JP3096494B2 - Method for producing polyvinyl ether polymer and method for producing polyvinyl alcohol polymer - Google Patents
Method for producing polyvinyl ether polymer and method for producing polyvinyl alcohol polymerInfo
- Publication number
- JP3096494B2 JP3096494B2 JP03194720A JP19472091A JP3096494B2 JP 3096494 B2 JP3096494 B2 JP 3096494B2 JP 03194720 A JP03194720 A JP 03194720A JP 19472091 A JP19472091 A JP 19472091A JP 3096494 B2 JP3096494 B2 JP 3096494B2
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- Prior art keywords
- polymer
- polymerization
- ether
- based polymer
- polyvinyl alcohol
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Description
【０００１】[0001]
【産業上の利用分野】本発明は新規なポリビニルエ−テ
ル系重合体の製法及びその製法により得られるポリビニ
ルエ−テル系重合体を出発物質としたポリビニルアルコ
−ル系重合体の製法に関する。The present invention relates to a novel Poribinirue - polyvinyl obtained by the method and its manufacturing method of the ether-based polymer
The present invention relates to a method for producing a polyvinyl alcohol- based polymer using a ruther-based polymer as a starting material.
【０００２】[0002]
【従来の技術】近年、いわゆるリビングカチオン重合法
が見い出され、温和な条件下で単分散に近い各種ポリビ
ニルエ−テルが得られるようになってきた。東村等は、
特開昭６０−２２８５０９号においてＨＩ／Ｉ 2 系開始
剤によるアルケニルエ−テルのリビングカチオン重合を
開示し、特開昭６１−１０３６５４号，６２−２５７９
１０号，特開平１−１０８２０２号及び１−１０８２０
３号において有機アルミニウム化合物とエ−テルあるい
はエステルとの組合せによるアルケニルエ−テルのリビ
ングカチオン重合を開示している。これらの文献により
開示された重量平均重合度と数平均重合度との比が１．
２以下である従来のポリビニルエ−テル系重合体は、１
級あるいは２級ビニルエ−テル単位からなる重合体であ
り、３級ビニルエ−テルを構成単位とし、重量平均重合
度と数平均重合度との比が１．２以下であるポリビニル
エ−テル系重合体については知られていなかった。2. Description of the Related Art In recent years, a so-called living cationic polymerization method has been found, and various kinds of polyvinyl ethers which are close to monodisperse under mild conditions have been obtained. Higashimura, etc.
Arukenirue In JP 60-228509 by HI / I 2 based initiator - discloses living cationic polymerization of ether, JP 61-103654, 62-2579
No. 10, JP-A-1-108202 and 1-108820
No. 3 discloses living cationic polymerization of alkenyl ether by a combination of an organoaluminum compound and an ether or an ester. The ratio between the weight average degree of polymerization and the number average degree of polymerization disclosed in these documents is 1.
The conventional polyvinyl ether polymer having 2 or less is 1
A polymer comprising a tertiary vinyl ether as a constituent unit and a ratio of a weight average polymerization degree to a number average polymerization degree of 1.2 or less. It was not known about coalescence.
【０００３】ポリビニルエ−テル系重合体からポリビニ
ルアルコ−ル系重合体を得る方法としては、ポリマ−中
のエ−テル結合を定量的に切断できる３級ビニルエ−テ
ル単位、ベンジルビニルエ−テル単位あるいはトリアル
キルシリルビニルエ−テル単位を含有するポリビニルエ
−テル系重合体の側鎖の開裂による方法が知られてい
る。この方法の中で、ベンジルビニルエ−テルをリビン
グ重合することにより分子量分布の狭いポリベンジルビ
ニルエ−テル系重合体が得られることが知られており、
該ポリベンジルビニルエ−テル系重合体の側鎖を開裂す
ることにより分子量分布の狭いポリビニルアルコ−ル系
重合体が得られることが知られている。しかし、ベンジ
ルビニルエ−テルは重合条件に関わらずアイソタクチッ
ク構造に富む重合体しか得られず、該ポリマ−を原料と
してシンジオタクチック構造に富む単分散ポリビニルア
ルコ−ル系重合体を得ることは困難である。さらに、側
鎖のベンジルアルコキシ基が酸化されやすいことから、
側鎖を定量的に開裂することが困難であるという欠点が
ある。As a method for obtaining a polyvinyl alcohol-based polymer from a polyvinyl ether-based polymer, a tertiary vinyl ether unit capable of quantitatively cleaving an ether bond in a polymer, benzyl vinyl ether A method is known in which a side chain of a polyvinyl ether-based polymer containing a unit or a trialkylsilylvinyl ether unit is cleaved. In this method, it is known that a polybenzyl vinyl ether polymer having a narrow molecular weight distribution can be obtained by subjecting benzyl vinyl ether to living polymerization.
