JPS6227407A - Production of alpha-methylstyrene copolymer - Google Patents
Production of alpha-methylstyrene copolymerInfo
- Publication number
- JPS6227407A JPS6227407A JP16669785A JP16669785A JPS6227407A JP S6227407 A JPS6227407 A JP S6227407A JP 16669785 A JP16669785 A JP 16669785A JP 16669785 A JP16669785 A JP 16669785A JP S6227407 A JPS6227407 A JP S6227407A
- Authority
- JP
- Japan
- Prior art keywords
- copolymer
- methylstyrene
- polymerization initiator
- carboxylic acid
- concentration
- 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
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- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はα−メチルスチレンの共重合体の製造方法に関
する。詳しくはセラミックバインダーなどとして好適な
分解性と相溶性に優れたα−メチルスチレンの共重合体
を製造する法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a copolymer of α-methylstyrene. Specifically, the present invention relates to a method for producing an α-methylstyrene copolymer having excellent decomposability and compatibility and suitable as a ceramic binder.
ことからセラミックのバインダー、光記録材料などに利
用することが期待されている。しかしながら、α−メチ
ルスチレンは天井温度が低(、高分子量体を得るために
は、低温アニオン重合を行う必要があるため、α−メチ
ルスチレンを主成分とする共1合体はほとんど知られて
いなかった。Therefore, it is expected to be used in ceramic binders, optical recording materials, etc. However, α-methylstyrene has a low ceiling temperature (in order to obtain a high molecular weight product, low-temperature anionic polymerization must be carried out, so comonomers containing α-methylstyrene as the main component are hardly known. Ta.
α−メチルスチレンの単独重合体は熱、光などによって
容易に分解し、単量体となる優れた重合体であるが、セ
ラミックのバインダーや光記録材料として用いようとす
ると、アルミナ、シリカ、シリコンカーバイト、シリコ
ンナイトライド、ボロンカーバイト、ボロンナイトライ
ドなどのセラミック粉となじみが悪く、バインダーとし
て不適であり、光記録材料としても基板に塗布して乾燥
した後基板とのなじみが悪く、はがれるなどという問題
があった。これに対しては、カルボン酸、カルボン酸ア
ミド、カルボン酸エステルなどの極性基を有する単量体
と共重合することが考えられるが、α−メチルスチレン
は上述のような重合特性を有するため他の極性基含有単
量体と共重合することが容易でな(、α−メチルスチレ
ンと極性基含有単量体を共重合した共重合体の開発が望
まれていた。α-Methylstyrene homopolymer is an excellent polymer that easily decomposes into monomers when exposed to heat, light, etc., but when it is used as a ceramic binder or optical recording material, alumina, silica, silicon It has poor compatibility with ceramic powders such as carbide, silicon nitride, boron carbide, and boron nitride, making it unsuitable as a binder, and also as an optical recording material.After being applied to a substrate and dried, it does not blend well with the substrate and peels off. There was such a problem. To deal with this, copolymerization with a monomer having a polar group such as carboxylic acid, carboxylic acid amide, or carboxylic acid ester may be considered, but since α-methylstyrene has the above-mentioned polymerization characteristics, other monomers may be used. Since it is difficult to copolymerize with a polar group-containing monomer, it has been desired to develop a copolymer in which α-methylstyrene and a polar group-containing monomer are copolymerized.
本発明者らは上記問題点を解決する方法について鋭意検
討し、本発明に到達した。The present inventors have conducted extensive studies on methods for solving the above problems, and have arrived at the present invention.
即ち、本発明は、α−メチルスチレンとジビニルベンゼ
ン及び/又はジイソプロペニルベンゼンとの木飽相基含
有共重合体と不飽和カルボン酸及び/又はその誘導体を
ラジカル重合開始剤の存在下に共重合することを特徴と
するα−メチルスチレンの共重合体の製造方法である。That is, the present invention co-produces a wood-saturated phase group-containing copolymer of α-methylstyrene, divinylbenzene and/or diisopropenylbenzene, and an unsaturated carboxylic acid and/or a derivative thereof in the presence of a radical polymerization initiator. This is a method for producing a copolymer of α-methylstyrene, which is characterized by polymerization.
本発明において用いる不飽和基含有共重合体はα−メチ
ルスチレンとジビニルベンゼン及び/又はジイソプロペ
ニルベンの共重合体である。この際α−メチルスチレン
の60重量%程度をスチレンやその誘導体を使用してい
てもかまわない。但し、303ii%を越えると分解性
が不良となるので好ましくない。The unsaturated group-containing copolymer used in the present invention is a copolymer of α-methylstyrene and divinylbenzene and/or diisopropenylben. In this case, about 60% by weight of α-methylstyrene may be styrene or its derivatives. However, if it exceeds 303ii%, decomposability becomes poor, which is not preferable.
