JPS60235631A - Non-selfpolymerising reactive cationic surface active agent - Google Patents

Abstract

PURPOSE:To enhance attractivity of rocks, clay, or talc, etc. to a negative electrifiable material thus improving the dispersibility thereof in an org. compd. by using a non-selfpolymerizing reactive cationic surface active agent expressed by the specified general formula. CONSTITUTION:The cationic surface active agent expressed by the formula is obtd. by allowing 2mol allyl halide to react with 1mol prim. or sec. amine having 1-2 8-24C hydrocarbon groups or 1-2 groups having 8-24C hydrocarbon, or by allowing further 1-50mol formaldehyde or 2-8C alkylene oxide to react therewith. In the above-described formula, R and R' are hydrocarbon groups having 1-24 carbon atoms as a total of R+R'; hydroxy-substituted hydrocarbon group; hydrocarbon groups having one ester linkage in the middle part of the chain and 3-27 carbon atoms as a total for R+R'; A<-> is halogen ion, or an org. or inorg. oxyacid ion.

Description

【発明の詳細な説明】 本発明はカチオン型の非自己重合性反応性界面活性剤に
関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a cationic non-self-polymerizable reactive surfactant.

さらに詳しくは、少なくとも１個の炭素数８−２４の炭
化水素基もしくはそれを有する基と少なくとも２個のア
リル基とで置換された構造よりなる第四級アンモニウム
塩型の新規なカチオン界面活拙剤に関するものである。More specifically, it is a novel cationic surfactant of the quaternary ammonium salt type having a structure substituted with at least one hydrocarbon group having 8 to 24 carbon atoms or a group having the same and at least two allyl groups. This is related to drugs.

従来より知られる反応性界面活性剤は、アニオン型とノ
ニオン型が大部分で、しかも、それらの多くは公知の界
面活性剤構造に対してビニル基、アクリル基、メタクリ
ル基、スチリル基等の重合反応性基を付属させたものよ
りなるが、自己重合性が大きく、例えば、塗料向けなど
の高分子エマルシヨンを製造する際の乳化重合剤として
使用した場合、対象モノモノマーと完全に共重合し得ず
、界面活性剤同士の反応よりなる親水性重合体をつくっ
てしまうために、期待された耐水性の改良等の長所は余
り見いだされていない。Most of the conventionally known reactive surfactants are anionic and nonionic, and many of them have polymerized vinyl groups, acrylic groups, methacrylic groups, styryl groups, etc. to the known surfactant structure. Although it has a reactive group attached, it has high self-polymerizability and, for example, when used as an emulsion polymerization agent in the production of polymer emulsions for paints, it cannot completely copolymerize with the target monomer. First, because a hydrophilic polymer is produced by a reaction between surfactants, the expected advantages such as improved water resistance have not been found.

それ以外のものとしてはアリル基を１個連結、するもの
やマレイン酸の片エステルなどが考えられるが、アリル
基１個よりなるものは重合性を示さず、また、マレイン
酸の片エステルも反応性が著しく低いために、実際には
重合反応を行なわしめる用途には殆ど使用されていない
。Other examples include those that link one allyl group and single esters of maleic acid, but those consisting of one allyl group do not show polymerizability, and single esters of maleic acid also react. Because of its extremely low properties, it is rarely used for polymerization reactions.

一方、ビニルベンジンルートリメチルアンモニウム−ハ
ライドやメチル−ビニルピリジニウム−ハライド等のカ
チオン性モノマーが仰られているが、それらは、自己重
合させて高分子電解質とした時に、はじめて界面活性剤
となり得るもので、それ自身では乳化、分散等の界面活
性能を全く示さない。On the other hand, cationic monomers such as vinylbenzine-trimethylammonium halide and methyl-vinylpyridinium halide are being talked about, but they can only become surfactants when they are self-polymerized to form a polymer electrolyte. By itself, it does not exhibit any surfactant ability such as emulsification or dispersion.

本発明者は種々研究の結果、次の一般式ｌ〔但し、ＲＩ
Ｒ’は炭素数合計１−２４の炭化水素基もしくはヒドロ
キシ置換炭化水素基、または、中間にエステル結合を１
個有する炭素数合計３−２７の炭化水素系基もしくはヒ
ドロ キシ置換炭化水素系基、中間にエーテル結合を１個有す
る炭素数合計２−２７の炭化水素系基もしくはヒドロキ
シ置換炭化水素系基、中間にアミド結合を１個有する炭
素数合計４−２７の炭化水素系基もしくはヒドロキシ置
換炭化水素系基、水素もしくは炭素数合計１−２４の炭
化水素基を末端に連結するポリ（但し、２−５０モル）
オキシアルキレン（但し、炭素数１−８）基であり、Ｅ
はハロゲンイオンもしくは有機または無機のオキシ酸イ
オンであり、かつ、Ｒ，Ｒ’のうちの少なくとも一方が
炭素数合計８以上の炭化水素基もしくはヒドロキシ置換
炭化水素基であるかまたは炭素数７以上の炭化水素基も
しくはヒドロキシ置換炭化水素基を連結する基である。As a result of various studies, the present inventor found the following general formula l [where RI
R' is a hydrocarbon group having a total of 1 to 24 carbon atoms or a hydroxy-substituted hydrocarbon group, or a group with an ester bond in the middle.
A hydrocarbon group or a hydroxy-substituted hydrocarbon group having a total of 3 to 27 carbon atoms, a hydrocarbon group or a hydroxy-substituted hydrocarbon group having a total of 2 to 27 carbon atoms and one ether bond in the middle, A hydrocarbon group having one amide bond and a total of 4 to 27 carbon atoms or a hydroxy-substituted hydrocarbon group, or a poly (2 to 50 mol) which has hydrogen or a hydrocarbon group having a total of 1 to 24 carbon atoms connected to the terminal. )
It is an oxyalkylene (however, carbon number 1-8) group, and E
is a halogen ion or an organic or inorganic oxyacid ion, and at least one of R and R' is a hydrocarbon group or a hydroxy-substituted hydrocarbon group having a total of 8 or more carbon atoms, or a hydroxy-substituted hydrocarbon group having 7 or more carbon atoms. A group that connects hydrocarbon groups or hydroxy-substituted hydrocarbon groups.

