JPH0841112A - New reactive surfactant, emulsifier for emulsion polymerization, and resin modifier - Google Patents

Abstract

PURPOSE:To obtain a new reactive surfactant which not only reacts as an emulsifier but also is gradually incorporated into a polymer through a chemical bond during polymerization by using a specified compound having a surface-active group and a polymerizable group in the molecule. CONSTITUTION:This surfactant is represented by the formula (wherein A<1> is 2-4C alkylene; R<1> is H or methyl; R<2> and R<3> are each H or a 1-4C hydrocarbon group; R<4> is an 8-24C hydrocarbon group or acyl; m is 0 to 50; and X is H or a nonionic, anionic, cationic or amphoteric hydrophilic group). It is desirable that the X in the formula is a group of -(A<2>O)n-H (wherein A<2> is 2-4C alkylene; and n is 1 to 100) or -(A<3>O)p-SO3M<1> (wherein A<3> is 2-4C alkylene; p is 0 to 100; and M<1> is H, an alkali metal, an alkaline earth metal, ammonium or 1-4C hydroxyalkylammonium).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel reactive surfactant. Further, the present invention relates to a novel emulsifier for emulsion polymerization and a novel vinyl resin modifier containing the surfactant as an active ingredient. Regarding

[0002]

2. Description of the Related Art Conventionally, surfactants have been emulsified, dispersed,
It has many functions such as cleaning, wetting, foaming, etc. By utilizing these functions, it is possible to use fiber, paper, rubber, plastic, metal, paint, ink, adhesive, pigment, civil engineering, etc. It is used in all fields. In particular, recently, the movement toward higher performance of terminal products using a surfactant has been activated, and along with this, a secondary defect of the surfactant has been pointed out. For example, paints, printing inks, adhesives, etc. are indispensable for surface active agents at the time of manufacturing the product, or for stabilizing the product, and in terms of workability, etc. A surfactant is not required when used for printing, adhesion, adhesion, etc., and rather the existing surfactants have properties such as water resistance and oil resistance of the coating film, printing surface, adhesive film, etc. Often worsens.

As measures against these problems, attempts have been made to reduce the compounding amount of surfactants and to polymerize the surfactants, but until the product stability and workability have been sufficiently solved. Has not reached.

Conventional emulsifying agents for emulsion polymerization include anionic surfactants such as alkyl sulfates, alkylbenzene sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters and pluronic type interfaces. Nonionic surfactants such as activators have been used.

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 freeze stability and the storage stability of the produced emulsion, and further, the emulsion. Emulsion physical properties such as particle size, viscosity and foamability, water resistance when formed into a film,
It is known that physical properties of the film such as weather resistance, adhesiveness, and heat resistance are greatly affected. However, the emulsion produced by emulsion polymerization using a normal emulsifier has a high foaming rate of the emulsion due to the emulsifier, and when the emulsion is made into a film, the emulsifier remains in the film in a free state, resulting in poor adhesion. It has been pointed out that there are problems such as deterioration of film physical properties such as water resistance, weather resistance and heat resistance.

In order to solve such a drawback, in recent years, a molecule having a group having surface activity and a group having a polymerizable group,
Proposals have been made regarding reactive surfactants that not only act as emulsifiers but are gradually incorporated into the polymer during polymerization by chemical bonds. For example, there are those described in JP-A-62-104802, but some monomers have poor reactivity and the above problems cannot be sufficiently solved.

Further, as a vinyl resin modifier, conventionally,
JP-A-1-174511 discloses a modifier for a vinyl polymer. However, when this modifier was used, a uniform copolymer could not be obtained because of poor compatibility with the monomer. Further, as an attempt to improve the compatibility, there is JP-A-1-174512, but there is a problem that the compatibility is still insufficient and the modifying effect on the polymer is insufficient. It was

Therefore, an object of the present invention is to provide a good novel reactive surfactant which does not have the above-mentioned drawbacks, a novel emulsifier for emulsion polymerization and a novel vinyl-based resin modifier containing the reactive surfactant as an active ingredient. To do.