α−メチルスチレンとジビニルベンゼン及び/又ハシイ
ソプロペニルベンゼンとの共重合体はラジカル重合法或
いはアニオン重合法で製造することが可能であり、α−
メチルスチレンとジビニルベンゼン及び/又はジイソプ
ロペニルベンゼンとの総和に対するジビニルベンゼン及
び/又はインプロペニルベンゼンの割合は2〜3ON量
%であるのが、共重合体の製造時の問題が少(、また次
の反応のためにも好ましい。A copolymer of α-methylstyrene and divinylbenzene and/or hashiisopropenylbenzene can be produced by a radical polymerization method or an anionic polymerization method.
The ratio of divinylbenzene and/or impropenylbenzene to the total of methylstyrene and divinylbenzene and/or diisopropenylbenzene is 2 to 3% ON, since problems during production of the copolymer are small (and Also preferred for the next reaction.
上記重合に際しては、過酸化物或いはアゾビスニトリル
などの公知のラジカル重合開始剤及び/又は、アルキル
リチウム、ナトリウムナフタレンなどの公知のアニオン
重合開始剤を用いることが可能であり、その重合条件に
格別の制限はないが、特開昭59−207905号など
に記載された方法を利用することもできる。In the above polymerization, it is possible to use a known radical polymerization initiator such as peroxide or azobisnitrile, and/or a known anionic polymerization initiator such as alkyllithium or sodium naphthalene, depending on the polymerization conditions. Although there is no limitation, the method described in Japanese Patent Application Laid-Open No. 59-207905 can also be used.
上述の方法で得られた共重合体は未反応の単量体から分
離され、ビニル基及び/又はインプロペニル基含有共重
合体(以下、重合体Aと略記する)が得られろ。これを
後述の反応に用いる。The copolymer obtained by the above method is separated from unreacted monomers to obtain a vinyl group- and/or impropenyl group-containing copolymer (hereinafter abbreviated as polymer A). This is used in the reaction described below.
本発明において用いられる不飽相カルボ/酸及び/又は
その誘導体としては、アクリル酸、メタアクリル酸、ア
クリル了ミド、N、 N−ジメチルアクリルアミド、メ
タクリルアミド、N、N−ジメチルメタ望クリルアミド
、アクリル酸エステル、メタアクリル酸エステル類があ
げられる。The unsaturated carboxylic acids and/or their derivatives used in the present invention include acrylic acid, methacrylic acid, acrylamide, N,N-dimethylacrylamide, methacrylamide, N,N-dimethylmethacrylamide, acrylic Examples include acid esters and methacrylic esters.
これらの不飽和カルボンは及び/又はその誘導体は、得
られるα−メチルスチレンの共重合体中で0,01〜6
0重量%となるように用いられる。0.01重量%未満
ではセラミック等とのなじみの改善がほとんどなされず
、又30MJi%を越えるとポリ−α−メチルスチレン
の特性が失なわれ好ましくない。These unsaturated carbons and/or derivatives thereof are present in the copolymer of α-methylstyrene obtained from 0,01 to 6
It is used so that it is 0% by weight. If it is less than 0.01% by weight, the compatibility with ceramics etc. will hardly be improved, and if it exceeds 30MJi%, the properties of poly-α-methylstyrene will be lost, which is not preferable.
上記重合体Aと不飽相カルボン酸及び/又はその誘導体
との共重合方法としては、ラジカル重合開始剤の存在下
に行われるかぎり特に制限はないが、通常1合体Aを溶
解した溶液にラジカル重合開始剤(前述のものが使用可
能である)と不飽相カルボン酸及び/又はその誘導体を
加え、ラジカ色靴
ル重合開始剤が作用する条件(加熱、光昭射など)に保
つことで行われる。この際、通常重合体への濃度は、5
〜6ON量%、不飽和カルボン酸及び/又はその誘導体
の濃度は[:1.05〜201量%、ラジカル重合開始
剤の濃度はo、ooi〜1゜重量%に保たれるのが好ま
しい。また反応温度としては一60°C〜150℃、好
ましくは000〜100°Cが適当である。The method of copolymerizing the above-mentioned polymer A with an unsaturated carboxylic acid and/or its derivative is not particularly limited as long as it is carried out in the presence of a radical polymerization initiator. It is carried out by adding a polymerization initiator (the ones mentioned above can be used) and an unsaturated phase carboxylic acid and/or its derivative, and maintaining the conditions (heating, light irradiation, etc.) under which the radical polymerization initiator acts. be exposed. At this time, the concentration to the polymer is usually 5
Preferably, the concentration of the unsaturated carboxylic acid and/or its derivative is maintained at 1.05 to 201% by weight, and the concentration of the radical polymerization initiator is maintained at 0, ooi to 1% by weight. The reaction temperature is suitably from -60°C to 150°C, preferably from 000°C to 100°C.