〕にて表わされるカチオン界面活性剤が乳化性、分散性
にすぐれており、かつ、それ自身は化学的に安定で自己
重合物をつくらず、対策モノマーとの間の共重合生成物
のみをつくり得るという発明に致達した。The cationic surfactant represented by ] has excellent emulsifying and dispersing properties, and is chemically stable itself and does not produce self-polymerization products, but only produces copolymerization products with the countermeasure monomer. We have arrived at an invention that allows us to obtain

ここで、本発明のカチオン型非自己重合性反応性界面活
性剤の製造方法について述べると、本発明のカチオン型
非自己重合性反応性界面活性剤は１）炭素数８−２４の
炭化水素基もしくはそれを有する基を１個もしくは２個
有する一級もしくは二級アミン１モルに対して、ハロゲ
ン化アリル２モル反応させるか、もしくは、さらに、ホ
ルムアルデヒド、炭素数２−８のアルキレンオキシドを
１−５００モル反応せるか ２）アリル基を２個有する二級もしくは三級アミン１モ
ルに対して、炭素数８−２４の炭化水素基とハロゲンを
同時に有する化合物１−２モル反応させるか、もしくは
、ざら−ζ、ホルムアルデヒド、炭素数２−８のアルキ
レンオキシドを１−５００モル反応せるか ３）炭素数８−２４の炭化水素基もしくはそれを有する
基１個とアリル基２個からなる三級アミン１モルに対し
て、有機酸もしくは無機酸を１グラム当量反応させた後
、さらに、ホルムアルデヒド、炭素ｆｉ２−８のアルキ
レンオキシドｊ）１−５０モル反応させるか ４）アリル基を２個有する二級もしくは三級アミン１モ
ルに対して、有機酸もしくは無機酸を１グラム当量反応
させた後、さらに、炭素数８−２４のアルキレンオキシ
ドを１−２モル反応させるかまたは ５）炭素数８−２４の炭化水素基もしくはそれを有する
基１個とアリル基２個からなる三級アミン１条件は通常
公知のカチオン界面活性剤を製造する際の条件とはゾ同
様であり、例えば、アミンとハロゲン化合物の反応は常
圧−１５Ｋｆ／−好ましくは常圧−５Ｋｔ／ｃｄ、２０
−２００℃、好ましくは５０−１５０℃で行なわれ、こ
の場合、アルコール、ジオキサン、グリコールエーテル
等の親水性溶媒の使用は反応の完結をより容易にする。Here, to describe the method for producing the cationic non-self-polymerizable reactive surfactant of the present invention, the cationic non-self-polymerizable reactive surfactant of the present invention has 1) a hydrocarbon group having 8 to 24 carbon atoms; Alternatively, 2 moles of allyl halide is reacted with 1 mole of a primary or secondary amine having 1 or 2 groups thereof, or, alternatively, formaldehyde or an alkylene oxide having 2-8 carbon atoms is reacted with 1-500 2) One mole of secondary or tertiary amine having two allyl groups is reacted with 1 to 2 moles of a compound having a hydrocarbon group having 8 to 24 carbon atoms and a halogen, or - ζ, formaldehyde, react with 1-500 moles of alkylene oxide having 2-8 carbon atoms or 3) Tertiary amine consisting of 1 hydrocarbon group having 8-24 carbon atoms or a group having it and 2 allyl groups 1 After reacting 1 gram equivalent of organic acid or inorganic acid per mole, further react with formaldehyde, alkylene oxide with carbon fi2-8 j) 1-50 moles, or 4) secondary or inorganic acid having two allyl groups. After reacting 1 gram equivalent of organic acid or inorganic acid with 1 mole of tertiary amine, further reacting 1 to 2 moles of alkylene oxide having 8 to 24 carbon atoms; The conditions for the tertiary amine consisting of one hydrocarbon group or a group having it and two allyl groups are the same as those for producing known cationic surfactants. The reaction is carried out at normal pressure -15Kf/- preferably at normal pressure -5Kt/cd, 20
It is carried out at -200°C, preferably 50-150°C, in which case the use of hydrophilic solvents such as alcohols, dioxane, glycol ethers etc. makes it easier to complete the reaction.

また、Ｎ−Ｈ基を残存する中間体とホルムアルデヒドも
しくはアルキレンオキシドとの間の反応は、常圧−１５
紛／−１好ましくは常圧−１０Ｋｆ／ｃｄ、ｚ。In addition, the reaction between the intermediate having a remaining N-H group and formaldehyde or alkylene oxide is carried out at atmospheric pressure -15
Powder/-1 preferably normal pressure -10 Kf/cd, z.

−２５０℃、好ましくは５０−２００℃で行なかれ、こ
の場合、酸、アルカリ等の触媒、ならびに水、アルコー
ル、ジオキサン、グリコールエーテル等の溶媒の使用は
反応の完結を速める。一方、アミンと有機酸もしくは無
機酸との反応は常圧下、０−１５０℃、好ましくは２０
−１００℃で容易に行なわれ、この場合も水、ジオキサ
ン、グリコールエーテル等の溶媒を使用すると、反応の
完結がより容易となる。It is carried out at −250° C., preferably 50-200° C., in which case the use of catalysts such as acids, alkalis, and solvents such as water, alcohols, dioxane, glycol ethers speeds up the completion of the reaction. On the other hand, the reaction between an amine and an organic or inorganic acid is carried out at normal pressure, at 0-150°C, preferably at 20°C.
It is easily carried out at -100°C, and in this case too, the use of a solvent such as water, dioxane, glycol ether, etc. makes it easier to complete the reaction.