[0009]

That is, the present invention has the general formula

Embedded image (In the formula, A ¹ is an alkylene group having 2 to 4 carbon atoms, and R ^{1 is}
Is a hydrogen atom or a methyl group, R ² and R ³ may be the same or different and are a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and R ⁴ is a hydrocarbon group having 8 to 24 carbon atoms. Or an acyl group, m is a number of 0 to 50, and X is a hydrogen atom, or a nonionic or anionic or cationic or zwitterionic hydrophilic group). Related to agents.

X in the general formula (1) is-(A ² O) _n-.
H (in the formula, A ² is an alkylene group having 2 to 4 carbon atoms, n
Is a number from 1 to 100).

Further, X in the general formula (1) is-(A ³ O) _p-.
SO ₃ M ¹ (In the formula, A ³ is an alkylene group having 2 to 4 carbon atoms, p is a number from 0 to 100, and M ¹ is a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or a carbon atom. Which is a hydroxyalkylammonium of the numbers 1 to 4).

X in the general formula (1) is

[Chemical 4] (In the formula, A ⁴ is an alkylene group having 2 to ⁴ carbon atoms, p is a number of 0 to 100, and M ² and M ³ are hydrogen atom, alkali metal, alkaline earth metal, ammonium or the number of carbon atoms. 1-4 hydroxyalkyl ammonium,
M ² and M ³ may be different or the same).

Furthermore, X in the general formula _{^{(1), - (A 5 O) s}} -
(CH _{2) r} -COOM ⁴ (wherein, A ⁵ is an alkylene group having 2 to 4 carbon atoms, s is a number of 0 to 100, r is 0
24, and M ⁴ is a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or a hydroxyalkylammonium having 1 to 4 carbon atoms).

Further, the present invention relates to a novel emulsifier for emulsion polymerization and a novel vinyl resin modifier, which contain the above-mentioned novel reactive surfactant as an active ingredient.

The above compound used in the present invention can be obtained, for example, as follows. That is, vinyl glycidyl ether and the general formula HO- (A ¹ O) _m -R ⁴ (2) (in the formula,
A ¹ is an alkylene group having 2 to ⁴ carbon atoms, R ⁴ is a hydrocarbon group having 8 to 24 carbon atoms or an acyl group, and m is 0 to
50, preferably a number of 0 to 20), a tertiary amine, a quaternary ammonium salt, a boron trifluoride ether complex salt, zinc borofluoride, tin tetrachloride, aluminum chloride, water. In the presence of a known catalyst such as sodium oxide or potassium hydroxide, the reaction is carried out at 50 ° C. to 160 ° C. for 3 hours to 20 hours until the epoxy groups disappear.
General formula

Embedded image (Wherein A ¹ , R ¹ , R ² , R ³ , R ⁴ and m have the same meanings as described above) are obtained.

Examples of the hydroxy compound or acid corresponding to the moiety represented by R ⁴ in the general formulas (2) and (3) include octanol, nonanol, decanol, undecanol, lauryl alcohol, myristyl alcohol, cetyl alcohol and stearyl alcohol. , Natural or synthetic alcohols such as oleyl alcohol, eicosanol,
Alkylphenols such as octylphenol, nonylphenol, dinonylphenol, and further caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid,
Examples thereof include acids such as myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, and arachidic acid (or reactive derivatives such as acid halides and acid anhydrides).

The compound of the general formula (3) corresponds to X = H in the general formula (1). As an example of producing a compound having a nonionic hydrophilic group as X in the general formula (1),
80 to 160 alkylene oxide having 2 to 4 carbon atoms is added to the compound of (3) in the presence of a catalyst such as sodium hydroxide, potassium hydroxide and boron trifluoride by using a pressure reactor.
Reaction at ℃, general formula

[Chemical 6] (Wherein A ¹ , A ² , R ¹ , R ² , R ³ , R ⁴ and m have the same meanings as described above, and n is a number from 1 to 100).

