JPH07165806A - Emulsifying agent for emulsion polymerization - Google Patents
Emulsifying agent for emulsion polymerizationInfo
- Publication number
- JPH07165806A JPH07165806A JP6210055A JP21005594A JPH07165806A JP H07165806 A JPH07165806 A JP H07165806A JP 6210055 A JP6210055 A JP 6210055A JP 21005594 A JP21005594 A JP 21005594A JP H07165806 A JPH07165806 A JP H07165806A
- Authority
- JP
- Japan
- Prior art keywords
- emulsion
- polymerization
- emulsion polymerization
- emulsifier
- acid
- 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
Landscapes
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、乳化重合用乳化剤に関
する。FIELD OF THE INVENTION The present invention relates to an emulsifier for emulsion polymerization.
【0002】[0002]
【従来の技術】通常、乳化重合では、乳化剤としてアル
キル硫酸塩、アルキルベンゼン硫酸塩、ポリオキシエチ
レンアルキルエーテル硫酸塩等のアニオン界面活性剤や
ポリオキシエチレンアルキルエーテル、ポリオキシエチ
レンアルキルフェニルエーテル、ポリオキシエチレン脂
肪酸エステル、プルロニック型界面活性剤等の非イオン
性界面活性剤が使用されている。2. Description of the Related Art Generally, in emulsion polymerization, anionic surfactants such as alkyl sulfates, alkylbenzene sulfates, polyoxyethylene alkyl ether sulfates, etc., as an emulsifier, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene Nonionic surfactants such as ethylene fatty acid ester and Pluronic type surfactant are used.
【0003】乳化重合用乳化剤は重合の開始反応や生成
反応に関与するだけでなく、生成したエマルジョンの機
械的安定性、化学的安定性、凍結安定性及び貯蔵安定性
にも関与し、さらにエマルジョンの粒子径、粘性及び起
泡性等のエマルジョン物性、フィルム化したときの耐水
性、耐候性、接着性、耐熱性等のフィルム物性にも大き
な影響を及ぼすことが知られている。The emulsifier for emulsion polymerization is involved not only in the initiation reaction and the formation reaction of the polymerization but also in the mechanical stability, the chemical stability, the freezing stability and the storage stability of the produced emulsion. It is known that the physical properties of the emulsion such as the particle size, viscosity, and foaming property, and the film physical properties such as water resistance when formed into a film, weather resistance, adhesiveness, and heat resistance are greatly affected.
【0004】[0004]
【発明が解決しようとする課題】しかし、通常の乳化剤
を使用して乳化重合したエマルジョンには乳化剤に起因
するエマルジョンの泡立が高くなること、またエマルジ
ョンからフィルムにした場合に乳化剤が遊離の状態でフ
ィルム中に残るため、接着性、耐水性、耐候性、耐熱性
等のフィルム物性の低下などの問題点が指摘されてい
る。However, an emulsion obtained by emulsion polymerization using an ordinary emulsifier has high foaming of the emulsion due to the emulsifier, and when the emulsion is formed into a film, the emulsifier is in a free state. Since it remains in the film, problems such as deterioration of film physical properties such as adhesiveness, water resistance, weather resistance and heat resistance have been pointed out.
【0005】従って、本発明の目的は上記の如き欠点が
なく、重合に際して乳化剤として働くと同時にモノマー
として重合体に取り込まれる乳化重合用乳化剤を提供す
ることにある。Therefore, an object of the present invention is to provide an emulsifier for emulsion polymerization which does not have the above-mentioned drawbacks and acts as an emulsifier during the polymerization and is incorporated into the polymer as a monomer.