It is known that a polyvinyl alcohol-based polymer having a narrow molecular weight distribution can be obtained by cleaving the side chain of the polybenzyl vinyl ether-based polymer. However, benzyl vinyl ether can obtain only a polymer rich in isotactic structure irrespective of polymerization conditions, and a monodisperse polyvinyl alcohol-based polymer rich in syndiotactic structure can be obtained using the polymer as a raw material. It is difficult. Furthermore, since the side chain benzylalkoxy group is easily oxidized,
The disadvantage is that it is difficult to quantitatively cleave the side chains.
【０００４】一方、トリアルキルシリルビニルエ−テル
はリビングカチオン重合に対する反応性が低く、かつ副
反応の制御が困難であるため、ポリトリアルキルシリル
ビニルエ−テル系重合体を原料として高重合度の単分散
ポリビニルアルコ−ル系重合体を得るのは困難である。
このように、従来は重量平均重合度と数平均重合度との
比が１．２以下である単分散ポリビニルアルコ−ル系重
合体の製法として満足のいく方法は知られていなかっ
た。On the other hand, trialkylsilyl vinyl ether has low reactivity to living cationic polymerization and it is difficult to control side reactions. It is difficult to obtain a monodispersed polyvinyl alcohol-based polymer.
As described above, a satisfactory method has not heretofore been known as a method for producing a monodispersed polyvinyl alcohol-based polymer having a ratio of the weight average polymerization degree to the number average polymerization degree of 1.2 or less.
【０００５】[0005]
【発明が解決しようとする課題】本発明の主たる目的
は、３級ビニルエ−テル単位を含有し、重量平均重合度
と数平均重合度との比が１．２以下である新規なポリビ
ニルエ−テル系重合体の製法を提供することである。さ
らに本発明のもう一つの目的は、該製法により得られる
ポリビニルエ−テル系重合体を出発物質とした単分散ポ
リビニルアルコ−ル系重合体の製法を提供することであ
る。The main object of the present invention is to provide a novel polyvinyl ether containing a tertiary vinyl ether unit and having a ratio of the weight-average degree of polymerization to the number-average degree of polymerization of 1.2 or less. An object of the present invention is to provide a method for producing a terpolymer. Yet another object of the present invention is obtained by the production method <br/> Poribinirue - monodispersed ether polymer were used as a starting material of polyvinyl alcohol - is to provide a method of Le polymer.
【０００６】[0006]
【課題を解決するための手段】本発明によれば上記の主
たる目的は、第３級ビニルエーテルを、 Ｒ 1.5 ＡｌＸ
1.5 （ここで、Ｒは炭化水素基を表し、Ｘはハロゲン原
子を表す）で表される有機アルミニウム系触媒と塩基性
添加剤の存在下に、有機溶媒中で、２０℃以下の温度で
反応させることを特徴とする、下記の化２で表されるビ
ニルエ−テル単位を含有し、重量平均重合度と数平均重
合度との比が１．２以下であり、かつ数平均重合度が１
０以上であるポリビニルエ−テル系重合体の製法を提供
することによって達成される。According to the present invention, there is provided the above-mentioned main device.
The purpose is to replace tertiary vinyl ether with R 1.5 AlX
1.5 (where R represents a hydrocarbon group and X is a halogen atom
Organoaluminum-based catalyst represented by
In an organic solvent in the presence of additives at a temperature of not more than 20 ° C.
