed to 58.57 g (0.204 mol). The yield of the obtained polymer was 98%, and the reduced viscosity was 0.46 dl/g under the same conditions as in Example 1. The degree of dispersion of the molecular weight distribution by GPC measurement w/n was 1.98. Example 3 The amount of 4,4'-dichlorodiphenyl sulfone
A polymer was obtained by carrying out an experiment in the same manner as in Example 1, except that the amount was changed to 57.27 g (0.196 mol). The yield of the obtained polymer was 96%, and the reduced viscosity was 0.43 dl/g under the same conditions as in Example 1. The degree of dispersion of the molecular weight distribution by GPC measurement w/n was 1.99. Example 4 The formulation of Example 2 was scaled up using a 40 reactor, and the reduced viscosity was 0.47 under the same conditions as in Example.
dl/g of polymer was obtained. The degree of dispersion of the molecular weight distribution by GPC measurement w/n was 1.97. Comparative Example 1 The same raw materials as in Example 1 were prepared except that 300 g of dimethyl sulfoxide was used as the solvent, and about 60 g of dimethyl sulfoxide was distilled off over 2 hours under a reduced pressure of 230 mmHg, and then refluxed at 160°C under reduced pressure. 4 more
Allowed time to react. After the reaction was completed, 120g of dimethyl sulfoxide was added to lower the viscosity of the crude reaction liquid.
Methyl chloride gas was blown in at 300 ml/min for 30 minutes.
Thereafter, the same operation as in Example 1 was performed to isolate the produced polymer. The yield of the obtained polymer was 95%, with 25% in 0.5% wt/vol chloroform solution.
The reduced viscosity at °C was 0.79 dl/g, and the dispersity of molecular weight distribution w/n = 2.13 by GPC measurement. [Effects of the Invention] As explained above, the aromatic polyether obtained by the present invention has a narrow molecular weight distribution, making it possible to provide high-quality products. Furthermore, the manufacturing method of the present invention does not require complicated steps and is a simple and economical method.
Claims (1)
的に等モル量のジハロゲノベンゼノイド化合物と
を、フエノール基一つに対し実質的に一つ以上の
アルカリ金属原子を有する量のアルカリ金属炭酸
塩の存在下で反応させる芳香族ポリエーテルの製
造方法であつて、 反応溶媒にＮ，Ｎ−ジメチルアセトアミドを二
価フエノールの重量に対して0.05〜30倍の重量の
範囲で使用し、反応により生成した水を共沸溶媒
の不存在下に蒸留除去することを特徴とする芳香
族ポリエーテルの製造方法。 ２ 上記二価フエノールが、ハイドロキノンおよ
び／または 下記式 （式中、Ｙは、直接結合、−Ｏ−、−Ｓ−、−SO2
−、−CO−、または二価の炭化水素基を示す）で
表される二価フエノールである特許請求の範囲第
１項記載の芳香族ポリエーテルの製造方法。 ３ 上記ジハロゲノベンゼノイド化合物が、下記
式 （式中、Ｘはハロゲノ原子、Ｚは−SO2−または
−CO−を示し、Ｘは、Ｚに対してオルト位又は
パラ位にある）で表されるハロゲノベンゼノイド
化合物の少なくとも一種である特許請求の範囲第
１項又は第２項に記載の芳香族ポリエーテルの製
造方法。[Claims] 1. A divalent phenol and a dihalogenobenzenoid compound in a substantially equimolar amount to the divalent phenol, which has substantially one or more alkali metal atoms per phenol group. A method for producing an aromatic polyether in which the reaction is carried out in the presence of an amount of alkali metal carbonate, the method comprising: N,N-dimethylacetamide being used as a reaction solvent in an amount ranging from 0.05 to 30 times the weight of dihydric phenol. 1. A method for producing an aromatic polyether, which comprises removing water produced by the reaction by distillation in the absence of an azeotropic solvent. 2 The above dihydric phenol is hydroquinone and/or the following formula (In the formula, Y is a direct bond, -O-, -S-, -SO2
