JPH0323561B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a polymer.
More specifically, when emulsion polymerizing ethylenically unsaturated monomers that are insoluble or sparingly soluble in aqueous media, excellent polymerization stability can be obtained by using a combination of copolymerizable hydrophilic monomers having a specific structure.
The present invention also relates to a method for producing polymers and polymer emulsions with good mechanical and chemical stability. Conventionally, when producing a polymer in an aqueous medium, a method using sulfosuccinic acid monoallyl monoalkyl ester sodium salt has been introduced. However, this method has poor emulsion polymerization stability and produces a large amount of aggregates during polymerization. Furthermore, the mechanical and chemical stability of the obtained polymer emulsion was also extremely insufficient from a practical standpoint. The inventors of the present invention have arrived at the present invention as a result of extensive research into methods for producing polymers, particularly polymer emulsions, which do not have the above-mentioned drawbacks. That is, the present invention emulsion polymerizes an ethylenically unsaturated monomer in an aqueous medium using the following general formula: (In the formula, R ₁ and R ₂ are residues of an alcoholic hydroxyl group-containing compound, and at least one of R ₁ and R ₂ is a residue of (meth)allylic alcohol or its oxyalkylene ether. M is an alkali metal , alkaline earth metal, ammonium or amine cation, m is the valence or ionic valence of M), double bonds other than compound (A) and sulfonic acid (salt) group, carboxylic acid ( Polymerization is carried out in the presence of a monomer (B) having a hydrophilic group selected from the group consisting of a salt) group, a sulfuric acid ester (salt) group, a phosphoric acid ester (salt) group, and a polyoxyethylene group. This is a method for producing a polymer. In the general formula (1) representing the compound (A) used in the present invention, R ₁ and R ₂ are residues of an alcoholic hydroxyl group-containing compound. Examples of the alcoholic hydroxyl group-containing compound include the following compounds. (a-1) Alcohols 1) Aliphatic unsaturated alcohols (meth)allyl alcohol, oleyl alcohol, etc. 2) Aliphatic saturated alcohols Straight chain or branched saturated alcohols having 1 to 24 carbon atoms, preferably 8 to 20 carbon atoms, such as methyl -,
Ethyl, butyl, hexyl, 2-ethylhexyl, dodecyl, tridecyl,
Tetradecyl, hexadecyl, octadecyl, eicosyl alcohol, Ziegler alcohol, oxo alcohol, [Dovanol (manufactured by Shell Sekiyu), Diadol (manufactured by Mitsubishi Kasei), etc.], secondary alcohol [Tajitol S (manufactured by UCC)], etc. 3 ) Alicyclic alcohols and aromatic alcohols cyclohexyl alcohol, benzyl alcohol, etc. (a-2) Oxyalkylene ethers (alkylene oxide adducts) of active hydrogen-containing compounds Active hydrogen-containing compounds include alcohols, phenols, carboxylic acids, and amines. There are many types. Examples of alcohols include the alcohols described in (a-1). Examples of the phenols include alkylphenols having an alkyl group having 0 to 20 carbon atoms (nonylphenol, octylphenol, dodecylphenol, etc.). Examples of carboxylic acids include fatty acids having 8 to 20 carbon atoms (lauric acid, oleic acid, stearic acid, etc.). In addition, as amines, alkylamines having 8 to 20 carbon atoms (laurylamine,
stearylamine, etc.). Alkylene oxide has 2 to 4 carbon atoms
alkylene oxides (ethylene oxide, propylene oxide, butylene oxide, two or more of these, etc.) and substituted alkylene oxides (styrene oxide, etc.). Among the alkylene oxides, preferred are ethylene oxide, propylene oxide, and combinations thereof (random, block). The number of moles of alkylene oxide added is usually 1 to 10, preferably 1 to 5. At least one of R ₁ and R ₂ is a residue of (meth)allyl alcohol or its oxyalkylene ether. Among R ₁ and R ₂ , one is preferably a residue of (meth)allylic alcohol and the other is a residue of an aliphatic saturated alcohol having 8 to 20 carbon atoms. In general formula (1), M is an alkali metal, alkaline earth metal, ammonium or amine cation. Alkali metals include Li, Na and K. Alkaline earth metals include Ca, St, and Ba. Examples of amine cations include lower alkylamines (methylamine, ethylamine, isopropylamine, dimethylamine, trimethylamine, etc.), alkanolamines (monoethanolamine, diethanolamine, triethanolamine, etc.), and cations of amines such as morpholine. Among M, preferred are alkali metals, ammonium and amine cations, and particularly preferred are alkali metals and ammonium. Specific examples of the compound (A) represented by general formula (1) include the following. (A-1) (meth)allyl alcohol diester salt of sulfosuccinic acid Sulfosuccinic acid diallyl ester (Na salt)
Sulfosuccinic acid dimethallyl ester (K salt), etc. (A-2) Mixed ester salt of sulfosuccinic acid with (meth)allylic alcohol and other alcoholic hydroxyl group-containing compound Sulfosuccinic acid allyl tridecyl ester (Na salt), sulfosuccinic acid methacrylate Oleyl ester (ammonium salt), methallyl polyethylene glycol sulfosuccinate (molecular weight of polyethylene glycol: 150) ester (Na
salt) etc. (A-3) Sulfosuccinic acid (meth)allyl alcohol alkylene oxide adduct diester salt Sulfosuccinic acid methallyl alcohol ethylene oxide adduct (number of moles added: 2) diester (K salt), etc. In the present invention, the other compound (A ) and a hydrophilic group selected from the group consisting of a sulfonic acid (salt) group, a carboxylic acid (salt) group, a sulfuric acid ester (salt) group, a phosphoric acid ester (salt) group, and a polyoxyethylene group. Monomer (B) is used. Among the above hydrophilic groups, preferred are sulfonic acid (salt) groups and carboxylic acid (salt) groups. Examples of the salt include salts of alkali metals (Li, Na, K, etc.), ammonium, and amines (lower alkyl amines, alkanolamines, etc.). Preferred among the salts are alkali metal and ammonium salts. Specific examples of monomer (B) include the following compounds. (B-1) Vinyl monomer containing sulfonic acid (salt) group 1) Aliphatic vinyl sulfonic acid (salt) General formula