Characterized by reacting , containing a vinyl ether unit represented by the following chemical formula 2, the ratio between the weight average polymerization degree and the number average polymerization degree is 1.2 or less, and the number average polymerization degree is 1
This is achieved by providing a method for producing a polyvinyl ether polymer having a value of 0 or more.
【化２】 （式中、Ｒ 1 、Ｒ 2 及びＲ 3 はそれぞれ炭化水素基を表
す。）まず、本発明の製法により得られるポリビニルエ
−テル系重合体について述べる。上記化２における
Ｒ 1 、Ｒ 2 及びＲ 3 の具体例としては、メチル、エチル、
プロピル、ブチルなどの低級アルキル基；フェニルなど
のアリ−ル基；シクロヘキシルなどのシクロアルキル基
などの炭素数１〜１８の炭化水素基が挙げられる。本発
明の製法により得られるポリビニルエ−テル系重合体を
重量平均重合度と数平均重合度との比が１．２以下であ
るポリビニルアルコ−ル系重合体の原料として用いる場
合にはＲ 1 、Ｒ 2 及びＲ 3 がそれぞれメチル基であること
が好ましい。また、上記ポリビニルエ−テル系重合体の
重合度については特に制限はなく、ポリマ−が使用され
る用途によって適宜選択されるが、１０以上が好ましく
１０〜１０ 5 がより好ましい。本発明の製法により得ら
れるポリビニルエ−テル系重合体は、本発明の目的を損
なわない範囲内において上記の化２で表されるビニルエ
−テル単位以外の単位を含有することができる。これら
の単位の具体例としては、下記の化３で表わされるビニ
ルエ−テル単量体とカチオン共重合する単量体、例えば
化３に表わされるビニルエ−テル以外のビニルエ−テ
ル、スチレン及びその誘導体、イソブテン等が挙げられ
る。Embedded image (In the formula, R 1 , R 2 and R 3 each represent a hydrocarbon group.) First, the polyvinyl ether polymer obtained by the production method of the present invention will be described. In the above formula 2,
Specific examples of R 1 , R 2 and R 3 include methyl, ethyl,
Lower alkyl groups such as propyl and butyl; aryl groups such as phenyl; and C1-C18 hydrocarbon groups such as cycloalkyl groups such as cyclohexyl. When the polyvinyl ether-based polymer obtained by the production method of the present invention is used as a raw material for a polyvinyl alcohol-based polymer having a ratio of the weight average polymerization degree to the number average polymerization degree of 1.2 or less, R 1 , R 2 and R 3 are each preferably a methyl group. The degree of polymerization of the polyvinyl ether-based polymer is not particularly limited and is appropriately selected depending on the use in which the polymer is used, but is preferably 10 or more, more preferably 10 to 10 5 . Obtained by the process of the present invention .
The polyvinyl ether-based polymer may contain a unit other than the vinyl ether unit represented by Chemical Formula 2 as long as the object of the present invention is not impaired. Specific examples of these units include monomers that cationically copolymerize with the vinyl ether monomer represented by the following chemical formula 3, for example, vinyl ethers other than the vinyl ether represented by the chemical formula 3, styrene and derivatives thereof. And isobutene.