The method for producing an aromatic polyether according to claim 1, wherein the aromatic polyether is a divalent phenol represented by -, -CO-, or a divalent hydrocarbon group. 3 The dihalogenobenzenoid compound has the following formula: (In the formula, X is a halogeno atom, Z represents -SO 2 - or -CO-, and X is at the ortho or para position with respect to Z.) At least one type of halogenobenzenoid compound represented by A method for producing an aromatic polyether according to claim 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3252788A JPH01207320A (en) | 1988-02-15 | 1988-02-15 | Production of aromatic polyether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3252788A JPH01207320A (en) | 1988-02-15 | 1988-02-15 | Production of aromatic polyether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01207320A JPH01207320A (en) | 1989-08-21 |
| JPH05408B2 true JPH05408B2 (en) | 1993-01-05 |
Family
ID=12361420
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3252788A Granted JPH01207320A (en) | 1988-02-15 | 1988-02-15 | Production of aromatic polyether |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01207320A (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01245018A (en) * | 1988-03-25 | 1989-09-29 | Daicel Chem Ind Ltd | Production of polysulfone having improved degree of pigmentation |
| US7169889B1 (en) | 1999-06-19 | 2007-01-30 | Biocon Limited | Insulin prodrugs hydrolyzable in vivo to yield peglylated insulin |
| US6867183B2 (en) | 2001-02-15 | 2005-03-15 | Nobex Corporation | Pharmaceutical compositions of insulin drug-oligomer conjugates and methods of treating diseases therewith |
| US6835802B2 (en) * | 2001-06-04 | 2004-12-28 | Nobex Corporation | Methods of synthesizing substantially monodispersed mixtures of polymers having polyethylene glycol moieties |
| US6713452B2 (en) | 2001-06-04 | 2004-03-30 | Nobex Corporation | Mixtures of calcitonin drug-oligomer conjugates comprising polyalkylene glycol, uses thereof, and methods of making same |
| US6858580B2 (en) | 2001-06-04 | 2005-02-22 | Nobex Corporation | Mixtures of drug-oligomer conjugates comprising polyalkylene glycol, uses thereof, and methods of making same |
| US6828297B2 (en) | 2001-06-04 | 2004-12-07 | Nobex Corporation | Mixtures of insulin drug-oligomer conjugates comprising polyalkylene glycol, uses thereof, and methods of making same |
| US7196059B2 (en) | 2001-09-07 | 2007-03-27 | Biocon Limited | Pharmaceutical compositions of insulin drug-oligomer conjugates and methods of treating diseases therewith |
| AU2003236521A1 (en) | 2002-06-13 | 2003-12-31 | Nobex Corporation | Methods of reducing hypoglycemic episodes in the treatment of diabetes mellitus |
| US20060182692A1 (en) | 2003-12-16 | 2006-08-17 | Fishburn C S | Chemically modified small molecules |
| HRP20140361T1 (en) | 2003-12-16 | 2014-05-23 | Nektar Therapeutics | MONODISPERSE MIXTURES OF PEGYLED NALOXOL |
| JP6169255B2 (en) * | 2013-05-02 | 2017-07-26 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Polyaryl ether sulfone copolymer |
| KR20160003802A (en) * | 2013-05-02 | 2016-01-11 | 바스프 에스이 | Polyarylethersulfone copolymers |
| US9353220B2 (en) * | 2013-08-13 | 2016-05-31 | Fresenius Medical Care Holdings, Inc. | Process for making polyarylethers and use in membrane preparation |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5523574A (en) * | 1978-08-08 | 1980-02-20 | Fujitsu Ltd | Check system of optical mark reader |
| JPS62195020A (en) * | 1986-02-21 | 1987-08-27 | Daicel Chem Ind Ltd | Production of aromatic polyether |
| DE3636558A1 (en) * | 1986-10-28 | 1988-05-05 | Basf Ag | HIGH TEMPERATURE RESISTANT POLYETHER SULPHONE / POLYETHER KETONE BLOCK COPOLY CONDENSATES |
-
1988
- 1988-02-15 JP JP3252788A patent/JPH01207320A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01207320A (en) | 1989-08-21 |
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