The alkylene oxide used is
Examples include ethylene oxide, propylene oxide, and butylene oxide. These may be used alone or as a mixture. Moreover, you may add and use in a block form.

As an example of producing a compound having an anionic hydrophilic group as X in the general formula (1), general formula (3) or
The compound of the formula (4) is converted to a sulfuric acid ester by a known method using sulfuric acid, anhydrous sulfuric acid, chlorosulfonic acid, sulfamic acid, etc.

[Chemical 7] (In the formula, A ¹ , A ³ , R ¹ , R ² , R ³ , R ⁴ and m have the same meanings as described above, p is a number of 0 to 100, M ¹ is a hydrogen atom, an alkali metal, Alkaline earth metal, ammonium, hydroxyalkylammonium having 1 to 4 carbon atoms) or a compound of the general formula (3) or (4) using phosphorus pentoxide, polyphosphoric acid, etc. Phosphoric acid esterified by the method

Embedded image (In the formula, A ¹ , A ⁴ , R ¹ , R ² , R ³ , R ⁴ and m have the same meaning as described above, q is a number from 0 to 100, and M ² and M ³
Is a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, or a hydroxyalkylammonium having 1 to 4 carbon atoms, and M ² and M ³ may be different or the same.) Or a compound of the general formula (3) or (4) is subjected to ether carboxylation by a known method using a monohalogenated lower carboxylic acid such as monochloroacetic acid, monobromoacetic acid, monochloropropionacetic acid, etc.

[Chemical 9] (In the formula, A ¹ , A ⁵ , R ¹ , R ² , R ³ , R ⁴ and m have the same meaning as described above, s is a number of 0 to 100, and r is 0 to 2
4 is a number, and M ⁴ is a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, or a hydroxyalkylammonium having 1 to 4 carbon atoms).

Alkali metals and ammonium are preferable as M ¹ , M ² , M ^{3 and} M ⁴ in the above general formulas (5), (6) and (7).

The novel reactive surfactant of the present invention is particularly a reactive surfactant having reactivity with a vinyl group, and it is an emulsifier for emulsion polymerization, a vinyl-based resin modification (hydrophilicity adjustment, compatibility improvement, Antistatic property, antifogging property, water resistance property, adhesive property property, dyeability property, film forming property property, weather resistance property, blocking resistance property, etc.).

The emulsifier for emulsion polymerization of the present invention contains the above-mentioned novel reactive surfactant as an active ingredient, and R
^The number of carbon atoms in ¹ is preferably 8 to 24, and m is 0 to
It is preferably 50, more preferably 0 to 20.

Suitable for applying the novel emulsion polymerization emulsifying agent of the present invention is emulsion polymerization of vinyl monomers, for example, vinyl compounds such as vinyl acetate, vinyl propionate, alkyl vinyl ether, alkyl vinyl ketone, and the like. Acrylic monomers such as acrylic acid, methyl acrylate, methyl methacrylate, acrylonitrile and acrylamide, ethylene, propylene, 1-butene, 1-pentene, 1-hexane, 1-heptene, 1-
Octene, 1-nonene, 1-decene, 1-undecene,
Monomers such as α-olefins having 2 to 30 carbon atoms such as 1-dodecene, 1-tridecene and 1-tetradecene, halogen-containing monomers such as vinyl chloride and vinylidene chloride, maleic anhydride, maleic acid esters and itaconic acid. Esters may be mentioned. The monomer used is not limited to the above.

The amount of the novel emulsifying agent for emulsion polymerization of the present invention can be optionally used within the range of the usual amount of the conventionally known emulsifying agent for emulsion polymerization. 0.1 to 20% by weight, preferably 0.2 to
10% by weight is good.