さらに、アミンと無機酸の低級アルコールエステルとの
反応は常圧−１５４／ｃｄ、好ましくは常圧−５Ｋｆ／
ｃｊ、２０−２００℃、好ましくは５〇−１５０℃で行
なわ′れ、この場合も親水性溶媒を使用すると、反応の
完結が容易となる。なお、本発明のカチオン型非自己重
合性反応性界面活性剤の代表例としては、下記構造のも
のを挙げることがＯＨｃｒ ＯＨＢ、− ｔ− ＣＨｊＳ　Ｏ。Furthermore, the reaction between the amine and the lower alcohol ester of an inorganic acid is carried out at normal pressure -154/cd, preferably at normal pressure -5Kf/cd.
cj, 20 DEG-200 DEG C., preferably 50 DEG-150 DEG C. Again, the use of a hydrophilic solvent facilitates the completion of the reaction. Incidentally, representative examples of the cationic non-self-polymerizable reactive surfactant of the present invention include those having the following structures: OHcr OHB, -t-CHjSO.

ＣＨｓＣＯＯ”− なお、本発明の非自己重合性反応性界面活性剤は岩石、
粘土、タルク、ガラス繊維および各檜無機質充填剤等の
一帯電性物質に対して良く吸着し４表面を有機化して有
機化合物中への分散性を改良せしめる作用をなし、しか
も、例えば、対象とする有機化合物が不飽和ポリエステ
ル、スチレン、各種ビニル系もしくはアクリル系モノＹ
−である場合には、固形物表面に吸着した本発明の非自
己重合性反応性界面活性剤がさらに共重合を行なって、
対象とする有機化合物中に取り込まれるので、上述の固
形物を充分に安定に分散せしめるという長所が生まれる
。CHsCOO”- The non-self-polymerizable reactive surfactant of the present invention is
It adsorbs well to monostatic substances such as clay, talc, glass fiber, and various cypress inorganic fillers, and has the effect of making the surface organic and improving dispersibility in organic compounds. The organic compound used is unsaturated polyester, styrene, various vinyl or acrylic compounds.
-, the non-self-polymerizable reactive surfactant of the present invention adsorbed on the surface of the solid material further undergoes copolymerization,
Since it is incorporated into the target organic compound, it has the advantage of sufficiently stably dispersing the above-mentioned solids.

一方、本発明の非自己重合性反応性界面活性剤と各種付
加重合性モノマーとを共重合させて得たカチオン性高分
子゛鴫解質は帯電防止剤、導電剤の用途のほかに、従来
のアニオン粒子型の各機高分子製品ではイオン反発を生
じるために、性能の満足が得られなかつたアスファルト
、セメントの強化剤、ガラス繊維の集束剤、紙、粘土の
疎水化剤等の用途に使用した場合、すぐれた効果を発揮
すると推測される。On the other hand, the cationic polymer ``chacolyte'' obtained by copolymerizing the non-self-polymerizable reactive surfactant of the present invention with various addition-polymerizable monomers has been used as an antistatic agent and a conductive agent. Due to ionic repulsion caused by anionic particle type polymer products, it is suitable for applications such as asphalt, reinforcing agents for cement, sizing agents for glass fibers, hydrophobizing agents for paper and clay, etc., for which the performance could not be achieved. It is estimated that it will have excellent effects when used.

以下、本発明の非自己重合性共重合性界面活性剤につい
て実施例を示す。Examples of the non-self-polymerizable copolymerizable surfactant of the present invention will be shown below.

実施例１ かきまぜ器、温度計、気体流入管、滴下ロート及びコン
デンサーに連結するアダプターを付した五ツロフラスコ
に、本発明の２−ヒドロキシオクタデシル−メチル−ジ
アリル−アンモニウム−クロリド２０．８ｙ（ｏ、ｏｓ
モル）と３７４．４Ｉｉの水を仕込み、４０℃にて混合
し、均一溶液とした。つづいて、スチレン１０４ＩＩ（
１モル）を滴下し、エマルシヨンを作成した後、Ｎｔガ
スを通じつつ、０，６ｊ’の過硫酸アンモニウムを４１
の水に溶かした液を添加し、８０℃まで昇温させた。次
いで、同温度で１２時間重合を行ない、安定な高分子エ
マルシヨンを得た。しかる後、−３０℃に静置させ、凍
結分離させた沈＃（生成高分子）についてケルプール法
でＮ（ｉを測定した結果、測定値０，５５チ（但し、計
算値０，５６チ）がめられ、２−ヒドロキシオクタデシ
ル−メチル−ジアリル−アンモニウム−クロリドかはゾ
完全にスチレンと共重合していることがわかりた。Example 1 20.8 y (o, os
mol) and 374.4Ii of water were charged and mixed at 40°C to form a homogeneous solution. Next, Styrene 104II (
1 mol) was added dropwise to create an emulsion, and then 0.6j' ammonium persulfate was added at 41 mol while passing Nt gas.
A solution dissolved in water was added thereto, and the temperature was raised to 80°C. Next, polymerization was carried out at the same temperature for 12 hours to obtain a stable polymer emulsion. After that, N (i) was measured by the Kelpool method on the precipitate # (produced polymer) that was left to stand still at -30°C and frozen, and the measured value was 0.55 cm (however, the calculated value was 0.56 cm). It was found that 2-hydroxyoctadecyl-methyl-diallyl-ammonium chloride was completely copolymerized with styrene.

なお、２−ヒドロキシオクタデシル−メチル−ジアリル
−アンモニウム−クロリド ンモニウムを添加して、８０℃で混合させても、重合反
応は起らなかつた。Incidentally, even when 2-hydroxyoctadecyl-methyl-diallyl-ammonium-chloridonmonium was added and mixed at 80°C, no polymerization reaction occurred.

実施例２ 実施例１と同様の装置に、本発明のジ（２−ヒドロキシ
テトロデシル）−ジアリル−アンモニウム−プロミド、
５．６７ｊｌ（０．０１モル）と、２　４　６．　８　
Ｊ’の水を仕込み、５０℃ｌこて混合し、均一溶液とし
た。Example 2 In an apparatus similar to Example 1, di(2-hydroxytetrodecyl)-diallyl-ammonium-bromide of the invention,
5.67jl (0.01 mol) and 2 4 6. 8
J' water was added and mixed with a trowel at 50°C to form a homogeneous solution.