【化３】 （式中、Ｒ 1 、Ｒ 2 及びＲ 3 は上記の化２における場合と
同じ意味を有する。）Embedded image (In the formula, R 1 , R 2 and R 3 have the same meaning as in the above Chemical Formula 2. )
【０００７】上記ポリビニルエ−テル系重合体は、上述
のごとく従来公知のリビングカチオン重合手法によって
は得られない。本発明において、上記の化３で表される
ビニルエ−テル単量体のカチオン重合時の生長末端は、
１級あるいは２級ビニルエ−テルに比して活性が高く不
安定であることに着眼し、生長末端を安定化し副反応を
抑える重合条件を検討した結果初めて可能になったもの
である。すなわち、上記ポリビニルエ−テル系重合体
は、リビングカチオン重合において、開始剤系として従
来公知のリビングカチオン重合開始剤に比して酸性度の
低い有機アルミニウム系触媒であるＲ 1.5 ＡｌＸ 1.5 （こ
こで、Ｒはメチル、エチル、プロピルなどの炭化水素基
を表し、Ｘは塩素、臭素などのハロゲン原子を表す）を
用い、かつこれに従来公知のリビングカチオン重合手法
において使用される添加剤に比して塩基性の強いＴＨＦ
等の添加剤を組み合わせ、ヘキサンあるいはトルエン等
の有機溶媒中で、２０℃以下、好ましくは０℃以下の低
温で第３級ビニルエーテルを重合することにより得られ
る。As described above, the polyvinyl ether polymer cannot be obtained by a conventionally known living cationic polymerization technique. In the present invention, the growing terminal at the time of cationic polymerization of the vinyl ether monomer represented by the above formula 3 is
Focusing on the fact that the activity is high and unstable as compared with primary or secondary vinyl ethers, this was made possible for the first time by examining polymerization conditions for stabilizing the growth terminal and suppressing side reactions. That is, the above-mentioned polyvinyl ether-based polymer
Is an organoaluminum-based catalyst having a lower acidity than a conventionally known living cationic polymerization initiator, R 1.5 AlX 1.5 (where R is a methyl, ethyl, propyl, etc.) X represents a halogen atom such as chlorine or bromine), and is more basic in THF than an additive used in a conventionally known living cationic polymerization method.
And tertiary vinyl ether in an organic solvent such as hexane or toluene at a low temperature of 20 ° C. or lower, preferably 0 ° C. or lower.
【０００８】次に、本発明のポリビニルアルコ−ル系重
合体の製法について述べる。本発明のポリビニルアルコ
−ル系重合体の製法は、上記製法により得られたポリビ
ニルエ−テル系重合体を原料とし、該ポリビニルエ−テ
ル系重合体中のエ−テル結合を開裂させることを特徴と
する。ポリビニルエ−テル系重合体中のエ−テル結合の
切断方法については、臭化水素、塩化水素、フッ化水
素、トリフルオロ酢酸等の酸によって切断する方法が用
いられる。これらの酸の中でも臭化水素による開裂が、
ポリビニルエ−テル系重合体中のエ−テル結合を定量的
に切断でき、反応時間が短く、副反応が少ないため好ま
しい。臭化水素を用いる場合は、本発明のポリビニルエ
−テル系重合体を酸性ガスに対して不活性な溶剤、例え
ばトルエンあるいはクロロホルム等に溶解し、臭化水素
ガスをバブリングしてポリビニルエ−テル系重合体中の
エ−テル結合を開裂させる。副反応を抑制するため、反
応は室温以下、好ましくは０℃以下の低温で行い、反応
はできるだけ短時間の内に終了することが好ましく、通
常１０分から１時間の範囲である。エ−テル結合を切断
したことにより析出したポリビニルアルコ−ル系重合体
を濾別し、アルカリ中和した後メタノ−ルで洗浄するこ
とにより目的とする重量平均重合度と数平均重合度との
比が１．２以下であるポリビニルアルコ−ル系重合体が
得られる。Next, a method for producing the polyvinyl alcohol-based polymer of the present invention will be described. The method for producing the polyvinyl alcohol-based polymer of the present invention uses the polyvinyl ether-based polymer obtained by the above-described method as a raw material, and forms ether bonds in the polyvinyl ether-based polymer. It is characterized by being cleaved. Poribinirue - d in ether polymer - For cutting method of ether bond, use bromide, hydrogen chloride, hydrogen fluoride, a method of cutting by acid such as trifluoroacetic acid
Irare Ru. Among these acids, cleavage by hydrogen bromide
It is preferable because the ether bond in the polyvinyl ether-based polymer can be quantitatively cleaved, the reaction time is short, and there are few side reactions. When hydrogen bromide is used, the polyvinyl ether-based polymer of the present invention is dissolved in a solvent inert to an acid gas, for example, toluene or chloroform, and hydrogen bromide gas is bubbled to form a polyvinyl ether. Cleavage of the ether bond in the system polymer. In order to suppress a side reaction, the reaction is carried out at a low temperature of room temperature or less, preferably 0 ° C. or less, and the reaction is preferably completed within as short a time as possible, usually in the range of 10 minutes to 1 hour. The polyvinyl alcohol-based polymer precipitated by cleavage of the ether bond is separated by filtration, neutralized with alkali, and washed with methanol to obtain the desired weight average polymerization degree and number average polymerization degree. A polyvinyl alcohol-based polymer having a ratio of 1.2 or less is obtained.