[Formula] (or salt) (2) (In the formula, R ₃ is H or a methyl group, and m is 0 or an integer from 1 to 4.) Vinyl alkanesulfonic acids (salts) are exemplified. Specific examples include vinylsulfonic acid (Na salt) and (meth)allylsulfonic acid (K, ammonium salt). 2) Aromatic vinyl sulfonic acid (salt) General formula (In the formula, R ₄ is H or a methyl group, n is 0 or 1, q is 1 or 2, R ₅ is a methyl group or ethyl group, and P is 0 or an integer from 1 to 4.) Aromatic sulfonic acid (salt)
can be given. Specifically, styrene sulfonic acid (o- and p-form) (Na salt or ammonium salt), styrene disulfonic acid (di-Na salt), 3-vinyltoluene-6-sulfonic acid (ammonium salt) and 3-vinyl Ethylbenzene-6-sulfonic acid (ammonium salt) is mentioned. 3) Acrylic sulfonic acid (salt) (meth)acryloyloxyalkane (or hydroxyalkane) sulfonic acid (salt) such as 3-(meth)acryloyloxypropanesulfonic acid (Na salt), 3-(meth)acryloyloxy-2 -Hydroxypropanesulfonic acid (ammonium salt), etc. and (meth)acrylamidoalkane (or hydroxyalkane)sulfonic acid (salt), such as 2-(meth)acrylamido-2-methylpropanesulfonic acid (Na salt), 3-(meth) Examples include acrylamide-2-hydroxypropanesulfonic acid (ammonium salt) and the compounds described in Japanese Patent Application No. 102200/1983. Among (B-1), preferred are the monomers described in 1) and 2), and particularly preferred are vinylsulfonic acid (salt), allylsulfonic acid (salt), and styrenesulfonic acid (salt). . (B-2) Vinyl monomer containing carboxylic acid (salt) group 1) Unsaturated monocarboxylic acid (salt) Unsaturated fatty acid (salt) such as (meth)acrylic acid (Na salt), crotonic acid (K salt), Examples include aromatic monocarboxylic acids (salts) such as vinylbenzoic acid (Na salt). 2) Unsaturated polycarboxylic acids (salts) Examples include maleic acid (Na salt), fumaric acid (ammonium salt), itaconic acid (Na salt), citraconic acid (K salt), and aconitic acid (Na salt). Among (B-2), unsaturated monocarboxylic acids (salts) are preferred, and (meth)acrylic acid (salts) is particularly preferred. (B-3) Vinyl monomer containing sulfate ester (salt) group 1) Sulfate ester (salt) of unsaturated alcohol
(Meth)allylic alcohol sulfate (Na
2) Sulfuric esters (salts) of unsaturated esters or ethers of polyols Examples of polyols include alkylene glycols, glycerin, and polyalkylene glycols. Specific examples include sulfuric acid esters (salts) such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and poly-oxyethylene-oxypropylene (random or block) glycol mono(meth)allyl ether. (B-4) Ethylene oxide adduct of polyoxyethylene group-containing vinyl monomer unsaturated alcohol or unsaturated carboxylic acid or block adduct of ethylene oxide and propylene oxide, etc. (B-5) Phosphoric acid ester (salt) Group-containing vinyl monomer Unsaturated alcohol phosphoric acid (mono, di) ester (di, mono) (salt), etc. Ethylenically unsaturated monomers used in the present invention include lipophilic vinyl monomers and weakly hydrophilic Examples include vinyl monomers. Lipophilic vinyl monomers include monoethylene vinyl monomers (ethylene, etc.), diene vinyl monomers (butadiene, chloroprene, etc.), aromatic vinyl monomers (styrenes, such as styrene,
α-alkylstyrene, etc.), halogen-containing vinyl monomers (vinyl chloride, vinylidene chloride, etc.) and higher alcohols (linear or branched natural or synthetic alcohols with 5 or more carbon atoms, such as 2-ethylhexyl alcohol, decyl alcohol, lauryl alcohol, Myristyl alcohol, cetyl alcohol, stearyl alcohol, oxo alcohol, Ziekler alcohol, paraffin oxidation alcohol, etc.) (meth)acrylate vinyl monomers are mentioned. Among these, preferred are (meth)acrylate vinyl monomers derived from higher alcohols, aromatic vinyl monomers, and halogen-containing vinyl monomers. Examples of weakly hydrophilic vinyl monomers include vinyl ester monomers (vinyl acetate, vinyl propionate, etc.), lower alcohols (linear or branched alcohols having 1 to 4 carbon atoms, such as methyl alcohol,
Examples include (meth)acrylate vinyl monomers (ethyl alcohol, butyl alcohol, etc.) and nitrile vinyl monomers (acrylonitrile, etc.). Among these, preferred are (meth)acrylate vinyl monomers and vinyl ester monomers derived from lower alcohols. These vinyl monomers may be used alone or in combination of two or more. The combinations when used together are not particularly limited, and include lipophilic monomers and lipophilic monomers, lipophilic monomers and weakly hydrophilic monomers, and weakly hydrophilic monomers and weakly hydrophilic monomers. Any combination may be used. (A) and (B) in the polymerization of ethylenically unsaturated monomers
The ratio is usually (A):(B)=10~95:90~ on a weight basis
5, preferably (A):(B)=20-70:80-30.