つづいて、メチルメタクリラート１００，ＩＩｉ（１モ
ル）を滴下し、エマルシヨンを作成した後、Ｎ，気流下
に０，ＯＩＪＩの過硫酸カリウムを投入した後、徐々に
内温を９５℃まで至らしめ、同温度で３時間重合を行な
りた。次いで、得られた高分子エマルシヨンを一３０℃
に静置させ、凍結分離させた沈＃（生成高分子）のＮ％
を測定した結果、測定値０１３％（但し、計算＋１０．
１３％）がめられ、ジ（２−ヒドロキシテトラデシル）
−ジアリル−アンモニウム−プロミドが完全にメチルメ
タクリラートと共重合していることがわかった。Subsequently, methyl methacrylate 100.IIi (1 mol) was added dropwise to create an emulsion, and then potassium persulfate of 0.00,000,000,000,000 ml was added under a stream of N gas, and the internal temperature was gradually brought to 95°C. , and polymerization was carried out at the same temperature for 3 hours. Next, the obtained polymer emulsion was heated to -30°C.
N% of precipitate # (produced polymer) that was left to stand still and freeze-separated
As a result of measuring, the measured value was 013% (however, the calculation +10.
13%) and di(2-hydroxytetradecyl)
It was found that -diallyl-ammonium-bromide was completely copolymerized with methyl methacrylate.

なお、比較試験きして、ジ（２−ヒドロキシテトラデシ
ル）−ジアリル−アンモニウム−プロミド単独の水溶液
ｆこ過硫酸カリウムを添加して、５０℃から９５℃まで
の温度範囲で混合攪拌を行なっても、重合反応は起らな
かった。In addition, in a comparative test, an aqueous solution of di(2-hydroxytetradecyl)-diallyl-ammonium-bromide alone was added with potassium persulfate, and mixed and stirred at a temperature range of 50°C to 95°C. However, no polymerization reaction occurred.

実施例３ グラス製オートクレーブに、本発明の３−トリデシルオ
キシ−２−ヒドロキシプロピル−ベンジル−ジアリル−
アンモニウム−クロリドｔｓｙ（ｏ．ｏｘモル）と０。Example 3 The 3-tridecyloxy-2-hydroxypropyl-benzyl-diallyl- of the present invention was placed in a glass autoclave.
Ammonium-chloride tsy (o.ox mol) and 0.

３Ｉの過硫酸カリウムと１８０９の水を仕込み、５０℃
で１６時間混合攪拌したが、重合反応は起らなかった。Prepare 3I potassium persulfate and 1809 water and heat to 50℃.
Although the mixture was mixed and stirred for 16 hours, no polymerization reaction occurred.

次に、スチレン２　６　ｇ（　０．　２　５モル）を注
入し、エマルシヨンを作成した系にブタジェン８　１．
　１　９　（　１．　５モル）を吹き込み、１−５々／
−の内圧条計下、５０℃で１６時間反応させたところ、
重合が行なわれ、安定な高分子ラテックスが得られた。Next, 26 g (0.25 mol) of styrene was injected and 1.8 g of butadiene was injected into the emulsion-forming system.
Blow in 19 (1.5 mol), 1-5/
- When reacted for 16 hours at 50°C under an internal pressure gauge,
Polymerization was carried out and a stable polymer latex was obtained.

しかる後、得られたラテックスの一部をガラス板上に注
ぎ、１２０℃で１時間乾燥させてつくった薄膜について
Ｎチを測定した結果、測定値０，１３チ（但し、計算値
０．１３％）がめられ、３−トリデシルオキシ−２−ヒ
ドロキシプロピルーベンジルージアリルーアンモキウム
ークロリドが完全に８８Ｒと結合していることがわかつ
た。After that, a part of the obtained latex was poured onto a glass plate and dried at 120°C for 1 hour, and the resulting thin film was measured for N. As a result, the measured value was 0.13 (however, the calculated value was 0.13 %), and it was found that 3-tridecyloxy-2-hydroxypropyl-benzyl-diaryl-ammonium chloride was completely bound to 88R.

実施例４ 実施例３と同様の装置ｌこ、本発明のオクタデシルーメ
千ルージアリルーアンモニウムーモノメチルサルファー
ト４．７ｊ’（０．０１モル）とオクチル−ヒドロキシ
メチル−ジアリル−アンモニウム−トルエンスルホナー
ト 硫酸アンモニウムと３４７．４．９の水を仕込み、Ｎ！
気流下に５０℃で６時間混合攪拌したが、重合反応は起
らなかりた。次に、亜硫酸ガス１９．２Ｆ（０１３モル
）を吹き込み、１−５〜／−の内圧条件下、５０℃で６
時間反応させたところ、重合が行なわれ、黄色透明粘稠
な高分子水溶液が得られた。Example 4 Apparatus similar to Example 3 except that octadecyl-diaryl-ammonium-monomethyl sulfate 4.7j' (0.01 mol) of the present invention and octyl-hydroxymethyl-diallyl-ammonium-toluenesulfonate ammonium sulfate were prepared. and 347.4.9 water, N!
Although the mixture was mixed and stirred at 50° C. for 6 hours under air flow, no polymerization reaction occurred. Next, 19.2 F (0.13 mol) of sulfur dioxide gas was blown in, and 6
When the reaction was allowed to proceed for a period of time, polymerization occurred and a yellow, transparent, viscous aqueous polymer solution was obtained.

