JPH0368888B2 - - Google Patents

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Publication number
JPH0368888B2
JPH0368888B2 JP58028686A JP2868683A JPH0368888B2 JP H0368888 B2 JPH0368888 B2 JP H0368888B2 JP 58028686 A JP58028686 A JP 58028686A JP 2868683 A JP2868683 A JP 2868683A JP H0368888 B2 JPH0368888 B2 JP H0368888B2
Authority
JP
Japan
Prior art keywords
vinyl acetate
meth
mol
allyl ether
polyoxyalkylene
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
Application number
JP58028686A
Other languages
Japanese (ja)
Other versions
JPS59155411A (en
Inventor
Kiichi Maruhashi
Takeo Kawabata
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Synthetic Chemical Industry Co Ltd
Original Assignee
Nippon Synthetic Chemical Industry Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nippon Synthetic Chemical Industry Co Ltd filed Critical Nippon Synthetic Chemical Industry Co Ltd
Priority to JP58028686A priority Critical patent/JPS59155411A/en
Publication of JPS59155411A publication Critical patent/JPS59155411A/en
Publication of JPH0368888B2 publication Critical patent/JPH0368888B2/ja
Granted legal-status Critical Current

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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Description

【発明の詳細な説明】[Detailed description of the invention]

酢酸ビニル樹脂は本質的には水に不溶性の樹脂
であるが、これに少量のエチレン性不飽和カルボ
ン酸アルカリ塩やアンモニウム塩あるいはエチレ
ン性不飽和スルホン酸アルカリ塩等を共重合させ
ることにより、水溶性化が可能となつて糊剤、接
着剤、紙加工剤等への水系用途にも多用されてい
る。 しかし、かかる水溶性タイプの酢酸ビニル樹脂
の用途が拡大されるにつれ、様々な性能が要求さ
れる様になり例えばセラミツクスバインダー等の
用途では、微量のアルカリ金属の存在がセラミツ
クスの性能を劣化させる原因となるので、該用途
への使用が不可能になる等、従来の製品では到底
多岐にわたる性能要求に応じきれない事態となつ
ている。 しかるに、本発明者等はかかるアルカリ金属が
存在しなくても水溶性である酢酸ビニル樹脂を開
発すべく鋭意研究を重ねた結果、 一般式
Vinyl acetate resin is essentially a water-insoluble resin, but by copolymerizing it with a small amount of ethylenically unsaturated carboxylic acid alkali salt, ammonium salt, or ethylenically unsaturated sulfonic acid alkali salt, it can be made water-soluble. It is now widely used in water-based applications such as pastes, adhesives, and paper processing agents. However, as the uses of water-soluble vinyl acetate resin expand, various performances are required. For example, in applications such as ceramic binders, the presence of trace amounts of alkali metals causes deterioration of the performance of ceramics. Therefore, conventional products cannot meet the wide variety of performance requirements, such as making it impossible to use them for these purposes. However, as a result of extensive research to develop a vinyl acetate resin that is water-soluble even in the absence of such alkali metals, the present inventors found that the general formula

【式】 で示されるポリオキシアルキレン(メタ)アリル
エーテルと酢酸ビニルとを共重合する際に、ポリ
オキシアルキレン(メタ)アリルエーテルの含有
量を1〜30モル%とすることを特徴とするオキシ
アルキレン基を重合体側鎖に有する変性酢酸ビニ
ル樹脂がその目的を満足することを見出し本発明
を完成するに至つた。 本発明でいうオキシアルキレン基とは一般式
[Formula] When copolymerizing the polyoxyalkylene (meth)allyl ether represented by the formula and vinyl acetate, the content of the polyoxyalkylene (meth)allyl ether is 1 to 30 mol%. The present inventors have discovered that a modified vinyl acetate resin having an alkylene group in the polymer side chain satisfies the objective and has completed the present invention. The oxyalkylene group referred to in the present invention has the general formula