【0006】[0006]
【課題を解決するための手段】即ち、本発明は、一般式That is, the present invention has the general formula
【化2】 (式中、Aは炭素原子数2〜4のアルキレン基であり、
Rは炭素原子数8〜24の炭化水素基またはアシル基で
あり、mは0〜50の数であり、M1及びM2は水素原
子、アルカリ金属、アルカリ土類金属、アンモニウムま
たは炭素原子数1〜4のヒドロキシアルキルアンモニウ
ムであり、M1及びM2は異なるものであっても、同一の
ものであってもよい)で表される、分子内にラジカル重
合可能な二重結合をもつ乳化重合用乳化剤に係る。[Chemical 2] (In the formula, A is an alkylene group having 2 to 4 carbon atoms,
R is a hydrocarbon group having 8 to 24 carbon atoms or an acyl group, m is a number of 0 to 50, and M 1 and M 2 are hydrogen atoms, alkali metals, alkaline earth metals, ammonium or the number of carbon atoms. 1 to 4 hydroxyalkylammonium, and M 1 and M 2 may be different or the same) and emulsified with a radically polymerizable double bond in the molecule It relates to emulsifiers for polymerization.
【0007】[0007]
【作用】本発明の乳化重合用乳化剤は分子内にラジカル
重合可能な二重結合をもち、重合時に乳化剤として働く
だけではなく、モノマーとしてポリマーと化学結合を形
成することを特徴とするものである。The emulsifier for emulsion polymerization of the present invention is characterized in that it has a double bond capable of radical polymerization in the molecule and not only acts as an emulsifier during polymerization but also forms a chemical bond with the polymer as a monomer. .
【0008】本発明の乳化重合用乳化剤は例えば以下の
ようにして製造できる。即ち、アリルグリシジルエーテ
ルと、一般式HO−(AO)m−R(2)(式中、Rは炭素原
子数8〜24の炭化水素基またはアシル基であり、Aは
炭化原子数2〜4のアルキレン基で、mは0〜50、好
ましくは0〜20の数である)で表されるヒドロキシル
化合物を、第3級アミン、第4級アンモニウム塩、三フ
ッ化ホウ素エーテル錯塩、ホウフッ化亜鉛、四塩化錫、
塩化アルミナウム、水酸化ナトリウム、水酸化カリウム
等の公知の触媒の存在下、50℃〜160℃で3時間〜
20時間エポキシ基がなくなるまで反応させ、一般式The emulsifying agent for emulsion polymerization of the present invention can be produced, for example, as follows. That is, allyl glycidyl ether and the general formula HO- (AO) m -R (2) (wherein R is a hydrocarbon group having 8 to 24 carbon atoms or an acyl group, and A is 2 to 4 carbon atoms). Is a alkylene group, m is a number of 0 to 50, preferably 0 to 20), a tertiary amine, a quaternary ammonium salt, a boron trifluoride ether complex salt, zinc borofluoride , Tin tetrachloride,
In the presence of a known catalyst such as alumina chloride, sodium hydroxide, potassium hydroxide, etc., at 50 ° C to 160 ° C for 3 hours-
React for 20 hours until the epoxy group disappears
【化3】 (式中、A、R及びmは上述と同意義をもつ)の化合物を
得る。[Chemical 3] (Wherein A, R and m have the same meanings as described above).
【0009】一般式(2)、(3)中のRで示される部分に
対応するヒドロキシル化合物または酸としては、例えば
オクタノール、ノナノール、デカノール、ウンデカノー
ル、ラウリルアルコール、ミリスチルアルコール、セチ
ルアルコール、ステアリルアルコール、オレイルアルコ
ール、エイコサノール等の天然または合成アルコール、
オクチルフェノール、ノニルフェノール、ジノニルフェ
ノール等のアルキルフェノール、更にカプリル酸、ペラ
ルゴン酸、カプリン酸、ウンデカン酸、ラウリン酸、ミ
リスチン酸、パルミチン酸、ステアリン酸、オレイン
酸、リノール酸、アラキン酸等の酸(または酸ハロゲン
化物、酸無水物等の反応性誘導体)が挙げられる。As the hydroxyl compound or acid corresponding to the moiety represented by R in the general formulas (2) and (3), for example, octanol, nonanol, decanol, undecanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, Natural or synthetic alcohols such as oleyl alcohol and eicosanol,
Alkylphenols such as octylphenol, nonylphenol, dinonylphenol, and further acids (or acid halogens such as caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, arachidic acid) Compounds, reactive derivatives such as acid anhydrides).