Suitable for applying the novel vinyl resin modifier of the present invention is a resin from a vinyl monomer, for example, vinyl acetate, vinyl propionate, alkyl vinyl ether, alkyl vinyl ketone, and other vinyl. Compounds and acrylic monomers such as acrylic acid, methyl acrylate, methyl methacrylate, acrylonitrile, acrylamide, ethylene, propylene, 1-butene,
1-pentene, 1-hexane, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-
Monomers such as α-olefins having 2 to 30 carbon atoms such as dodecene, 1-tridecene, 1-tetradecene, halogen-containing monomers such as vinyl chloride and vinylidene chloride, maleic anhydride, maleic acid esters, itaconic acid esters Is mentioned. The monomer used is not limited to the above.

The novel vinyl resin modifier of the present invention can simultaneously improve the compatibility with the monomer and the modifying effect. Further, by using the novel vinyl resin modifier of the present invention, the resin used is permanently antistatic,
It is possible to impart anti-fogging property.

The amount of the novel vinyl resin modifier used in the present invention can be variously changed according to the kind of the monomer, the purpose of the modification, the required performance and the like. 0.1 to 95% by weight can be used. Particularly, when a water-soluble resin having insufficient hydrophilicity is to be made into a highly hydrophilic polymer, etc., 10 to 80% by weight based on the monomer. Preference is given to using.

Polymers for other uses such as water resistance, adhesiveness, antistatic property, antifogging property, dyeability, film forming property, weather resistance, blocking resistance, etc., or for polymer alloys. When it is intended to impart compatibilization property to the monomer, it is preferably used in an amount of 0.1 to 20% by weight based on the monomer.

When the novel vinyl-based resin modifier of the present invention is used, in order to improve the physical properties of the polymer, a cross-linkable divinyl compound such as divinylbenzene, ethylene glycol dimethacrylate, methylenebisacrylamide, etc. is usually used in the usual amount range. Can be used at will.

[0030]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited thereto. Production Example A 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 performed at 30 ° C. under a reduced pressure of 10 mmHg or less for 30 minutes. The pressure is returned to normal pressure with nitrogen, cooled to 90 ° C., and 200 g of vinyl glycidyl ether is added dropwise using a dropping funnel.
After dropping, the mixture was aged at 90 ± 5 ° C. for 5 hours. The product obtained in 1. was charged into a pressure reactor and ethylene oxide 10, 20, 40, 80 mol (in the table below, 10 EO, 20 EO, 40 EO, 80 E respectively)
Each of which is referred to as O) was added to obtain a novel reactive surfactant (A) as a pale yellow solid product.

Production Example B Dobanol 23 [Mitsubishi Petrochemical Co., Ltd. was used instead of nonylphenol.
Co., Ltd., mixed alcohols having 12 and 13 carbon atoms, average molecular weight 195) and using boron trifluoride ethyl ether complex as a catalyst, the same reaction as in Production Example A was performed to obtain white solid ethylene oxide 10 A new reactive surfactant (B) was obtained as a 40, 80 mol adduct.

Production Example C An ethylene oxide adduct of a mixed secondary alcohol having 12 to 14 carbon atoms (average number of moles of ethylene oxide added: 3 moles) was used in place of nonylphenol, and a boron trifluoride ethyl ether complex was used as a catalyst. Then, the same reaction as in Production Example A is performed to obtain white solid ethylene oxide 10,
New reactive surfactant (C) as 40,80 mol adduct
I got

Production Example D A similar reaction was carried out using methyl vinyl glycidyl ether instead of the vinyl glycidyl ether of Production Example A,
The novel reactive surfactant (D) was obtained as a white solid of 10 mol of ethylene oxide adduct.