【式】〔但し、R1、R2は水素又は アルキル基、nは1〜100の整数を示す〕で表さ
れる構造を有するものである。nの数が有利には
1〜50、好ましくは3〜50程度のオキシアルキレ
ン基が実用的であり、ポリオキシエチレン基、ポ
リオキシプロピレン基、ポリオキシブチレン基等
が効果的である。又Rは水素又はメチル基であ
る。 一般式
It has a structure represented by the formula: [wherein R 1 and R 2 are hydrogen or an alkyl group, and n is an integer from 1 to 100]. Oxyalkylene groups in which n is advantageously 1 to 50, preferably about 3 to 50 are practical, and polyoxyethylene groups, polyoxypropylene groups, polyoxybutylene groups, etc. are effective. Further, R is hydrogen or a methyl group. general formula

【式】 で示される〔R、R1、R2、nは前記と同様〕ポ
リオキシアルキレン(メタ)アリルエーテルの具
体例としてはポリオキシエチレン(メタ)アリル
エーテル、ポリオキシプロピレン(メタ)アリル
エーテル等が挙げられる。 酢酸ビニルとの共重合に当たつて、特に制限は
なく公知の重合方法が任意に用いられるが普通メ
タノールあるいはエタノール等のアルコールを溶
媒とする溶液重合が実施される。かかる方法に於
いて単量体の仕込み方法としてまず酢酸ビニルの
全量と前記ポリオキシアルキレン(メタ)アリル
エーテルの一部を仕込み、重合を開始し、残りの
ポリオキシアルキレン(メタ)アリルエーテルを
重合期間中に連続的に又は分割的に添加する方
法、両者を一括仕込みする方法等任意の手段を用
いて良い。共重合反応は、アゾビスイソブチロニ
トリル、過酸化アセチル、過酸化ベンゾイル、過
酸化ラウロイルなどの公知のラジカル重合触媒を
用いて行われる。又反応温度は50℃〜沸点程度の
範囲から選択される。反応御は常法に従つて未反
応単量体を除去し目的物を得る。 本願において基本的にはポリオキシアルキレン
(メタ)アリルエーテルと酢酸ビニルとの二元共
重合体であるが、発明の趣旨を損なわない範囲で
これらと共重合可能なモノマーを少量共重合させ
ることも出来る。 本発明の酢酸ビニル樹脂中に占めるポリオキシ
アルキレン(メタ)アリルエーテルの割合は任意
に変動出来る。即ち、単に酢酸ビニル樹脂に水と
の親和性を付与するだけの目的であればその割合
は比較的少なくて良い、水溶性化まで目的とする
時はかなり多量の導入が必要である。水溶性を得
るために通常1モル%以上の導入が必要となる。
望ましい含有量は1〜30モル%、好ましくは1〜
20モル%である。 該酢酸ビニル樹脂は粉末、ブロツク、溶液いず
れの形態でも各種用途に使用出来る。 それらを次に具体的に挙げる。 (1) 成型物関係 繊維、フイルム、シート、パイプ、チユー
ブ、防漏膜、暫定皮膜、ケミカルレース用水溶
性繊維 (2) 接着剤関係 木材、紙、アルミ箔、プラスチツクス等の接
着剤、粘着剤、再湿剤、不織布用バインダー、
繊維状バインダー、石膏ボードや繊維板等の各
種建材用バインダー、各種粉体造粒用バインダ
ー、セラミツクスバインダー、セメントやモル
タル用添加剤、ホツトメルト型接着剤、感圧接
着剤、染料の固着剤 (3) 被覆剤関係 紙のクリアーコーテイング剤、紙の顔料コー
テイング剤、紙の内添サイズ剤、感熱記録紙用
バインダー及びオーバーコート剤、繊維製品用
サイズ剤、経紙糊剤、繊維加工剤、皮革仕上げ
剤、塗料、防曇剤、金属腐食防止剤、亜鉛メツ
キ用光沢剤、帯電防止剤、導電剤 (4) 疎水性樹脂用ブレンド剤関係 疎水性樹脂の帯電防止剤、及び親水性付与
剤、複合繊維、フイルムその他成型物用添加剤 (5) 懸濁用分散安定剤関係 塗料、墨汁、水彩カラー、接着剤等の顔料分
散安定剤、塩化ビニル、塩化ビニリデン、スチ
レン、(メタ)アクリレート、酢酸ビニル等の
各種ビニル化合物の懸濁重合用分散安定剤、及
び分散助剤 (6) 乳化剤関係 エチレン性不飽和化合物、ブタジエン性化合
物の乳化重合用乳化剤、ポリオレフイン、ポリ
エステル樹脂等疎水性樹脂、エポキシ樹脂、パ
ラフイン、ビチユウメン等の後乳化剤 (7) 増粘剤関係 各種エマルジヨンの増粘剤 (8) 凝集剤関係 水中懸濁物及び溶存物の凝集剤、パルプスラ
リーの水性向上剤 (9) 土壌改良剤関係 (10) 感光剤、感電子剤関係 次に実例を挙げて本発明の方法を更に詳しく説
明する。 実例 1 還流冷却器、滴下ロート、温度計、攪拌器を備
えた重合缶に酢酸ビニル900部、ポリオキシエチ
レンアリルエーテル(n=15)415部、メタノー
ル105部を仕込み攪拌しながら温度を上昇させ60
℃においてアゾビスイソブチロニトリル0.12部を
メタノール20部に溶解した溶液を投入して重合を
開始した。8時間後、重合率が96%になつた時点
で重合を停止した。共重合溶液を常法に従つて精
製しポリオキシエチレンモノアリルエーテル/酢
酸ビニル共重合体を得た。 得られた共重合体の特性値は次の通りであつ
た。 ポリオキシエチレンアリルエーテル含有量;
4.1モル% 酢酸ビニル含有量; 95.9モル% 20℃における4%水溶液粘度;1.2センチポイズ
(ヘプラー粘度計) NMR(δppm) 3.7δppmに−(CH2CH2O)−のピークが認められ
る。 実例 2 実例1におけるポリオキシエチレンアリルエー
テル(n=15)に代えてn=50のポリオキシエチ
レンアリルエーテル429部を用いた以外は同例と
同様の方法を行つた。 得られた共重合体の特性値は次の通りであつ
た。 ポリオキシエチレンモノアリルエーテル含有
量; 1.8モル% 酢酸ビニル含有量; 98.2モル% NMR(δppm)は実例1と同一 実例 3 実例1におけるポリオキシエチレンアリルエー
テルに代えてn=10のポリオキシプロピレンアリ
ルエーテルを用いた以外は同例に準じて実験を行
つた。 得られた共重合体の組成は次の通りであつた。 ポリオキシプロピレンアリルエーテル含有量;
3.8モル% 酢酸ビニル含有量; 96.2モル%