【0010】一般式(1)で示される化合物を製造する例
としては一般式(3)の化合物を五酸化リン、ポリリン酸
等を用い、公知の方法でリン酸エステル化して得る方法
等がある。As an example of producing the compound represented by the general formula (1), there is a method in which the compound represented by the general formula (3) is phosphorylated by a known method using phosphorus pentoxide, polyphosphoric acid and the like. .
【0011】尚、上記式(1)中のM1及びM2として好ま
しいものはアルカリ金属、アンモニウムであり、更に好
ましくはナトリウムである。Preferred as M 1 and M 2 in the above formula (1) are alkali metal and ammonium, and more preferred is sodium.
【0012】本発明の乳化重合用乳化剤を使用して乳化
重合することができるエチレン性不飽和モノマーには酢
酸ビニル等のビニルエステルモノマー、アクリル酸、ア
クリル酸メチル、メタクリル酸メチル、アクリロニトリ
ル、アクリルアミド等のアクリル系モノマー、スチレン
等の芳香族系モノマー、エチレン、ブタジエン、クロロ
プレン等のオレフィン系モノマー、塩化ビニル、塩化ビ
ニリデン等のハロゲン含有モノマー等のモノマーを挙げ
ることができるが、使用されるモノマーは上記例には特
に限定されるものではなく、また、ポリマー物性の改善
のために公知の架橋性モノマーを任意に使用することが
できる。The ethylenically unsaturated monomers which can be emulsion polymerized by using the emulsifier for emulsion polymerization of the present invention include vinyl ester monomers such as vinyl acetate, acrylic acid, methyl acrylate, methyl methacrylate, acrylonitrile and acrylamide. The acrylic monomers, aromatic monomers such as styrene, olefinic monomers such as ethylene, butadiene and chloroprene, and halogen-containing monomers such as vinyl chloride and vinylidene chloride can be used. The examples are not particularly limited, and known crosslinkable monomers can be optionally used to improve the physical properties of the polymer.
【0013】本発明の乳化重合用乳化剤を使用して乳化
重合を行う場合の反応温度は0〜100℃であり、不活
性ガス中で重合開始剤と重合調節剤を加えて反応させる
ことができる。When emulsion polymerization is carried out using the emulsifier for emulsion polymerization of the present invention, the reaction temperature is 0 to 100 ° C., and a polymerization initiator and a polymerization regulator can be added and reacted in an inert gas. .
【0014】重合開始剤としては過酸化水素、過硫酸カ
リウム、過硫酸アンモニウム等の水溶性無機系過酸化
物、アゾビスイソブチロニトリル等のアゾ化合物、ベン
ゾイルペルオキシド、過酢酸等の有機過酸化物など公知
の開始剤が使用でき、これらと亜硫酸水素ナトリウム、
チオ硫酸ナトリウム、硫酸第1鉄等の還元性物質を使用
しレドックス重合を行ってもよい。As the polymerization initiator, water-soluble inorganic peroxides such as hydrogen peroxide, potassium persulfate and ammonium persulfate, azo compounds such as azobisisobutyronitrile, organic peroxides such as benzoyl peroxide and peracetic acid. Known initiators can be used, such as sodium bisulfite,
Redox polymerization may be carried out using a reducing substance such as sodium thiosulfate or ferrous sulfate.
【0015】重合調節剤の使用は任意であるが、使用す
る場合にはメルカプタン類、ハロゲン化物等の公知の調
節剤を用いることができる。The use of the polymerization regulator is optional, but when it is used, known regulators such as mercaptans and halides can be used.
【0016】本発明の乳化重合用乳化剤を使用して乳化
重合を行なう場合の使用量は重合体の種類、モノマーの
組成によって変えることができるが、通常0.1〜20
重量%(対樹脂エマルジョン固形分)の範囲である。ま
た、本発明の目的の範囲内で通常のアニオン、ノニオン
系の界面活性剤を併用することも可能である。The amount used when emulsion polymerization is carried out using the emulsifier for emulsion polymerization of the present invention can be varied depending on the type of polymer and the composition of the monomer, but is usually 0.1 to 20.
It is in the range of% by weight (based on solid content of resin emulsion). Further, within the scope of the object of the present invention, it is also possible to use ordinary anionic and nonionic surfactants in combination.
