JPS61185514A - Production of resin emulsion - Google Patents

Abstract

PURPOSE:To obtain a resin emulsion having excellent chemical stability and giving a coating film having excellent water-resistance and adhesivity, by carrying out the emulsion polymerization of an unsaturated monomer in the presence of a specific monomer. CONSTITUTION:The objective emulsion can be produced by the emulsion polymerization of an unsaturated monomer (e.g. acrylic acid, styrene, etc.) in the presence of preferably 0.5-10wt% polyalkylene glycol mono(meth)allyl ether monomer of formula I [R1 is H or methyl; m is 1-100; R2 is 2-4C alkylene; (OR2)m may contain different kind of recurring unit] and/or an allyl ether monomer of formula II [p is 1-4; q and r are 0-100; R3 and R4 are 2-4C alkylene; (OR3)q and (OR4)r may contain different kind of recurring unit; Y and Z are OH, 1-4C alkoxy, univalent or bivalent phosphoric acid group or sufonic acid group or sulfuric acid group, etc.] (e.g. 3-allylxypropane-1,2-diol).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a resin emulsion with excellent stability by copolymerizing a specific monomer when producing a resin emulsion by emulsion polymerization of unsaturated monomers.

Conventionally, resin emulsions obtained by emulsion polymerization have been widely used as raw materials in fields such as paints, adhesives, paper processing, fiber processing, mortar mixing, etc. from the viewpoint of environmental hygiene and quality saving. Emulsification of such a resin emulsion 1
In general, anionic emulsifiers, cationic emulsifiers, nonionic emulsifiers, or additives are used in the production of resin emulsions to reduce the generation of aggregates or improve the chemical stability of the resulting resin emulsion. It is necessary to use a large amount of emulsifier, and the resulting resin emulsion tends to generate bubbles, which reduces the water resistance and adhesion of the film obtained by applying the emulsion, and causes the film to soften. has.

For example, when used as a binder for paper processing or a paint binder, the emulsifier may cause bubbles and pinholes in the film, or the emulsifier in the film may reduce the water resistance and slipperiness of the film.

Furthermore, when used as a cement mixture, a large amount of emulsifier is added to prevent agglomeration of the resin emulsion due to polyvalent metal ions such as Ca2+ and At3+ eluted from the cement. This may cause bubbles to be generated during kneading or reduce the water resistance of the polymer cement.

The present inventors have conducted intensive studies to improve the drawbacks of such resin emulsions, and have found that by copolymerizing a specific monomer during emulsion polymerization, it is possible to polymerize very stably. and the obtained bottle; and completed the present invention.

That is, the present invention involves copolymerizing the following monomer (1) and/or monomer (2) when producing a resin emulsion by emulsion polymerizing one or more unsaturated monomers. The present invention relates to a method for producing a resin emulsion characterized by the following.

(Note) Monomer (II has the general formula CH2=C-CH2(-ORz+mol((
1) (However, in the formula, R1 represents hydrogen or a methyl group, m
represents an integer of 1 to 100, R2 represents an alkylene group having 2 to 4 carbon atoms, and the N+ORt+m portion may be randomly bonded with different types of repeating structural units. ) A polyalkylene glycol mono(meth)allyl ether monomer.

Monomer (2) has the general formula (wherein p represents an integer of 1 to 4, q and r each independently represent O or an integer of 1 to 100, R3 and R4 each independently represent the number of carbon atoms Represents 2 to 4 alkylene groups, +ORs +q and +OR4+r may each have different repeating structural units randomly bonded,
Y and 2 each independently represent a hydroxyl group, an alkoxyl group having 1 to 4 carbon atoms, a monovalent phosphoric acid group (however, a monovalent metal,
It includes salts of divalent metals, ammonia or organic amines, or mono- or diesters of alkyl groups having 1 to 4 carbon atoms. ), a monovalent sulfonic acid group (however, a monovalent metal, a divalent metal, ammonia or organic amine salt, or a carbon number 1
-4 alkyl groups), or a monovalent sulfate group (including salts of monovalent metals, divalent metals, ammonia or organic amines, or esters of alkyl groups having 1 to 4 carbon atoms). or ■Y and 2 together represent 2
It represents a valent phosphoric acid group, a divalent sulfonic acid group, or a divalent sulfuric acid group. ) is an ether type monomer shown by

The monomer (1) used in the present invention is a polyalkylene glycol mono(meth)allyl ether monomer represented by the above general formula (1), and has an added mole number m of acyl and alkylene oxide of 1 to 100. It is.