[Formula] [R, R 1 , R 2 , n are the same as above] Specific examples of polyoxyalkylene (meth)allyl ether include polyoxyethylene (meth)allyl ether, polyoxypropylene (meth)allyl Examples include ether. Copolymerization with vinyl acetate is not particularly limited and any known polymerization method may be used, but solution polymerization using an alcohol such as methanol or ethanol as a solvent is usually carried out. In this method, the monomers are charged by first charging the entire amount of vinyl acetate and a portion of the polyoxyalkylene (meth)allyl ether to start polymerization, and then polymerizing the remaining polyoxyalkylene (meth)allyl ether. Any method may be used, such as adding continuously or in parts during the period, or adding both at once. The copolymerization reaction is carried out using a known radical polymerization catalyst such as azobisisobutyronitrile, acetyl peroxide, benzoyl peroxide, and lauroyl peroxide. Further, the reaction temperature is selected from a range of about 50°C to the boiling point. The reaction is carried out by removing unreacted monomers in accordance with conventional methods to obtain the desired product. In this application, it is basically a binary copolymer of polyoxyalkylene (meth)allyl ether and vinyl acetate, but a small amount of monomers that can be copolymerized with these may be copolymerized without detracting from the spirit of the invention. I can do it. The proportion of polyoxyalkylene (meth)allyl ether in the vinyl acetate resin of the present invention can be varied arbitrarily. That is, if the purpose is simply to impart affinity with water to the vinyl acetate resin, the proportion may be relatively small, but if the purpose is to make the vinyl acetate resin water-soluble, it is necessary to introduce a considerably large amount. In order to obtain water solubility, it is usually necessary to introduce 1 mol% or more.
Desirable content is 1 to 30 mol%, preferably 1 to 30 mol%
It is 20 mol%. The vinyl acetate resin can be used for various purposes in the form of powder, block, or solution. These are listed below. (1) Molded products Fibers, films, sheets, pipes, tubes, leak-proof membranes, temporary coatings, water-soluble fibers for chemical laces (2) Adhesives Adhesives and adhesives for wood, paper, aluminum foil, plastics, etc. , rewetting agent, binder for nonwoven fabrics,
Fibrous binders, binders for various building materials such as gypsum board and fiberboard, binders for various powder granulation, ceramic binders, additives for cement and mortar, hot melt adhesives, pressure sensitive adhesives, dye fixing agents (3 ) Coating agent Clear coating agent for paper, pigment coating agent for paper, internal sizing agent for paper, binder and overcoating agent for thermal recording paper, sizing agent for textile products, paper sizing agent, fiber processing agent, leather finishing