しかる後、得られた高分子水溶液を５倍量のアセトン中
に注入し、再結晶させ、減圧乾燥させて得た結晶につい
て８％を測定した結果、測定値２．９５％（但し、計算
１１［２，９４％）がめられ、オクタデシル請メチル閘
ジアリルーアンモニウムーモノメチルサルファートとオ
クチル−ヒドロキシメチル−ジアリルーアンモニウムー
トルエンスルホナートカ完全に亜硫酸ガスと共重合して
いることがわかった。After that, the resulting aqueous polymer solution was injected into 5 times the amount of acetone, recrystallized, and dried under reduced pressure. As a result of measuring 8% of the obtained crystals, the measured value was 2.95% (however, calculation 11 It was found that octadecyl-diaryl-ammonium-monomethyl sulfate and octyl-hydroxymethyl-diaryl-ammonium-toluenesulfonate were completely copolymerized with sulfur dioxide gas.

実施例５ 実施例３と同様の装置に、本発明のリグノセロイルオキ
シプロピル−リグノセラミドプロピル−ジアリル−アン
モニウム−クロリド４．７５１！（０，００５モル）と
カプリロイルオキシエチル璽２−エチルヘキシラミドエ
チルージアリルーアンモニウムークロリド４７．３＃（
０，１モル）と０．５８　Ｆの過硫酸アンモニウムと５
７．ＴＩｌの水を仕込み、Ｎｔ気流下に５０℃でｌθ時
間混合攪拌したが、重合反応は起らなかつだ。Example 5 Into the same apparatus as in Example 3, 4.751 liters of lignoceloyloxypropyl-lignoceramide propyl-diallyl-ammonium chloride of the present invention! (0,005 mol) and capryloyloxyethyl 2-ethylhexylamide ethyldiarylammonium chloride 47.3# (
0.1 mol) and 0.58 F ammonium persulfate and 5
7. Water of TIl was charged, and the mixture was mixed and stirred at 50° C. for lθ hours under a Nt stream, but no polymerization reaction occurred.

次に、インブチレン５．６　ＩＩ（０，１モル）を吹き
込み、３々／−の内圧条件下で１０時間反応させたとこ
ろ、重合が行なわれ、黄褐色半透明な高分子粘稠溶液が
得られた。しかる後、得られた溶液の１部をステンレス
板に注ぎ、１１０℃にて２時間乾燥させ、脱水させた後
の固形物について８％を測定した結果、測定値５，１０
チ（但し、計算値５６１０％）がめられ、リグノセロイ
ルオキシプロピル−リグノセラミドプロピル−ジアリル
−アンモニウム−クロリドとカプリロイルオキシエチル
−２−エチルへキシラミドエチル−ジアリル−アンモニ
ウムークロリドが完全にイソブチレンと共重合している
ことがわかった。Next, inbutylene 5.6 II (0.1 mol) was blown in and reacted for 10 hours under an internal pressure condition of 3/-, resulting in polymerization and a yellow-brown translucent viscous polymer solution. Obtained. After that, a part of the obtained solution was poured onto a stainless steel plate and dried at 110°C for 2 hours. After dehydration, 8% of the solid matter was measured, and the measured value was 5.10.
However, lignocelloyloxypropyl-lignoceramidepropyl-diallyl-ammonium-chloride and capryloyloxyethyl-2-ethylhexylamidoethyl-diallyl-ammonium-chloride were completely combined with isobutylene. It was found that it was polymerized.

実施例６ 実施例１と同様な装置に、ノニルフェノキシポリ（９モ
ル）エチレンオキシエチル−メチル−シアーアンモニウ
ムークロリド３．　１　６　Ｆ　（　０．　０　０　４
モル）と０．　４　５　＃の過硫酸カリウムと２　０　
８．　３　１１の水を仕込み、Ｎ．気流下に７０℃で３
時間反応させても重合反応は起らなかつた。次に、内温
を５０℃とし、約１５分を要して、酢酸ビニル８　６．
　ｌ　Ｉ？　（　１モル）を注入して、乳化状態をつく
り、５０℃で２時間反応させ、つづいて、７０℃で５時
間反応させたところ、重合が行なわれ、安定な高分子エ
マルシランが得られた。Example 6 Into the same apparatus as in Example 1, 3.0% of nonylphenoxypoly(9 mol) ethyleneoxyethyl-methyl-cyammonium chloride was added. 1 6 F (0. 0 0 4
mole) and 0. 4 5 # potassium persulfate and 2 0
8. 3. Pour 11 water, N. 3 at 70℃ under air flow
No polymerization reaction occurred even after a long reaction time. Next, the internal temperature was set to 50°C, and it took about 15 minutes to convert the vinyl acetate 8 6.
l I? (1 mol) was injected to create an emulsified state and reacted at 50°C for 2 hours, and then at 70°C for 5 hours, polymerization occurred and a stable polymeric emulsilane was obtained.

次いで、得られた高分子エマルションを一３０℃に静置
させ、凍結分離させた沈澱（生成高分子）のＮチを測定
した結果、測定値０．６２チ（但し、計算値０、６３％
）がめられ、ノニルフェノキシポリ（９ｅル）玉子しン
オキ込エチルーメチルージアリル−アンモニウム−クロ
リド 共重合していることがわかった。Next, the obtained polymer emulsion was allowed to stand at -30°C, and the N-thickness of the frozen and separated precipitate (produced polymer) was measured.
), and it was found that nonylphenoxypoly(9el), ethylmethyl, diallyl, ammonium, and chloride were copolymerized.

実施７ 実施例１と同様な装置に、°テトラコシルオキシポリ（
２０（−／ｌ／）７”ロピレンオキシボリ（２９モル）
玉子しンオキシエ千ルーアセトイルオキシメチル−ジア
リル調アンモニウムーアセター）　３．　０　５　＃（
０．００１モル）とオレイルオキシポリ（３モル）オク
チレンオキシボリ（１６モル）エチレンオキシェチルー
ヒドロキシアセトイルオキシメチルージアリルーアンモ
ニウムーヒドロキシアセタート１．６５ｊ＋（０．００
１モル）と０．６Ｉの過硫酸カリウムと２１０．９の水
を仕込み、〜気流下に７０℃で５時間反応させても重合
反応は起らなかった。Example 7 Into the same apparatus as in Example 1, °tetracosyloxypoly(
20(-/l/)7”ropyleneoxybori (29 mol)
1,000-ru-acetoyloxymethyl-diallylic ammonium-aceter) 3. 0 5 #(
0.001 mol) and oleyloxypoly(3 mol)octyleneoxyboly(16 mol)ethyleneoxyethyl-hydroxyacetoyloxymethyl-diarylammonium-hydroxyacetate 1.65j+(0.00
Even if 1 mol), 0.6 I of potassium persulfate, and 210.9 I of water were charged and allowed to react at 70° C. for 5 hours under a stream of air, no polymerization reaction occurred.

