JPH0368888B2 - - Google Patents
Info
- 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
Links
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical class CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 19
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 claims description 17
- 229920005989 resin Polymers 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- -1 carboxylic acid alkali salt Chemical class 0.000 description 17
- 239000003795 chemical substances by application Substances 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 7
- 239000000123 paper Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 239000008394 flocculating agent Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical class C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011094 fiberboard Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000013055 pulp slurry Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Description
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)
【式】 ここで〔Rは水素又はメチル基、R1及びR2は
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.
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)
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)
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)
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 |
-
1983
- 1983-02-22 JP JP58028686A patent/JPS59155411A/en active Granted
Patent Citations (6)
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)
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 |
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JPS59155411A (en) | 1984-09-04 |
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