【0017】[0017]
【実施例】以下に実施例を挙げ、本発明を更に説明する
が、本発明は以下の実施例に限定されるものではない。 実施例1 1リットルガラス製4つ口フラスコにノニルフェノー
ル440g、NaOH4.4gを仕込み、105±5
℃、10mmHg以下の減圧下で30分間脱水を行っ
た。窒素で常圧に戻し、90℃に冷却し、滴下ロートを
用いてアリルグリシジルエーテル228gを滴下した。
滴下後90±5℃で5時間熟成した。 で得られた生成物200gを500mlのガラス製
4つ口フラスコに入れ、40℃にて五酸化リン35gを
投入した。投入後、60℃に加熱して2時間反応を行
い、更に80℃にて2時間熟成した。その後、水酸化ナ
トリウム水溶液で中和し、ソーダ塩として生成物を得
た。The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples. Example 1 A 1 liter glass four-necked flask was charged with 440 g of nonylphenol and 4.4 g of NaOH and charged to 105 ± 5.
Dehydration was carried out for 30 minutes at a temperature of 10 ° C. and a reduced pressure of 10 mmHg or less. The pressure was returned to normal pressure with nitrogen, the temperature was cooled to 90 ° C., and 228 g of allyl glycidyl ether was added dropwise using a dropping funnel.
After dropping, the mixture was aged at 90 ± 5 ° C for 5 hours. 200 g of the product obtained in 1. was placed in a 500 ml four-neck glass flask, and 35 g of phosphorus pentoxide was added at 40 ° C. After charging, the mixture was heated to 60 ° C., reacted for 2 hours, and further aged at 80 ° C. for 2 hours. Then, it neutralized with sodium hydroxide aqueous solution and obtained the product as a soda salt.
【0018】実施例2 ノニルフェノールの代わりにドバノール23(三菱油
化製、炭素数12、13の混合アルコール、平均分子量
195)を用いて実施例1のと同様の反応を行った。 で得られた生成物200gを500mlのガラス製
4つ口フラスコに入れ、40℃にて五酸化リン37gを
投入した。投入後、60℃に加熱して2時間反応を行
い、更に80℃にて2時間熟成した。その後、水酸化ナ
トリウム水溶液で中和し、ソーダ塩として生成物を得
た。Example 2 The same reaction as in Example 1 was carried out using dovanol 23 (manufactured by Mitsubishi Petrochemical Co., Ltd., mixed alcohol having 12 and 13 carbon atoms, average molecular weight 195) instead of nonylphenol. 200 g of the product obtained in 1. was placed in a 500 ml glass four-necked flask, and 37 g of phosphorus pentoxide was added at 40 ° C. After the addition, the mixture was heated to 60 ° C., reacted for 2 hours, and further aged at 80 ° C. for 2 hours. Then, it neutralized with sodium hydroxide aqueous solution and obtained the product as a soda salt.
【0019】実施例3 アンモニア水溶液を用いて中和した他は実施例2と同様
にして生成物を得た。Example 3 A product was obtained in the same manner as in Example 2, except that the aqueous solution was neutralized.
【0020】実施例4 水酸化カリウム水溶液を用いて中和した他は実施例2と
同様にして生成物を得た。Example 4 A product was obtained in the same manner as in Example 2, except that the aqueous solution of potassium hydroxide was used for neutralization.
【0021】実施例5 ノニルフェノールの代わりにノニルフェノールのエチレ
ンオキサイド30モル付加物を用いて実施例1と同様の
反応を行い生成物を得た。Example 5 A product was obtained by the same reaction as in Example 1 except that 30 mol of ethylene oxide adduct of nonylphenol was used in place of nonylphenol.