次に、内温を５０℃とし、約１５分を要して酢酸ビニル
８　６．　１　１　（　１モル）を注入して、乳化状態
をつくり、５０℃で４時間反応させ、つづいて、７３℃
で６時間反応させたところ、重合が行なわれ、安定す高
分子エマルシ璽ンが得られた。Next, the internal temperature was set to 50°C, and vinyl acetate 8 was added for about 15 minutes. 1 1 (1 mol) was injected to create an emulsified state, reacted at 50°C for 4 hours, and then heated to 73°C.
When the mixture was reacted for 6 hours, polymerization occurred and a stable polymer emulsion was obtained.

次いで、得られた高分子エマルシ璽ンを一３０℃に静置
させ、凍結分離させた沈澱（生成高分子）のＮ係を測輩
した結果、測定値０．０３％（但し、計算値０、０３チ
）がめられ、上記二種類の本発明の反応性界面活性剤が
光分に酢酸ビニルと共重合していることがわかった。Next, the resulting polymer emulsion was left to stand at -30°C, and the N factor of the frozen and separated precipitate (produced polymer) was measured, and the measured value was 0.03% (however, the calculated value was 0. It was found that the above two types of reactive surfactants of the present invention were copolymerized with vinyl acetate in the optical spectrum.

実施例８ 実施例１と同様な装置に、リグノセロイルオキシブロヒ
ルーメトキシエトキシエチル一ジアリルーアンモニウム
ーブロミド１．　３　８　＃　（　０．　Ｏ　Ｏ　２モ
ル）とりグノセラミドプロピルーヒドロキシボリ（９モ
ル）エチレンオキシエチルージアリルーアンモニウム一
クロリド１．９６２（０，００２モル）と１．４１１の
α２α′−アゾジイソブチロニトリルと１００５’のイ
ソプロピルアルコールを仕込み、Ｎ、気流下に５０℃で
６時間反応させても重合反応は起こらなかった。次に、
この中ｆこ酢酸ビニル３０１．４　Ｆ　（３，５モル）
を注入し、５０℃で１２時間反応させたところ、重合が
行なわれ、淡黄色粘稠な高分子溶液が得られた。Example 8 In an apparatus similar to Example 1, lignocelloyloxybrohy-methoxyethoxyethyl monodiaryl-ammonium bromide 1. 3 8 # (0. O O 2 mol), gnoceramide propyl-hydroxyboly (9 mol), ethyleneoxyethyl-diaryl-ammonium monochloride 1.962 (0,002 mol) and 1.411 α2α'-azodiisobutylene Even when tyronitrile and 1005' isopropyl alcohol were charged and reacted at 50°C for 6 hours under a N gas flow, no polymerization reaction occurred. next,
Among these, vinyl acetate 301.4 F (3.5 mol)
was injected and allowed to react at 50°C for 12 hours, resulting in polymerization and a pale yellow viscous polymer solution was obtained.

つづいて、内温を１３０℃に高めた後、５Ｏ−１００Ｈ
Ｈ１の減圧下にイソプロピルアルコールヲ系外に留出さ
せ、生成高分子を取り出した後、細かく砕いてからｉｏ
ｏ℃で３時間乾燥を行ない、イソプロピルアルコールを
完全に除去した。Next, after increasing the internal temperature to 130℃, 5O-100H
The isopropyl alcohol is distilled out of the system under the reduced pressure of H1, and the produced polymer is taken out, then finely crushed and then io
Drying was performed at 0° C. for 3 hours to completely remove isopropyl alcohol.

次いで、得られた生成高分子についてＮｌを測定した結
果、測定値０，０２チ（但し、計算値０．０２２％）が
められ、上記二櫓類の本発明の反応性界面活性剤かは＼
゛完全酢酸ビニルと共重合していると推定された。Next, as a result of measuring Nl of the resulting polymer, the measured value was found to be 0.02% (however, the calculated value was 0.022%), and it was found that the reactive surfactant of the present invention was of the above two types.
``It was estimated that it was completely copolymerized with vinyl acetate.

実施例９ 実施例１と同様な装置ｔＩＣ、テトラコシルーメトキシ
メチル−ジアリル−アンモニウム−クロリド５１．４ｇ
（０，１モル）と２．３４ｇのベンゾイルパーオキシド
と４００５１のジオキサンを仕込み％’％気流下に８０
℃で６時間反応させても重合反応は起らなかった。Example 9 Apparatus tIC as in Example 1, 51.4 g of tetracosylmethoxymethyl-diallyl-ammonium-chloride
(0.1 mol), 2.34 g of benzoyl peroxide and 40051 dioxane were prepared and heated to 80% under air flow.
No polymerization reaction occurred even after 6 hours of reaction at °C.

次に、この中にメチルスチレン４７２ＩＩ（４モル）を
注入し、８０℃で１６時間反応させたところ、重合が行
なわれ、橙黄色粘稠な高分子溶液が得られた。Next, methylstyrene 472II (4 mol) was injected into this and reacted at 80°C for 16 hours, resulting in polymerization and an orange-yellow viscous polymer solution was obtained.