【０００９】[0009]
【実施例】以下、実施例により本発明をさらに説明する
が、本発明は実施例によって何等限定されるものではな
い。 実施例１ 三方活栓をつけたガラス容器を準備し、窒素置換後、窒
素ガス雰囲気下で加圧しガラス容器内の吸着水を除い
た。容器内にｔ−ブチルビニルエ−テル（０．７６モ−
ラ−（以下Ｍと略記する））、ＴＨＦ（１．０Ｍ）、１
−ブトキシエチルアセテ−ト（４．０ミリモ−ラ−（以
下ｍＭと略記する））及びヘキサンを入れ、系内温度が
−２０℃に達したところでＥｔ 1.5 ＡｌＣｌ 1.5 （２０ｍ
Ｍ）のヘキサン溶液を加えて重合を開始した。５７時間
後０．２５重量％（以下ｗｔ％と略記する）のアンモニ
ア性メタノ−ルで重合を停止した。反応停止後、０．６
規定（以下Ｎと略記する）塩酸水溶液で洗浄し開始剤残
渣を除き、希水酸化ナトリウム水溶液で中和した後、反
応液を濃縮し減圧乾燥することによってポリマ−を回収
した。重合率は９６％であった。Ｓｉｚｅ ｅｘｃｌｕ
ｓｉｏｎ ｃｈｒｏｍａｔｏｇｒａｐｈｙ（以下ＳＥＣ
と略記する）により、クロロホルム中、４０℃で測定
し、標準ポリスチレン検量線により求めた数平均重合度
（以下Ｐｎと略記する）及び重量平均重合度と数平均重
合度との比（以下Ｐｗ／Ｐｎと略記する）はそれぞれ１
７１及び１．０８であった。EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited to the examples. Example 1 A glass container equipped with a three-way cock was prepared, and after replacement with nitrogen, pressure was applied in a nitrogen gas atmosphere to remove adsorbed water in the glass container. T-Butyl vinyl ether (0.76 m-
(Hereinafter abbreviated as M), THF (1.0 M), 1
-Butoxyethyl acetate (4.0 millimoles (hereinafter abbreviated as mM)) and hexane were added, and when the temperature in the system reached -20 ° C, Et 1.5 AlCl 1.5 (20 m
The polymerization was initiated by adding a hexane solution of M). After 57 hours, the polymerization was terminated with 0.25% by weight (hereinafter abbreviated as wt%) of ammoniacal methanol. After stopping the reaction, 0.6
After washing with a normal (hereinafter abbreviated as N) hydrochloric acid aqueous solution to remove the initiator residue and neutralizing with a dilute sodium hydroxide aqueous solution, the reaction solution was concentrated and dried under reduced pressure to recover a polymer. The conversion was 96%. Size exclu
sion chromatography (hereinafter SEC)
), Measured in chloroform at 40 ° C, and determined by a standard polystyrene calibration curve (hereinafter abbreviated as Pn) and the ratio between the weight average polymerization degree and the number average polymerization degree (hereinafter Pw / Pn) is 1
71 and 1.08.