Agents, paints, antifogging agents, metal corrosion inhibitors, brighteners for galvanizing, antistatic agents, conductive agents (4) Blending agents for hydrophobic resins Antistatic agents for hydrophobic resins, hydrophilicity imparting agents, composites Additives for fibers, films, and other molded products (5) Dispersion stabilizers for suspension Pigment dispersion stabilizers for paints, India ink, watercolor colors, adhesives, etc., vinyl chloride, vinylidene chloride, styrene, (meth)acrylate, vinyl acetate Dispersion stabilizers and dispersion aids for suspension polymerization of various vinyl compounds such as (6) Emulsifiers Emulsifiers for emulsion polymerization of ethylenically unsaturated compounds and butadiene compounds, hydrophobic resins such as polyolefins and polyester resins, epoxy resins, Post-emulsifiers such as paraffin and bitumen (7) Thickeners Thickeners for various emulsions (8) Flocculants Flocculants for suspended and dissolved substances in water, aqueous improvers for pulp slurry (9) Soil conditioners (10) Related to photosensitive agent and electrosensitive agent Next, the method of the present invention will be explained in more detail by giving examples. Example 1 900 parts of vinyl acetate, 415 parts of polyoxyethylene allyl ether (n=15), and 105 parts of methanol were placed in a polymerization tank equipped with a reflux condenser, dropping funnel, thermometer, and stirrer, and the temperature was raised while stirring. 60
A solution prepared by dissolving 0.12 parts of azobisisobutyronitrile in 20 parts of methanol was added at 0.degree. C. to initiate polymerization. After 8 hours, the polymerization was stopped when the polymerization rate reached 96%. The copolymerization solution was purified according to a conventional method to obtain a polyoxyethylene monoallyl ether/vinyl acetate copolymer. The characteristic values of the obtained copolymer were as follows. Polyoxyethylene allyl ether content;
4.1 mol% Vinyl acetate content: 95.9 mol% 4% aqueous solution viscosity at 20°C: 1.2 centipoise (Hepler viscometer) NMR (δppm) A peak of −(CH 2 CH 2 O) − is observed at 3.7 δppm. Example 2 The same method as in Example 1 was carried out except that 429 parts of polyoxyethylene allyl ether (n=50) was used in place of the polyoxyethylene allyl ether (n=15) in Example 1. The characteristic values of the obtained copolymer were as follows. Polyoxyethylene monoallyl ether content: 1.8 mol% Vinyl acetate content: 98.2 mol% NMR (δppm) is the same as Example 1. Example 3 Polyoxypropylene allyl with n=10 was used instead of polyoxyethylene allyl ether in Example 1. The experiment was conducted in accordance with the same example except that ether was used. The composition of the obtained copolymer was as follows. Polyoxypropylene allyl ether content;
3.8 mol% Vinyl acetate content; 96.2 mol%