つづいて、内温を１５０℃に高めた後、５０ｕＨｊ’の
減圧下にジオキサンを系外に留出させ、生成高分子を取
出した後、細かく砕いてから１２０℃で３時間乾燥を行
ない、ジオキサンを完全に除去した。し力）る後、生成
高分子を３倍量の水に分数させ、次いで、−３０℃に静
置させて凍結分離させた沈澱についてＮチを測定した結
果、測定値０．２　ｓ　％　（但し、計算値０．２７　
％　）がめられ、本発明のテトラコシル−メトキシメチ
ル−ジアリル−アンモニウム−クロリドかはゾ完全にメ
チルスチレンと共重合していることが確、かめられた。Subsequently, after raising the internal temperature to 150°C, dioxane was distilled out of the system under a reduced pressure of 50 uHj', and the produced polymer was taken out. After finely pulverizing the polymer, it was dried at 120°C for 3 hours to remove dioxane. was completely removed. After that, the produced polymer was fractionated into 3 times the volume of water, and then the precipitate was frozen and separated by standing at -30°C. As a result, the N concentration was measured, and the measured value was 0.2 s % ( However, the calculated value is 0.27
%), and it was confirmed that the tetracosyl-methoxymethyl-diallyl-ammonium chloride of the present invention was completely copolymerized with methylstyrene.

実施例１０ 実施例１と同様な装置に、ドデシルベンジル−ヒドロキ
シポリ（４９モル）エチレンオキシエチル−ジアリル−
アンモニウム−アセタート５．２４１Ｉ（０，００２モ
ル）と０．１２　Ｆの過硫酸カリウムと２１８１の水を
仕込み、Ｎ！気流下に７５℃で６時間攪拌しても重合反
応は起らなかった。次に、メチルアクリラート８６．１
＃（１モル）とスチレン２６．９（０，２５モル〕を注
入し、７５℃で６時間、８５℃で３時間反応させたとこ
ろ、重合が行なわれ、安定な高分子エマルションが得ら
れた。しかる後、得られた高分子エマルションを一３０
℃に静置させ、凍結分離させた沈澱（生成高分子）のＮ
ｌを測定した結果、測定値０．０２チ（但し、計算値０
．０２４％）がめられ、本発明のドデシルベンジル−ヒ
ドロキシポリ（４９モル）エチレンオキシエチル−ジア
リル−アンモニウム−アセタートがはり完全にスチレン
−アクリル樹脂と共重合していることがわかった。Example 10 In an apparatus similar to Example 1, dodecylbenzyl-hydroxypoly(49 mol) ethyleneoxyethyl-diallyl-
Prepare ammonium acetate 5.241I (0,002 mol), 0.12 F potassium persulfate, and 2181 water, N! No polymerization reaction occurred even after stirring at 75° C. for 6 hours under a stream of air. Next, methyl acrylate 86.1
# (1 mol) and styrene 26.9 (0.25 mol) were injected and reacted at 75°C for 6 hours and at 85°C for 3 hours, polymerization occurred and a stable polymer emulsion was obtained. After that, the obtained polymer emulsion was
The N of the precipitate (produced polymer) that was left to stand still at ℃ and freeze-separated
As a result of measuring l, the measured value is 0.02ch (however, the calculated value is 0.
．． It was found that the dodecylbenzyl-hydroxypoly(49 mol) ethyleneoxyethyl-diallyl-ammonium-acetate of the present invention was completely copolymerized with the styrene-acrylic resin.

実施例１１ 実施例１と同様な装置に、ドデシルオキシプロピル−ヒ
ドロキシエトキシメチル論ジアリル−アンモニウム−ナ
イトラード４．６１１１（０，０１モル）と０．５１の
過謔酸アンモニウムと４２４．２１９の水を仕込み５０
℃で１２時間攪拌混合しても重合反応は起らなかった。Example 11 In an apparatus similar to Example 1, 4.6111 (0.01 mol) of dodecyloxypropyl-hydroxyethoxymethyl diallyl-ammonium-nitride, 0.51 of ammonium performate, and 424.219 of water were added. Prepare 50
No polymerization reaction occurred even after stirring and mixing at ℃ for 12 hours.

次に、２−クロロブタジェン１７７．２　Ｎ（２モル）
を注入し、乳化状帳をつくった後、５０℃で１２時間反
応させたところ、重合が行なわれ、安定な高分子エマル
ションが得られた。つづいて、食塩６０ｇを添加し、エ
マルションを破壊した後、５３１．６１のトルエンを注
入し、生成高分子を溶液として取出した。しかる後、ト
ルエン溶液の一部をガラス板上に注ぎ、１３０℃で２時
間乾燥させてつくった薄膜についてＮｌを測定した結果
、測定値０１６％（但し、計算値０１５％）がめられ、
本発明のドデシルオキシブロビルーヒドロキシエトキシ
メチルージアリルーアンモニウムーナイトラートが完全
に２−クロロブタジェンと結合していることがわかった
。Next, 2-chlorobutadiene 177.2 N (2 mol)
was injected to form an emulsion and then reacted at 50°C for 12 hours, resulting in polymerization and a stable polymer emulsion. Subsequently, 60 g of common salt was added to break the emulsion, and then 531.61 g of toluene was injected and the produced polymer was taken out as a solution. After that, a portion of the toluene solution was poured onto a glass plate and dried at 130°C for 2 hours, and the resulting thin film was measured for Nl. As a result, the measured value was 016% (however, the calculated value was 015%).
It has been found that the dodecyloxybrobyl-hydroxyethoxymethyl-diaryl ammonium nitrate of the present invention is completely bound to 2-chlorobutadiene.

実施例１２ 実施例１と同様の装置に、ジエチレングリコール２３３
、４　Ｆ　（２，２モル）と無水マレイン酸１９６．１
、？（２，０モル）を仕込み、１９０℃でポリエステル
化反応を行ない、１８ｊ’の水と２１．２Ｆのジエチレ
ングリコール（過剰分）を系外に留出させた。Example 12 In a device similar to Example 1, diethylene glycol 233
, 4F (2.2 mol) and maleic anhydride 196.1
,? (2.0 mol) was charged, a polyesterification reaction was carried out at 190°C, and 18j' water and 21.2F diethylene glycol (excess) were distilled out of the system.