【００１０】比較例１ 三方活栓をつけたガラス容器を準備し、窒素置換後、窒
素ガス雰囲気下で加圧しガラス容器内の吸着水を除い
た。容器内にｔ−ブチルビニルエ−テル（０．７６
Ｍ）、酢酸メチル（１．０Ｍ）、１−ブトキシエチルア
セテ−ト（４．０ｍＭ）及びヘキサンを入れ、系内温度
が０℃に達したところでＥｔＡｌＣｌ 2 （２０ｍＭ）の
ヘキサン溶液を加えて重合を開始した。０．２時間後
０．２５ｗｔ％のアンモニア性メタノ−ルで重合を停止
した。反応停止後、０．６Ｎ塩酸水溶液で洗浄し開始剤
残渣を除き、希水酸化ナトリウム水溶液で中和した後、
反応液を濃縮し減圧乾燥することによってポリマ−を回
収した。重合率は１００％であった。ＳＥＣにより、ク
ロロホルム中、４０℃で測定し、標準ポリスチレン検量
線により求めた数平均重合度（Ｐｎ）及び重量平均重合
度と数平均重合度との比（Ｐｗ／Ｐｎ）はそれぞれ８３
及び１．６３であった。Comparative Example 1 A glass container provided with a three-way cock was prepared, and after replacement with nitrogen, pressure was applied in a nitrogen gas atmosphere to remove adsorbed water in the glass container. T-Butyl vinyl ether (0.76
M), methyl acetate (1.0 M), 1-butoxyethyl acetate (4.0 mM) and hexane, and when the temperature in the system reached 0 ° C., a hexane solution of EtAlCl 2 (20 mM) was added to polymerize. Started. After 0.2 hours, the polymerization was stopped with 0.25% by weight of ammoniacal methanol. After the reaction was stopped, the residue was washed with a 0.6N aqueous hydrochloric acid solution to remove the initiator residue, and neutralized with a dilute aqueous sodium hydroxide solution.
The polymer was recovered by concentrating the reaction solution and drying it under reduced pressure. The polymerization rate was 100%. The number-average degree of polymerization (Pn) and the ratio of the weight-average degree of polymerization to the number-average degree of polymerization (Pw / Pn) measured by SEC at 40 ° C. in chloroform and determined by a standard polystyrene calibration curve are 83, respectively.
And 1.63.
【００１１】比較例２ 比較例１の重合条件に準じて、イソブチルビニルエ−テ
ルを重合した。重合開始７時間後の重合率は９６％であ
った。比較例１と同様に求めたＰｎ及びＰｗ／Ｐｎはそ
れぞれ１８０及び１．０３であった。Comparative Example 2 Isobutyl vinyl ether was polymerized under the polymerization conditions of Comparative Example 1. The polymerization rate after 7 hours from the start of the polymerization was 96%. Pn and Pw / Pn obtained in the same manner as in Comparative Example 1 were 180 and 1.03, respectively.
【００１２】比較例３ 比較例１の重合条件に準じて、ｓｅｃ−ブチルビニルエ
−テルを重合した。重合開始０．２時間後の重合率は１
００％であった。比較例１と同様に求めたＰｎ及びＰｗ
／Ｐｎはそれぞれ１８５及び１．１０であった。Comparative Example 3 According to the polymerization conditions of Comparative Example 1, sec-butyl vinyl ether was polymerized. A polymerization rate of 0.2 hours after the start of polymerization is 1
00%. Pn and Pw determined in the same manner as in Comparative Example 1.
/ Pn was 185 and 1.10.
【００１３】実施例２ 実施例１で得られたポリマ−１．０ｇをトルエン１００
ｍｌに溶解して０℃氷浴中で臭化水素ガスを吹き込みな
がら充分に撹拌した。反応を開始してから約３分後に生
成したポリビニルアルコ−ルが析出して系内が白濁し
た。さらに７分間臭化水素ガスを吹き込んだ後、沈澱し
たポリマ−を濾別しアンモニア性メタノ−ル及びメタノ
−ルにて中和した後、メタノ−ルによるソックスレ−洗
浄を実施しポリビニルアルコ−ルを得た。ＳＥＣによ
り、１，１，１，３，３，３−ヘキサフルオロ−２−プ
ロパノ−ル中、２５℃で測定して求めた重量平均重合度
と数平均重合度との比（Ｐｗ／Ｐｎ）は１．１０であっ
た。Example 2 1.0 g of the polymer obtained in Example 1 was mixed with 100 parts of toluene.
The mixture was dissolved in the resulting solution and stirred sufficiently while blowing hydrogen bromide gas in an ice bath at 0 ° C. About 3 minutes after the start of the reaction, the produced polyvinyl alcohol was precipitated and the inside of the system became cloudy. After blowing hydrogen bromide gas for further 7 minutes, the precipitated polymer was separated by filtration, neutralized with ammoniacal methanol and methanol, and then subjected to Soxhlet washing with methanol and polyvinyl alcohol. I got The ratio of the weight average degree of polymerization to the number average degree of polymerization (Pw / Pn) determined by measuring at 25 ° C. in 1,1,1,3,3,3-hexafluoro-2-propanol by SEC. Was 1.10.