Production Example E 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 performed at 30 ° C. under a reduced pressure of 10 mmHg or less for 30 minutes. The pressure is returned to normal pressure with nitrogen, cooled to 90 ° C., and 200 g of vinyl glycidyl ether is 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 cooled to 0 to 5 ° C. 72.8 g of chlorosulfonic acid was added dropwise thereto using a dropping funnel. After dropping, stir at the same temperature for 1 hour,
The generated HCl was removed by blowing nitrogen. afterwards,
The solution was neutralized with an aqueous sodium hydroxide solution to obtain a soda salt, and a new reactive surfactant (E) was obtained.

Production Example F The same reaction as in Production Example E was carried out using dovanol 23 instead of nonylphenol to obtain a novel reactive surfactant (F) as a product.

Production Example G The same reaction as in Production Example E was carried out by using a 3 mol adduct of ethylene oxide with a secondary alcohol having 12 to 14 carbon atoms instead of nonylphenol, and a novel reactive surfactant (G) was obtained as a product. Got

Production Example H A novel reactive surfactant (H) was obtained as a product by carrying out the same reaction as in Production Example E using 30 mol of ethylene oxide adduct of nonylphenol instead of nonylphenol.

Production Example I 10 mol of ethylene oxide was added to the compound obtained in Production Example E-, and this was treated with chlorosulfonic acid to synthesize a sulfuric acid ester, and a novel reactive surfactant (I ) Got.

Production Example J The same reaction as in Production Example E- was carried out using dovanol 23 instead of nonylphenol. 200 g of the product obtained in 1. was placed in a 500 ml glass four-neck flask, and 37 g of phosphorus pentoxide was added at 40 ° C.
Was thrown in. After the introduction, the mixture was heated to 60 ° C. and reacted for 2 hours, and then aged at 80 ° C. for 2 hours. Then, the solution was neutralized with an aqueous sodium hydroxide solution to obtain a novel reactive surfactant (J) as a soda salt.

Production Example K A new reactive surfactant (K) was obtained in the same manner as in Production Example E except that the reaction was neutralized with an aqueous ammonia solution.

Production Example L A novel reactive surfactant (L) was obtained in the same manner as in Production Example J except that it was neutralized with an aqueous potassium hydroxide solution.

Preparation Example M Dobanol 23 was used in place of nonylphenol to carry out the same reaction as Preparation Example E-. 200 g of the product obtained in 1. and monochloroacetic acid 6
4 g was charged and the reaction was carried out under reduced pressure of 60 ± 5 ° C. and 10 mmHg or less to obtain a new surfactant (M) as a product.

The following reactive surfactants were used for comparison. Comparative Example 1 General formula described in JP-A-62-104802

[Chemical 10] R ₁ is a hydrogen atom, R ₂ is a nonylphenyl group,
There an ethylene group, m is 0, X is _{- (CH 2 CH 2 O)} 10 -H compounds.

Comparative Example 2 R ₁ of the general formula (8) in Comparative Example ₁ is a hydrogen atom and R ₂
Is a nonylphenyl group, A is an ethylene group, m is 0, and X is-.
_{(CH 2 CH 2 O) 10} -SO 3 Compound of NH _4.

Example 1 Novel reactive surfactants (A) to (M) of the present invention and comparative examples
Regarding (1) and (2), the surface tension of the aqueous solution was measured (the surface tension was measured by the Wilhelmy method). The results are shown in Table 1.

[0046]

[Table 1]

Example 2 Surfactants (A) to (M) of the present invention, Comparative Example (1), and
Regarding (2), the dispersion performance of carbon black and the emulsification performance of toluene were measured. The results are shown in Table 2.