以下、実施例を挙げ、本発明をさらに説明する。 Hereinafter, the present invention will be further explained with reference to Examples.
なお、1合体の極限粘度数は30°トルエン溶液で測定
した。In addition, the intrinsic viscosity of one coalescence was measured using a 30° toluene solution.
実施例1
トルエンm媒中でα−メチルスチレン(10vot%)
とジビニルベンゼア (0,5voL%)をアニオン重
合開始剤ブチルリチウム(15wt%ヘキサン溶液、0
、15 vo1%)により−10℃で重合し、次いで大
量のメタノール中に投じて得たα−メチルスチレン−ジ
ビニルベンゼン共重合体(極限粘度数0.19、ジビニ
ルベンゼン5.2wt%含有)!Mをトルエン90m1
に浴解し、N、N−ジメチルアクリルアミド0.5−、
アクリル酸0.1ツおよび重合開始剤として過酸化ベン
ゾイル0.251を加え、80°Cで5時間反応した後
、多量のメタノール中に投じた。得られた重合体(共重
合体1)の極限粘度数0.21であり、元素分析及び赤
外吸収スペクトルより算出したN。Example 1 α-methylstyrene (10 vot%) in toluene medium
and divinylbenzea (0.5 vol%) in anionic polymerization initiator butyl lithium (15 wt% hexane solution, 0.5 wt% hexane solution,
An α-methylstyrene-divinylbenzene copolymer (intrinsic viscosity number 0.19, containing 5.2 wt% divinylbenzene) obtained by polymerizing at -10°C with 15 vol%) and then pouring into a large amount of methanol! M to toluene 90ml
N,N-dimethylacrylamide 0.5-,
After adding 0.1 part of acrylic acid and 0.251 part of benzoyl peroxide as a polymerization initiator and reacting at 80°C for 5 hours, the mixture was poured into a large amount of methanol. The intrinsic viscosity of the obtained polymer (copolymer 1) was 0.21, and N was calculated from elemental analysis and infrared absorption spectrum.
N−ジメチルアクリルアミド及びアクリル酸の含量はそ
れぞれ2.5wt%、[3,8wt%であった。The contents of N-dimethylacrylamide and acrylic acid were 2.5 wt% and 3.8 wt%, respectively.
実施例2
アクリルばにかえてヒドロキシエチルメタクリル酸エス
テルo、 i rntを用いる他は実施例1と同様にし
て重合体(共重合体2)を得た。得られた共重合体の極
限粘度数は0.20であり、N、 N−ジメチルアクリ
ルアミド及びヒドロキシエチルメタクリル酸エステルの
含量はそれぞれ2.4wt%、0.7wt%であった。Example 2 A polymer (copolymer 2) was obtained in the same manner as in Example 1, except that hydroxyethyl methacrylate o, i rnt was used instead of acrylic. The intrinsic viscosity of the obtained copolymer was 0.20, and the contents of N,N-dimethylacrylamide and hydroxyethyl methacrylate were 2.4 wt% and 0.7 wt%, respectively.
実施例3
トルエン溶媒中テα−メチルスチレン(20vat%)
、ジイソプロペニルベンゼン(1vot%)ラブチルリ
チウム(10wt%ヘキサン溶液、0.2vot%)に
より−10℃で0.5時間重合し、実施例1と同様に大
量のメタノール中に投じ分離した。得られた共重合体は
極限粘度数1.66、ジイソプロペニルベンゼン含量5
.7wt%であった。Example 3 α-methylstyrene (20vat%) in toluene solvent
, diisopropenylbenzene (1 vot%) and butyl lithium (10 wt% hexane solution, 0.2 vot%) were polymerized at -10°C for 0.5 hours, and the mixture was poured into a large amount of methanol and separated in the same manner as in Example 1. The obtained copolymer had an intrinsic viscosity of 1.66 and a diisopropenylbenzene content of 5.
.. It was 7wt%.
この共重合体102をジメチルホルムアミド100艷に
溶解し、アクリルアミド0.5Fおよびアゾビスイソブ
チロニトリル0.52を加え、70℃で10時間重合し
た。得られた共重合体3は元素分析よりアクリルアミド
を3wt%含しており、その極限粘度数は1.72であ
った。This copolymer 102 was dissolved in 100 g of dimethylformamide, 0.5 F of acrylamide and 0.52 F of azobisisobutyronitrile were added, and the mixture was polymerized at 70° C. for 10 hours. According to elemental analysis, the obtained copolymer 3 contained 3 wt% of acrylamide, and its intrinsic viscosity was 1.72.