Claims (1)

【特許請求の範囲】 1 一般式
【式】 ここで〔Rは水素又はメチル基、R1及びR2
水素又はアルキル基、nは1〜100の整数で示さ
れるポリオキシアルキレン(メタ)アリルエーテ
ルと酢酸ビニルとをポリオキシアルキレン(メ
タ)アリルエーテルの含有量が1〜30モル%とな
る割合で共重合することを特徴とするオキシアル
キレン基を重合体側鎖に有する変性酢酸ビニル樹
脂の製造方法。
[Scope of Claims] 1 General Formula [Formula] Here, [R is hydrogen or a methyl group, R 1 and R 2 are hydrogen or an alkyl group, and n is a polyoxyalkylene (meth)allyl represented by an integer from 1 to 100. Production of a modified vinyl acetate resin having an oxyalkylene group in the polymer side chain, which is characterized by copolymerizing ether and vinyl acetate at a ratio such that the content of polyoxyalkylene (meth)allyl ether is 1 to 30 mol%. Method.
JP58028686A 1983-02-22 1983-02-22 Production of modified vinyl acetate resin Granted JPS59155411A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP58028686A JPS59155411A (en) 1983-02-22 1983-02-22 Production of modified vinyl acetate resin

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP58028686A JPS59155411A (en) 1983-02-22 1983-02-22 Production of modified vinyl acetate resin

Publications (2)

Publication Number Publication Date
JPS59155411A JPS59155411A (en) 1984-09-04
JPH0368888B2 true JPH0368888B2 (en) 1991-10-30

Family

ID=12255366

Family Applications (1)

Application Number Title Priority Date Filing Date
JP58028686A Granted JPS59155411A (en) 1983-02-22 1983-02-22 Production of modified vinyl acetate resin

Country Status (1)

Country Link
JP (1) JPS59155411A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011158521A1 (en) 2010-06-16 2011-12-22 三菱重工業株式会社 Combustion system

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2613198B2 (en) * 1986-10-15 1997-05-21 株式会社クラレ Melt molding material
JP3799136B2 (en) * 1997-06-11 2006-07-19 日本合成化学工業株式会社 Dispersion stabilizer
DE19939266B4 (en) * 1999-07-13 2006-11-09 Clariant Produkte (Deutschland) Gmbh Aqueous polymer dispersion, its preparation and use
JP5177925B2 (en) * 2001-09-21 2013-04-10 日本合成化学工業株式会社 Melt molded product
DE102006049381A1 (en) * 2006-10-19 2008-04-24 Süd-Chemie AG Amphiphilic graft polymers
JP6638930B2 (en) * 2015-05-08 2020-02-05 国立大学法人福井大学 Alkenyl ether-vinyl ester copolymer
CN114426621A (en) * 2020-10-14 2022-05-03 中国石油化工股份有限公司 Nonionic modified polyvinyl alcohol and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS49130486A (en) * 1973-04-03 1974-12-13
JPS5222086A (en) * 1975-08-08 1977-02-19 Hoechst Ag Preparation of systhetic resin dispersion
JPS53113885A (en) * 1977-03-15 1978-10-04 Japan Exlan Co Ltd Preparation of microemulsion
JPS5446239A (en) * 1977-08-29 1979-04-12 Nat Starch Chem Corp Copolymer latex binderrcontaining composition* and method of using it for making nonwoven material
JPS5767672A (en) * 1980-10-13 1982-04-24 Nippon Oil & Fats Co Ltd Antifouling coating
JPS5920377A (en) * 1982-07-27 1984-02-02 Nippon Shokubai Kagaku Kogyo Co Ltd Antifogging agent

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS49130486A (en) * 1973-04-03 1974-12-13
JPS5222086A (en) * 1975-08-08 1977-02-19 Hoechst Ag Preparation of systhetic resin dispersion
JPS53113885A (en) * 1977-03-15 1978-10-04 Japan Exlan Co Ltd Preparation of microemulsion
JPS5446239A (en) * 1977-08-29 1979-04-12 Nat Starch Chem Corp Copolymer latex binderrcontaining composition* and method of using it for making nonwoven material
JPS5767672A (en) * 1980-10-13 1982-04-24 Nippon Oil & Fats Co Ltd Antifouling coating
JPS5920377A (en) * 1982-07-27 1984-02-02 Nippon Shokubai Kagaku Kogyo Co Ltd Antifogging agent

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011158521A1 (en) 2010-06-16 2011-12-22 三菱重工業株式会社 Combustion system

Also Published As

Publication number Publication date
JPS59155411A (en) 1984-09-04

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