Outside the above-mentioned normal range, stable polymerization is difficult and it is difficult to obtain a polymer with excellent performance. The total weight of (A) and (B) is usually 0.2 to 20%, preferably 0.5 to 5%, based on the ethylenically unsaturated monomer. If the total weight is less than 0.2%, a significant amount of aggregates will be generated due to insufficient dispersion stability, and if it exceeds 20%, the entire system will become gel-like during the reaction due to an increase in the number of particles. The aqueous medium is water or water and water-soluble organic solvents (methanol, isopropanol, acetone, etc.)
Examples include mixed solvents with In the present invention, the polymer can be obtained by a known emulsion polymerization method. Known polymerization methods include [] Batch charging method [Ethylenically unsaturated monomer
(a), (A), (B), catalyst (b), aqueous medium (C), etc. are charged all at once into a reaction vessel at a relatively low temperature (for example, 50
or below 60°C], [] Monomer addition method [(A), (C) and if necessary
A part of (a) is charged into a reaction vessel together with (b), and (a)
A polymerization method in which [and (b) if necessary] is added as the polymerization progresses. Here (B) is (A) in advance
It may be charged into the reaction vessel together with (a), it may be added later together with (a), or these methods may be used in combination. ] and [] Monomer emulsion addition method [part of (A) or/and (B), (C), (b), etc. is charged into a reaction vessel, and the remaining (A) or/and (B)
(a) is emulsified in (C), and as the polymerization progresses, this emulsion (and (b) as well) is added sequentially. Among these three types of polymerization methods, the preferred methods are [] monomer addition method and [] monomer emulsion addition method. As the catalyst (initiator for polymerization) (b), inorganic peroxides (persulfates such as ammonium persulfate, potassium persulfate, etc.), organic peroxides (diacyl peroxides such as benzoyl peroxide, dialkyl peroxides such as di-t-butyl peroxide, hydroperoxides such as cumene hydroperoxide), azo compounds (azobisisobutyronitrile, azobisdimethylvaleronitrile, etc.)
and combination systems of inorganic or organic peroxides and reducing agents (sulfites such as sodium sulfite; acidic sulfites such as sodium bisulfite; ferrous salts such as ferrous ammonium sulfate). Among these, inorganic peroxides are preferred as catalysts. The amount of catalyst used is usually 0.01 to 2%, preferably 0.1 to 1%, based on the total ethylenically unsaturated monomers. The polymerization temperature is usually -5 to 100°C, preferably 50 to 90°C. The polymerization time is usually 0.1 to 50 hours, but it is determined depending on the required polymerization rate and is not particularly limited. In the present invention, a polymerization regulator may be used if necessary for purposes such as controlling the molecular weight of the polymer. Examples of polymerization modifiers include mercaptans (primary dodecyl mercaptan, tertiary dodecyl mercaptan, tertiary tetradecyl mercaptan, tertiary hexadecyl mercaptan, etc.), thiuram disulfide, xanthogen disulfide, polyatomic phenols, sulfur, selenium, substituted phosphine, Examples include carbon tetrachloride, amines, Schiff's bases, nitroso compounds, and diazomine derivatives. Further, a PH regulator such as sodium hydrogen carbonate may be used for the purpose of smoothly proceeding the polymerization. In the present invention, the polymer may be used as an emulsion, but the polymer can also be fractionated if necessary. Coagulants (mineral acids,
Examples include methods using inorganic salts, alcohol, etc.), methods using freezing, and methods using drying. Among these methods, the preferred method is the method using a coagulant because it is economical. In addition to having low foaming properties, the polymer emulsion obtained by the method of the present invention is compared to a polymer emulsion obtained using only the compound (A) or a hydrophilic monomer (B) other than (A). Stability (standing stability,
It has extremely excellent chemical stability, mechanical stability, etc.) and excellent polymerization stability, so the amount of aggregates generated during polymerization is extremely small. The polymer emulsion produced by the method of the present invention is effective for a wide range of uses such as paint vehicles, adhesives, paper processing agents, and fiber processing agents. It is effective for use as. The present invention will be further explained below with reference to Examples.
The present invention is not limited to these examples. All parts and percentages shown in the examples are based on weight unless otherwise specified. Example 1 150 parts of degassed ion-exchanged water, 2 parts of the compound (A) of the present invention,
Add and dissolve 2 parts of hydrophilic monomer (B), 0.1 part of sodium bicarbonate, and 0.3 part of ammonium persulfate, and after bubbling nitrogen gas at room temperature for 15 minutes, heat the mixture to 80°C. The mixture was added dropwise uniformly over a period of time to carry out polymerization while stirring. After finishing dropping 1
A polyethyl acrylate emulsion was obtained by aging for a period of time. The test results are shown in Table 1.