次いで、テトラコシルーメトキシメチル−ジアリル−ア
ンモニウム−クロリド１０．３Ｆ（０，０２モル）トス
チレン１６６．４ｊ’（１，６モル）と２Ｊ’のベンゾ
イルパーオキシドを投入し、５分間混合攪拌した後、Ｎ
２気流下に金属板上に写し取り、２５℃で６時間静置さ
せ、橋かけ重合物を得た。Next, tetracosylmethoxymethyl-diallyl-ammonium chloride 10.3F (0.02 mol), tostyrene 166.4j' (1.6 mol) and 2J' of benzoyl peroxide were added, and after stirring for 5 minutes. , N
The mixture was transferred onto a metal plate under two air currents and left to stand at 25°C for 6 hours to obtain a crosslinked polymer.

しかる後、得られた重合物のＮ％を測定した結果、測定
値０．０５％（但し、計算値０．０５％）がめられ、ま
た、重合物を砕いて、５μの粒子としたものを５０倍量
の水で３回洗浄し、乾燥させたものについてＮ％を測定
した結果も、同様に測定値０．０５１＋であった。After that, as a result of measuring the N% of the obtained polymer, the measured value was 0.05% (however, the calculated value was 0.05%). The result of measuring N% of the product washed three times with 50 times the amount of water and dried was also 0.051+.

したがりて、本発明のテトラコシルーメトキシメチル−
ジアリル−アンモニウム−クロリドがポリエステル・ス
チレン樹脂と完全に共重合していることが確かめられた
。Therefore, the tetracosylmethoxymethyl-
It was confirmed that diallyl-ammonium-chloride was completely copolymerized with the polyester-styrene resin.

特許出願人　東邦化学工業株式会社Patent applicant: Toho Chemical Industry Co., Ltd.

Claims (1)

【特許請求の範囲】 １一般式１ 〔但し、Ｒ，Ｗは炭素数合計１−２４の炭化水素基もし
くはヒドロキシ置換炭化水素基、または、中間にエステ
ル結合を１個有する炭素数合計３−２７の炭化水素系基
もしくはヒドロキシ置換炭化水素系基、中間にエーテル
結合を１個有する炭素数合計２−２７の炭化水素系基も
しくはヒドロキシ置換炭化水素系基、中間にアミド結合
を１個有する炭素数合計４−２７の炭化水素系基もしく
はヒドロキシ置換炭化水素系基、水素もしくは炭素数合
計１−２４の炭化水素基を末端に連結するポリ（但し、
２−５０モル）オキシアルキレン（但し、炭素ａｌ−８
）基であり、Ａ−はハロゲンイオンもしくは有機または
無情のオキシ酸イオンであり、かつ％ＲＩＲ’のうちの
少なくとも一方が、炭素数合計８以上の炭化水素基もし
くはヒドロキシ置換炭化水素基であるかまたは炭素数７
以上の炭化水素基もしくはヒドロキシ置換炭化水素基を
連結する基である。〕にて表わされる非自己重合性反応
性カチオン界面活性剤。 ２一般式Ｉにて表わされる化合物が２−ヒドロキシオク
タデシル−メチル−ジアリル−アンモニウム−クロリド 重合性反応性カチオン界面活性剤。 ６一般式１にて表わされる化合物がジ（２−ヒドロキシ
テトラデシル）−ジアリル−アンモニウム−プロミドで
ある特許請求の範囲第１項記載の非自己重合性反応性カ
チオン界面活性剤。 ４一般式■にて表わされる化合物が３＾トリデシルオキ
シ−２−ヒドロキシプロピル−ベンジル−ジアリル−ア
ンモニウム−クロリド 囲第１ＪＪＩ記載の非自己重合性反応性カチオン界面活
性剤。 ５一般式１＃ごて表わされる化合物がノニルフェノキシ
ポリ（９モル）エチレンオキシエチル−メチル−ジアリ
ル−アンモニウム−クロリドである特許請求の範囲第１
項記載の非自己重合性反応性カチオン界面活性剤。[Claims] 1 General formula 1 [However, R and W are a hydrocarbon group or a hydroxy-substituted hydrocarbon group having a total of 1 to 24 carbon atoms, or a total of 3 to 27 carbon atoms having one ester bond in the middle. hydrocarbon group or hydroxy-substituted hydrocarbon group, a hydrocarbon group or hydroxy-substituted hydrocarbon group with a total of 2 to 27 carbon atoms having one ether bond in the middle, a carbon number having one amide bond in the middle A polycarbonate group having a total of 4 to 27 hydrocarbon groups or a hydroxy-substituted hydrocarbon group, hydrogen or a hydrocarbon group having a total of 1 to 24 carbon atoms connected to the terminal (however,
2-50 mol) oxyalkylene (however, carbon al-8
) group, A- is a halogen ion or an organic or ruthless oxyacid ion, and at least one of %RIR' is a hydrocarbon group or a hydroxy-substituted hydrocarbon group having a total of 8 or more carbon atoms. or carbon number 7
This is a group that connects the above hydrocarbon groups or hydroxy-substituted hydrocarbon groups. ] A non-self-polymerizable reactive cationic surfactant. 2 The compound represented by the general formula I is a 2-hydroxyoctadecyl-methyl-diallyl-ammonium-chloride polymerizable reactive cationic surfactant. 6. The non-self-polymerizable reactive cationic surfactant according to claim 1, wherein the compound represented by general formula 1 is di(2-hydroxytetradecyl)-diallyl-ammonium-bromide. 4. The non-self-polymerizable reactive cationic surfactant described in No. 1 JJI, wherein the compound represented by the general formula (1) is 3^tridecyloxy-2-hydroxypropyl-benzyl-diallyl-ammonium-chloride. Claim 1, wherein the compound represented by the general formula 5 is nonylphenoxypoly(9 mol) ethyleneoxyethyl-methyl-diallyl-ammonium chloride.
Non-self-polymerizable reactive cationic surfactant as described in .