【００１４】[0014]
【発明の効果】比較例１、２及び３に示すように、１級
あるいは２級ビニルエ−テル単位からなる単分散ポリビ
ニルエ−テル系重合体が得られる従来公知のリビングカ
チオン重合手法によっては、３級ビニルエ−テルを構成
単位とし、重量平均重合度と数平均重合度との比が１．
２以下であるポリビニルエ−テル系重合体を得ることは
できない。これに対して、本発明は実施例１に示すよう
に従来公知のリビングカチオン重合手法に比して開始剤
の酸性度を弱めるとともに添加塩基の塩基性を強くし、
重合温度を下げ副反応を抑えることによって初めて目的
とするポリマ−が得られることを見出したものである。
本発明によれば、比較的高重合度のポリマ−が得やす
く、重合条件によってポリマ−のタクチシチ−が制御可
能であり、かつポリマ−中のエ−テル結合を容易に切断
することが可能である等、単分散ポリビニルアルコ−ル
系重合体の原料として非常に有用なポリビニルエ−テル
系重合体を提供できる。本発明の製法により得られたポ
リビニルアルコ−ル系重合体は、従来のポリビニルアル
コ−ル系重合体に比して重合度の制御が非常に容易であ
り、かつ熱、光等の外部刺激に対する応答が鋭敏である
ことに特徴があり、従来のポリビニルアルコ−ル系重合
体の用途にはもちろん、本発明のポリビニルアルコ−ル
系重合体の特徴を活かした用途等に好適に用いられる。
これらの用途として、熱、光等の外部刺激応答性ポリマ
−あるいは刺激応答性ゲル状物の原料等が例示され、工
業的な価値が極めて高いものである。また本発明の製法
により得られたポリビニルアルコ−ル系重合体は重合度
の制御が容易であり、重合体の片末端、あるいは両末端
に官能基が容易に導入可能であるため、これを構成単位
として成るグラフト共重合体あるいはブロック共重合体
の出発物質として有用である。As shown in Comparative Examples 1, 2 and 3, depending on the conventionally known living cationic polymerization method capable of obtaining a monodispersed polyvinyl ether polymer comprising a primary or secondary vinyl ether unit, The tertiary vinyl ether is a constituent unit, and the ratio between the weight average degree of polymerization and the number average degree of polymerization is 1.
It is not possible to obtain a polyvinyl ether polymer having a molecular weight of 2 or less. On the other hand, the present invention weakens the acidity of the initiator and increases the basicity of the added base as compared with the conventionally known living cationic polymerization method as shown in Example 1,
Polymer to be first object by suppressing the side reactions reduce the polymerization temperature - in which has headings can be obtained.
According to the present invention, a polymer having a relatively high degree of polymerization can be easily obtained, the tacticity of the polymer can be controlled by the polymerization conditions, and the ether bond in the polymer can be easily cleaved. For example, it is possible to provide a very useful polyvinyl ether-based polymer as a raw material of a monodispersed polyvinyl alcohol-based polymer. The polyvinyl alcohol-based polymer obtained by the production method of the present invention is very easy to control the degree of polymerization as compared with the conventional polyvinyl alcohol-based polymer, and is resistant to external stimuli such as heat and light. It is characterized by its sharp response, and is suitably used not only for conventional polyvinyl alcohol-based polymers but also for applications utilizing the characteristics of the polyvinyl alcohol-based polymers of the present invention.
As these applications, heat, external stimulus responsive polymers such as light - there have is exemplified raw material stimuli responsive gel-like material, is very high industrial value. In addition, the polyvinyl alcohol-based polymer obtained by the production method of the present invention can easily control the degree of polymerization, and a functional group can be easily introduced into one end or both ends of the polymer. It is useful as a starting material for a graft copolymer or a block copolymer as a unit.