【table】

【table】

[Table] Example 2 A polystyrene emulsion was obtained by carrying out the same polymerization as in Example 1 except that styrene was used as the ethylenically unsaturated monomer in Example 2. The compound (A) and hydrophilic monomer (B) used and the performance test method were the same as in Example 1. Table 2 shows the test results.
Shown below.

【table】

【table】

Claims (1)

[Claims] 1. When emulsion polymerizing an ethylenically unsaturated monomer in an aqueous medium, the following general formula (In the formula, R ₁ and R ₂ are residues of an alcoholic hydroxyl group-containing compound, and at least one of R ₁ and R ₂ is a residue of (meth)allyl alcohol or its oxyalkylene ether. M is an alkali metal, alkaline earth metal, ammonium or amine cation, m is the valence or ionic valence of M), a double bond other than (A) and a sulfonic acid (salt) group, Carboxylic acid (salt)
Polymerization is carried out in the presence of a monomer (B) having a hydrophilic group selected from the group consisting of a polyoxyethylene group, a sulfuric acid ester (salt) group, a phosphoric acid ester (salt) group, and a polyoxyethylene group. Polymer manufacturing method. 2 The weight ratio of (A) and (B) is (A):(B)=10~95:90~5
The manufacturing method according to claim 1. 3. The manufacturing method according to claim 1 or 2, wherein the total weight of (A) and (B) is 0.2 to 20% based on the ethylenically unsaturated monomer. 4. The production method according to any one of claims 1 to 3, wherein the ethylenically unsaturated monomer is a lipophilic vinyl monomer and/or a weakly hydrophilic vinyl monomer.