The test method is as follows. <Dispersion performance test method> 1 g of the surfactant and 10 g of carbon black were placed in a graduated cylinder with a stopper of 100 ml, and dissolved and dispersed in water to adjust to 100 ml. next,
After shaking the graduated cylinder 100 times a minute,
It was allowed to stand at 25 ° C for 1 hour. After that, 30c from the liquid surface
105 ℃ after filtering through a glass filter
After drying, the dispersibility was measured by the following formula from the weight of the residue on the glass filter. Dispersion performance (%) = residue weight of glass filter (g) / 3
(g) x 100

<Emulsification performance test method> 5 ml of a 0.5% aqueous solution of a surfactant and 5 ml of kerosene were added to a test tube with a stopper having a capacity of 20 ml, and the mixture was shaken 100 times for 1 minute and then at 25 ° C for 1 hour. And let it stand. Then the volume of the emulsified layer
(ml) was measured, and the emulsifying property was measured by the following formula. Emulsification performance (%) = emulsified layer (ml) / 10 (ml) x 100

[0050]

[Table 2]

Example 3 Novel reactive surfactants (A) to (M) of the present invention and comparative examples
Using the reactive surfactants of (1) and (2), emulsion polymerization was carried out using a styrene monomer as a monomer. With respect to the obtained polymer emulsion, its mechanical stability, foamability, and reaction rate of the reactive surfactant were measured from the obtained polymer emulsion. Table 3 shows the results.

<Polymerization method> 180 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, 10 g of the novel reactive surfactants (A) to (M) of the present invention and 10 g of the surfactants of Comparative Examples (1) and (2) were dissolved in 100 g of styrene, and 33 g and potassium persulfate of 0.
6 g was added to the reaction vessel, and polymerization was initiated at 70 ° C. Then, the remaining monomer and the reactive surfactant mixture were continuously dropped into the reactor over 2 hours, and after the dropping was completed, the mixture was aged for 2 hours to obtain an emulsion.

<Measurement / Evaluation Method> Mechanical Stability Emulsion 50 g was measured with a Marron stability tester at 10 k.
g, 1000 rpm, rotating for 5 minutes, the produced coagulum was filtered through a 100 mesh wire mesh, the filter residue was washed with water and dried at 105 ° C. for 2 hours, and this weight was expressed in% by weight based on the solid content. Represent Effervescent emulsion is diluted twice with water and 20 ml of this diluted emulsion is put into a 100 ml graduated test tube.
Measure the foam height when shaken up and down for 2 seconds and display in ml. Reaction rate The polymer emulsion was analyzed by HPLC, the content of unreacted surfactant was determined from the calibration curve of the reactive surfactant, and the reaction rate was calculated. Table 3 shows the results.

[0054]

[Table 3]

Example 4 Novel reactive surfactants (A) to (M) of the present invention and comparative examples
Emulsion polymerization was carried out in the same manner as in Example 3 except that styrene / butadiene (1/1 weight ratio) was used as the monomer, using the reactive surfactants of (1) and (2). The reaction rate of the reactive surfactant was measured for the obtained polymer emulsion. The results are shown in Table 4.

[0056]

[Table 4]

Example 5 100 g of xylene 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, 150 g of styrene, 7.5 g of the novel reactive surfactants (A) to (M) of the present invention and the reactive surfactants of Comparative Examples (1) and (2) were used as modifiers, respectively, and 2 g of benzoyl peroxide was used. A mixed solution of 1 g of di-tert-butyl peroxide was prepared, and the mixed solution was continuously added dropwise into the reaction vessel at a reaction temperature of 130 ° C. over 2 hours. Furthermore, xylene 10 g, benzoyl peroxide 0.5
g, and a mixed solution of 0.5 g of di-tert-butyl peroxide was added dropwise, and the mixture was reacted for 2 hours. Then cool down,
90 g of xylene was added to obtain a polymer solution. A polymer film having a thickness of 0.2 mm was prepared from each of the obtained polymer solutions by a conventional method, and water resistance, antifogging property,
The antistatic property was evaluated. The results are shown in Table 5.