以上の実施例1〜5で得られた共重合体1〜3、実施例
1および3で得たα−メチルスチレンとジヒニルヘンゼ
ンまたハシイソプロペニルベンゼンとの共重合体を用い
、各101を30m1のトルエンに溶解した溶液にアル
ミナ(粒径2μm)30Fを入れ混練して分散性を調べ
た。Using copolymers 1 to 3 obtained in Examples 1 to 5 above and copolymers of α-methylstyrene and dihinylhenzene or hashiisopropenylbenzene obtained in Examples 1 and 3, 101 of each was Alumina (particle size 2 μm) 30F was added to a solution dissolved in toluene and kneaded to examine dispersibility.
共重合体1〜3を用いたものでは、アルミナが均一に分
散したスラリーとなったが、不飽和カルボン酸及び/又
はその誘導体を共重合していない重合体を用いた場合に
はアルミナが均一に分散しなかった。When copolymers 1 to 3 were used, alumina was uniformly dispersed in the slurry, but when a polymer that was not copolymerized with unsaturated carboxylic acid and/or its derivative was used, alumina was uniformly dispersed. was not dispersed.
本発明の方法を実施することによりポリ−α−メチルス
チレン自身のものフ分解性を保持し、しかもセラミック
、基板などとのなじみのよいα−メチルスチレンの共重
合体を得ることが可能となり、工業的に極めて価値があ
る。By carrying out the method of the present invention, it is possible to obtain a copolymer of α-methylstyrene that maintains its own decomposability and is compatible with ceramics, substrates, etc. It is extremely valuable industrially.
Claims (1)
ジイソプロペニルベンゼンとの不飽和基含有共重合体と
不飽和カルボン酸及び/又はその誘導体をラジカル重合
開始剤の存在下に共重合することを特徴とするα−メチ
ルスチレンの共重合体の製造方法。1. Characterized by copolymerizing an unsaturated group-containing copolymer of α-methylstyrene and divinylbenzene and/or diisopropenylbenzene with an unsaturated carboxylic acid and/or its derivative in the presence of a radical polymerization initiator. A method for producing a copolymer of α-methylstyrene.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP60166697A JPH0617417B2 (en) | 1985-07-30 | 1985-07-30 | Method for producing α-methylstyrene copolymer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP60166697A JPH0617417B2 (en) | 1985-07-30 | 1985-07-30 | Method for producing α-methylstyrene copolymer |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6227407A true JPS6227407A (en) | 1987-02-05 |
JPH0617417B2 JPH0617417B2 (en) | 1994-03-09 |
Family
ID=15836065
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP60166697A Expired - Lifetime JPH0617417B2 (en) | 1985-07-30 | 1985-07-30 | Method for producing α-methylstyrene copolymer |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0617417B2 (en) |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5584303A (en) * | 1978-12-20 | 1980-06-25 | Asahi Chem Ind Co Ltd | Preparation of filler for chromatography |
JPS58201682A (en) * | 1982-05-20 | 1983-11-24 | Matsushita Electric Ind Co Ltd | Optical printer |
JPS5966406A (en) * | 1982-10-07 | 1984-04-14 | Sumitomo Chem Co Ltd | Preparation of fine particulate polymer |
JPS59128512A (en) * | 1983-01-12 | 1984-07-24 | Matsushita Electric Ind Co Ltd | Light printer |
JPS6083865A (en) * | 1983-10-14 | 1985-05-13 | Matsushita Electric Ind Co Ltd | Optical printer |
JPS60166696A (en) * | 1984-02-08 | 1985-08-29 | Asahi Chem Ind Co Ltd | Dna of novel physiologically active polypeptide |
-
1985
- 1985-07-30 JP JP60166697A patent/JPH0617417B2/en not_active Expired - Lifetime
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5584303A (en) * | 1978-12-20 | 1980-06-25 | Asahi Chem Ind Co Ltd | Preparation of filler for chromatography |
JPS58201682A (en) * | 1982-05-20 | 1983-11-24 | Matsushita Electric Ind Co Ltd | Optical printer |
JPS5966406A (en) * | 1982-10-07 | 1984-04-14 | Sumitomo Chem Co Ltd | Preparation of fine particulate polymer |
JPS59128512A (en) * | 1983-01-12 | 1984-07-24 | Matsushita Electric Ind Co Ltd | Light printer |
JPS6083865A (en) * | 1983-10-14 | 1985-05-13 | Matsushita Electric Ind Co Ltd | Optical printer |
JPS60166696A (en) * | 1984-02-08 | 1985-08-29 | Asahi Chem Ind Co Ltd | Dna of novel physiologically active polypeptide |
Also Published As
Publication number | Publication date |
---|---|
JPH0617417B2 (en) | 1994-03-09 |
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