【0022】実施例6 1リットルガラス製4つ口フラスコにラウリン酸40
0g、NaOH4.4gを仕込み、105±5℃、10
mmHg以下の減圧下で30分間脱水を行った。窒素で
常圧に戻し、90℃に冷却し、滴下ロートを用いてアリ
ルグリシジルエーテル228gを滴下した。滴下後90
±5℃で5時間熟成した。 で得られた生成物200gを500mlのガラス製
4つ口フラスコに入れ、40℃にて五酸化リン40gを
投入した。投入後、60℃に加熱して2時間反応を行
い、更に80℃にて2時間熟成した。その後、水酸化ナ
トリウム水溶液で中和し、ソーダ塩として生成物を得
た。EXAMPLE 6 Lauric acid 40 was added to a 1 liter glass four-necked flask.
Charge 0 g and NaOH 4.4 g, 105 ± 5 ℃, 10
Dehydration was performed for 30 minutes under a reduced pressure of mmHg or less. The pressure was returned to normal pressure with nitrogen, the temperature was cooled to 90 ° C., and 228 g of allyl glycidyl ether was added dropwise using a dropping funnel. 90 after dropping
It was aged at ± 5 ° C for 5 hours. 200 g of the product obtained in 1. was placed in a 500 ml glass four-necked flask, and 40 g of phosphorus pentoxide was added at 40 ° C. After the addition, the mixture was heated to 60 ° C., reacted for 2 hours, and further aged at 80 ° C. for 2 hours. Then, it neutralized with sodium hydroxide aqueous solution and obtained the product as a soda salt.
【0023】比較例1 ノニルフェノールのエチレンオキサイド40モル付加物 比較例2 アルキルベンゼンスルホン酸ソーダComparative Example 1 Ethylene oxide 40 mol adduct of nonylphenol Comparative Example 2 Sodium alkylbenzene sulfonate
【0024】参考例1(乳化重合用乳化剤使用例) 実施例1〜6で得られた化合物及び比較例1〜2の化合
物を用いて、アクリル酸エチルをモノマーとして乳化重
合反応を行なった。得られた重合体エマルジョンについ
て、その固形分、機械安定性、発泡性及び重合体エマル
ジョンから得られるポリマーフィルムについて耐水性を
測定した。その結果を表1に示す。Reference Example 1 (Example of Using Emulsifier for Emulsion Polymerization) Using the compounds obtained in Examples 1 to 6 and the compounds of Comparative Examples 1 to 2, an emulsion polymerization reaction was carried out using ethyl acrylate as a monomer. With respect to the obtained polymer emulsion, the solid content, mechanical stability, foamability and water resistance of the polymer film obtained from the polymer emulsion were measured. The results are shown in Table 1.
【0025】重合方法 還流冷却器、撹拌器、滴下ロート及び温度計を備えた反
応容器に水120gを仕込み、系内を窒素ガスで置換し
た。別にアクリル酸エチル80gに乳化重合用乳化剤4
gを溶解し、このうちの8.4gと過硫酸カリウム0.0
8g、亜硫酸水素ナトリウム0.04gを反応容器に加
え、50℃で重合を開始した。そして残りのモノマー・
乳化重合用乳化剤混合物を2時間にわたって反応器内に
連続的に滴下し、滴下終了後2時間熟成しエマルジョン
を得た。Polymerization method 120 g of water was charged into a reaction vessel equipped with a reflux condenser, a stirrer, a dropping funnel and a thermometer, and the system was replaced with nitrogen gas. Separately, emulsifier for emulsion polymerization 4 in 80 g of ethyl acrylate
g was dissolved, and 8.4 g of this was dissolved and potassium persulfate 0.0
8 g and 0.04 g of sodium hydrogen sulfite were added to the reaction vessel, and polymerization was started at 50 ° C. And the remaining monomers
The emulsifier mixture for emulsion polymerization was continuously added dropwise to the reactor over 2 hours, and after completion of the addition, the mixture was aged for 2 hours to obtain an emulsion.