<Measurement / Evaluation Method> Water resistance of film 1 g of polymer film was placed in boiling water and boiled for 24 hours,
Then, it was dried at 105 ° C. for 2 hours and the change of the film was observed. ⊚: No change, ◯: Part of the film surface is clouded, Δ: Part of the film is deformed, ×: Entire film is deformed Anti-fog property of the film The contact angle of water with respect to the polymer film was measured. Antistatic Agent of Film The polymer film was allowed to stand in an atmosphere of a temperature of 20 ° C. and a humidity of 45% for 24 hours, and the surface resistivity was measured.

[0059]

[Table 5]

Example 6 100 g of xylene 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, 75 g of styrene, 75 g of butadiene, the novel reactive surfactants (A) to (M) of the present invention and Comparative Example (1)
In addition, a mixed solution of 7.5 g, benzoyl peroxide 2 g, and di-tert-butyl peroxide 0.5 g as the modifying agents of each of the reactive surfactants of (2) was prepared, and the mixed solution was prepared at a reaction temperature of 130 ° C. Was continuously added dropwise into the reaction vessel over 2 hours. Further, a mixed solution of 10 g of xylene, 0.5 g of benzoyl peroxide and 0.5 g of di-tert-butyl peroxide was added dropwise and the reaction was carried out for 2 hours. Then, the mixture was cooled and 90 g of xylene was added to obtain a polymer solution. A polymer film having a thickness of 0.2 mm was prepared from each of the obtained polymer solutions by a conventional method, and water resistance, antifogging property and antistatic property were evaluated in the same manner as in Example 5.
The results are shown in Table 6.

[0061]

[Table 6]

[0062]

The effect of the present invention is to provide a good novel reactive surfactant which does not have the above-mentioned drawbacks. Another effect of the present invention is to provide a good novel emulsifier for emulsion polymerization which does not have the above-mentioned drawbacks. Further, another effect of the present invention is to provide a good novel vinyl resin modifier without the above-mentioned drawbacks.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location C08F 299/02 MRS

Claims (7)

[Claims] 1. A compound of the general formula (In the formula, A ¹ is an alkylene group having 2 to 4 carbon atoms, and R ^{1 is}
Is a hydrogen atom or a methyl group, R ² and R ³ may be the same or different and are a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and R ⁴ is a hydrocarbon group having 8 to 24 carbon atoms. Or an acyl group, m is a number of 0 to 50, and X is a hydrogen atom, or a nonionic or anionic or cationic or zwitterionic hydrophilic group). Agent. 2. X in the general formula (1) is-(A ² O) _n --H.
The novel reactive surfactant according to claim 1, wherein A ² is an alkylene group having 2 to 4 carbon atoms and n is a number of 1 to 100. X of wherein general formula _{^{(1), - (A 3 O) p}} -SO
₃ M ¹ (In the formula, A ³ is an alkylene group having 2 to 4 carbon atoms, p is a number of 0 to 100, and M ¹ is a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or the number of carbon atoms. Is a hydroxyalkylammonium of 1 to 4), and the novel reactive surfactant according to claim 1. 4. X in the general formula (1) is represented by: (In the formula, A ⁴ is an alkylene group having 2 to ⁴ carbon atoms, p is a number of 0 to 100, and M ² and M ³ are hydrogen atom, alkali metal, alkaline earth metal, ammonium or the number of carbon atoms. 1 to 4 hydroxyalkylammonium, and M ² and M ³ may be different or the same). The novel reactive surfactant according to claim 1. X of 5. The general formula _{^{(1), - (A 5 O) s}} - (C
H _{2) r} -COOM ⁴ (wherein, A ⁵ is an alkylene group having 2 to 4 carbon atoms, s is a number of 0 to 100, r is 0 to 2
4 is a number, and M ⁴ is a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or a hydroxyalkylammonium having 1 to 4 carbon atoms).
The novel reactive surfactant described. 6. A novel emulsifier for emulsion polymerization, which comprises the novel reactive surfactant according to any one of claims 1 to 5 as an active ingredient. 7. A novel vinyl-based resin modifier containing the novel reactive surfactant according to claim 1 as an active ingredient.