───────────────────────────────────────────────────── フロントページの続き 審査官 佐々木 秀次 (56)参考文献 特開 平１−108202（ＪＰ，Ａ) 特開 平１−234478（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C08F 16/18,116/18,216/18 C08F 4/52 C08F 8/12 C08F 16/06,116/06,216/06 ＣＡ（ＳＴＮ)──────────────────────────────────────────────────続 き Continued from the front page Examiner Hideji Sasaki (56) References JP-A-1-108202 (JP, A) JP-A-1-234478 (JP, A) (58) Fields investigated (Int. Cl. 7) , DB name) C08F 16 / 18,116 / 18,216 / 18 C08F 4/52 C08F 8/12 C08F 16 / 06,116 / 06,216 / 06 CA (STN)
Claims (2)
1.5 （ここで、Ｒは炭化水素基を表し、Ｘはハロゲン原
子を表す）で表される有機アルミニウム系触媒と塩基性
添加剤の存在下に、有機溶媒中で、２０℃以下の温度で
反応させることを特徴とする、下記の化１で表されるビ
ニルエ−テル単位を含有し、重量平均重合度と数平均重
合度との比が１．２以下であり、かつ数平均重合度が１
０以上であるポリビニルエ−テル系重合体の製法。 【化１】 （式中、Ｒ 1 、Ｒ 2 及びＲ 3 はそれぞれ炭化水素基を表
す。）1. A tertiary vinyl ether is represented by R 1.5 AlX
1.5 (where R represents a hydrocarbon group and X is a halogen atom
Organoaluminum-based catalyst represented by
In an organic solvent in the presence of additives at a temperature of not more than 20 ° C.
Characterized by reacting , containing a vinyl ether unit represented by the following chemical formula 1, the ratio of the weight average polymerization degree to the number average polymerization degree is 1.2 or less, and the number average polymerization degree is 1
A method for producing a polyvinyl ether polymer having a value of 0 or more. Embedded image (In the formula, R 1 , R 2 and R 3 each represent a hydrocarbon group.)
リビニルエ−テル系重合体を酸と反応させることを特徴
とする重量平均重合度と数平均重合度との比が１．２以
下であるポリビニルアルコ−ル系重合体の製法。2. The method according to claim 1 , wherein the reaction between the weight average polymerization degree and the number average polymerization degree is 1 wherein the polyvinyl ether-based polymer obtained by the production method according to claim 1 is reacted with an acid. 2. A method for producing a polyvinyl alcohol-based polymer of not more than 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03194720A JP3096494B2 (en) | 1991-04-15 | 1991-04-15 | Method for producing polyvinyl ether polymer and method for producing polyvinyl alcohol polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03194720A JP3096494B2 (en) | 1991-04-15 | 1991-04-15 | Method for producing polyvinyl ether polymer and method for producing polyvinyl alcohol polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04318004A JPH04318004A (en) | 1992-11-09 |
| JP3096494B2 true JP3096494B2 (en) | 2000-10-10 |
Family
ID=16329127
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03194720A Expired - Fee Related JP3096494B2 (en) | 1991-04-15 | 1991-04-15 | Method for producing polyvinyl ether polymer and method for producing polyvinyl alcohol polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3096494B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019003558A1 (en) | 2017-06-26 | 2019-01-03 | 丸善石油化学株式会社 | Protein adsorption preventing agent, protein adsorption preventing film, and medical tool using same |
| WO2022009968A1 (en) | 2020-07-09 | 2022-01-13 | 丸善石油化学株式会社 | Composition for cancer cell adhesion, filter for capturing cancer cells, and method for detecting cancer cells |
-
1991
- 1991-04-15 JP JP03194720A patent/JP3096494B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019003558A1 (en) | 2017-06-26 | 2019-01-03 | 丸善石油化学株式会社 | Protein adsorption preventing agent, protein adsorption preventing film, and medical tool using same |
| WO2022009968A1 (en) | 2020-07-09 | 2022-01-13 | 丸善石油化学株式会社 | Composition for cancer cell adhesion, filter for capturing cancer cells, and method for detecting cancer cells |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04318004A (en) | 1992-11-09 |
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