【0026】測定・評価方法 (固形分)エマルジョン約1gを精秤し、105±5℃で
2時間乾燥した後の乾燥重量を測定して重量%で表す。 (機械安定性)エマルジョン50gをマロン法安定度試験
器で10kg、1000rpmの条件で5分間回転さ
せ、生成した凝塊物を100メッシュの金網でろ過し、
ろ過残渣を水で洗浄後、105℃で2時間乾燥し、この
重量を固形分に対する重量%で表す。 (発泡性)エマルジョンを水で2倍に希釈し、この希釈エ
マルジョン20mlを100mlの目盛り付試験管に入
れ、10秒間上下に強振したときの泡高を測定してml
で表示する。 (フィルムの耐水性)0.2mmのポリマーフィルムの水
浸漬法による白化に要する時間により、◎:1日以上、
○:1時間以上、×:1時間未満という基準で評価す
る。Measurement / Evaluation Method (solid content) About 1 g of emulsion was precisely weighed and dried at 105 ± 5 ° C. for 2 hours, and then the dry weight was measured and expressed in% by weight. (Mechanical stability) 50 g of the emulsion was rotated for 5 minutes under the conditions of 10 kg and 1000 rpm in a Maron stability tester, and the produced agglomerate was filtered through a 100 mesh wire mesh,
The filtration residue was washed with water and then dried at 105 ° C. for 2 hours, and this weight is represented by% by weight based on the solid content. (Effervescent) Dilute the emulsion twice with water, put 20 ml of this diluted emulsion in a 100 ml graduated test tube, and measure the foam height when shaken up and down for 10 seconds to obtain ml.
Display with. (Water resistance of film) Depending on the time required for whitening the 0.2 mm polymer film by the water immersion method, ◎: 1 day or more,
◯: Evaluated on the basis of 1 hour or more and x: less than 1 hour.
【0027】[0027]
【表1】 [Table 1]
【0028】参考例2(乳化重合用乳化剤使用例) 実施例1〜6で得られた化合物及び比較例1〜2の化合
物を用い、スチレン、アクリル酸ブチル(重量比1/1)
をモノマーとして参考例1と同様の方法で乳化重合を行
ない、得られた重合体エマルジョンについて同様に測定
した。その結果を表2に示す。Reference Example 2 (Example of Using Emulsifier for Emulsion Polymerization) Using the compounds obtained in Examples 1 to 6 and the compounds of Comparative Examples 1 to 2, styrene and butyl acrylate (weight ratio 1/1).
Was used as a monomer, emulsion polymerization was carried out in the same manner as in Reference Example 1, and the obtained polymer emulsion was measured in the same manner. The results are shown in Table 2.
【0029】[0029]
【表2】 [Table 2]
【0030】[0030]
【発明の効果】本発明の乳化重合用乳化剤を使用して造
られたエマルジョンは乳化剤分子がポリマー分子と化学
結合しているためにポリマーフィルムの接着性、耐水
性、耐候性及び耐熱性等のポリマー物性を低下させず、
エマルジョンの泡立も低い。また、エマルジョンを凝集
させ、ポリマーをろ別し、ろ液から未反応モノマーを蒸
発回収除去した後、有機物量を測定するために化学的酸
素要求量(COD)を測定したが、ほとんどゼロであり、
使用した乳化重合用乳化剤はポリマー中に含まれ排水処
理の必要のないことがわかった。更に、固形分%で明ら
かな如く本発明の乳化重合用乳化剤は重合禁止剤的に挙
動することは殆どなく、ポリマーの収率を低下させるこ
とが殆どない。The emulsion prepared by using the emulsifier for emulsion polymerization of the present invention has the adhesive property, water resistance, weather resistance and heat resistance of the polymer film because the emulsifier molecule is chemically bonded to the polymer molecule. Without deteriorating the physical properties of the polymer,
The foaming of the emulsion is also low. Also, the emulsion was flocculated, the polymer was filtered off, the unreacted monomer was evaporated and recovered from the filtrate, and then the chemical oxygen demand (COD) was measured to measure the amount of organic matter, but it was almost zero. ,
It was found that the emulsifying agent for emulsion polymerization used was contained in the polymer and did not require wastewater treatment. Further, as is apparent from the solid content%, the emulsifier for emulsion polymerization of the present invention hardly behaves as a polymerization inhibitor, and hardly lowers the yield of the polymer.
Claims (1)
Rは炭素原子数8〜24の炭化水素基またはアシル基で
あり、mは0〜50の数であり、M1及びM2は水素原
子、アルカリ金属、アルカリ土類金属、アンモニウムま
たは炭素原子数1〜4のヒドロキシアルキルアンモニウ
ムであり、M1及びM2は異なるものであっても、同一の
ものであってもよい)で表される、分子内にラジカル重
合可能な二重結合をもつ乳化重合用乳化剤。1. A general formula: (In the formula, A is an alkylene group having 2 to 4 carbon atoms,
R is a hydrocarbon group having 8 to 24 carbon atoms or an acyl group, m is a number of 0 to 50, and M 1 and M 2 are hydrogen atoms, alkali metals, alkaline earth metals, ammonium or the number of carbon atoms. 1 to 4 hydroxyalkylammonium, and M 1 and M 2 may be different or the same) and emulsified with a radically polymerizable double bond in the molecule Emulsifier for polymerization.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6210055A JP2617093B2 (en) | 1985-07-24 | 1994-09-02 | Emulsifier for emulsion polymerization |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP16205585 | 1985-07-24 | ||
JP60-162055 | 1985-07-24 | ||
JP6210055A JP2617093B2 (en) | 1985-07-24 | 1994-09-02 | Emulsifier for emulsion polymerization |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP61171816A Division JPS62104802A (en) | 1985-07-24 | 1986-07-23 | Emulsifier for emulsion polymerization |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH07165806A true JPH07165806A (en) | 1995-06-27 |
JP2617093B2 JP2617093B2 (en) | 1997-06-04 |
Family
ID=26487979
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP6210055A Expired - Lifetime JP2617093B2 (en) | 1985-07-24 | 1994-09-02 | Emulsifier for emulsion polymerization |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2617093B2 (en) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62104802A (en) * | 1985-07-24 | 1987-05-15 | Asahi Denka Kogyo Kk | Emulsifier for emulsion polymerization |
-
1994
- 1994-09-02 JP JP6210055A patent/JP2617093B2/en not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62104802A (en) * | 1985-07-24 | 1987-05-15 | Asahi Denka Kogyo Kk | Emulsifier for emulsion polymerization |
Also Published As
Publication number | Publication date |
---|---|
JP2617093B2 (en) | 1997-06-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JPH0575001B2 (en) | ||
EP1318157B1 (en) | Surfactant for emulsion polymerization | |
EP2221319A1 (en) | Surfactant composition for emulsion polymerization | |
JP3756391B2 (en) | Surfactant composition for emulsion polymerization | |
JPH0124141B2 (en) | ||
EP0121140A1 (en) | Fluoroacrylic copolymer | |
JPH07165806A (en) | Emulsifying agent for emulsion polymerization | |
EP0102707B1 (en) | Process for production of sterically stabilised wholly non-charged aqueous polymer dispersions | |
JPH07228613A (en) | Emulsifying dispersion agent for polymerization | |
JP2617094B2 (en) | Emulsifier for emulsion polymerization | |
JP3962130B2 (en) | New compounds and surfactants | |
EP2657289A1 (en) | Vinyl chloride copolymer latex and method for producing same | |
JP4663934B2 (en) | New phosphate ester type surfactant | |
JPH06248005A (en) | Emulsifier for emulsion polymerization | |
JP3995763B2 (en) | Surfactant | |
JPH0575002B2 (en) | ||
US4772670A (en) | Emulsion polymerization compositions containing 2-alkyl-1-alkanol polyglycolethers | |
JP3412185B2 (en) | Aqueous suspension of lauroyl peroxide | |
JPS6315805A (en) | Production of paste formable vinyl chloride polymer and vinyl chloride compound containing 30 weight percent or lessof copolymerizable monomer | |
JP3112207B2 (en) | Manufacturing method of polymer latex | |
JP4160438B2 (en) | Novel sulfate ester type surfactant | |
JPH0240082B2 (en) | ||
JP2004277678A (en) | Novel nonionic surfactant | |
JP2000344805A (en) | Reactive surfactant | |
JPH07228614A (en) | Emulsifying dispersion agent for polymerization |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
EXPY | Cancellation because of completion of term | ||
S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
R370 | Written measure of declining of transfer procedure |
Free format text: JAPANESE INTERMEDIATE CODE: R370 |