If the number m of added moles exceeds 100, the copolymerization reactivity is low and the resin emulsion of the present invention cannot be obtained. Preferably, those having an added mole number m in the range of 5 to 90 are effectively used.

The monomer (2) is an allyl ether monomer represented by the general formula (1), for example, 3-allyloxypropane-
1,2-diol, 3-allyloxypropane-1,2-
Diol phosphate, 3-allyloxypropane-1*
2 Volsulfone), 3-allyloxypropane-1,2-diolpurphate, 3-allyloxy-1
, 2-di(poly)oxyethylene ether propane, 3
-Allyloxy-1,z-cy(poly)oxyethylene ether propane phosphate, 3-allyloxy-1,2-
di(poly)oxyethylene ether propane sulfone)
Di(poly)oxypropylene ether propane phosphate, 3-allyloxy-1,2-di(poly)oxypropylene ether propane sulfonate, 6-allyloxydihexipun-1-2=L 4-5-pentaol, 6-
Allyloxy dihexibun-1.2.3.4.5-pentaol phosphate, 6-aryloki dihexibun-1.2.
L 4.5-Pentaol sulfonate, 6-allyloxy-Is L 3e 4* 5-penta(poly)oxyethylene ether propane, 6-allyloxy-1= L
3.4* 5-penta(poly)oxypropylene ether hexane, 3-allyloxy-2-hydroxypropanesulfonic acid and its monovalent metal salt, divalent metal salt, ammonium salt or organic amine salt, or compounds thereof Phosphoric acid ester or sulfuric acid ester and their monovalent metal salt, divalent metal salt, ammonium salt or organic amine salt: 3-A! j o # Fucy - (poly)oxyethylenepropanesulfonic acid and its monovalent metal salt, divalent metal salt, ammonium salt or organic amine salt, or phosphoric acid ester or sulfuric acid ester of these compounds, and 1 thereof Valent metal salt, divalent metal salt, ammonium salt or organic amine salt: 3-allyloxy-2-(poly)oxypropylenepropanesulfonic acid and its monovalent metal salt, divalent metal salt,
Ammonium salts or organic amine salts, phosphoric acid esters or sulfuric acid esters of these compounds, and monovalent metal salts, divalent metal salts, ammonium salts or organic amine salts thereof, etc. can be used.

To carry out the method of the present invention, one or more unsaturated monomers are added by a conventionally known emulsion polymerization method in the presence of monomer (1) and/or monomer (2). Copolymerization is sufficient.

The present invention does not particularly require an emulsifier, but has advantages such as excellent stability during polymerization, excellent chemical stability of the resulting emulsion, and excellent water resistance of the film. Conventionally known anionic surfactants, cationic surfactants, nonionic surfactants, protective colloids, etc. can also be used in combination in amounts that do not inhibit. In particular, by using an anionic surfactant in combination, it is possible to further enhance the stability during polymerization and the chemical stability of the resulting emulsion. It is rather preferable to use a surfactant in combination.

As the polymerization catalyst, inorganic peroxides such as ammonium persulfate and hydrogen peroxide; organic peroxides such as t-butyl hydroperoxide; and other radical-forming polymerization initiators can be used. The amount used is 1 unsaturated monomer
0.01 to 3 parts by weight, preferably 0.00 parts by weight
．． The ratio is 1 to 1 part by weight. If peroxides are used, reducing the reaction temperature by increasing the polymerization rate is necessary, reducing agents such as soluble sulfites or ascorbic acid or generating heavy metal ions in water such as ferrous sulfate can be used. Metal compounds can be combined with peroxides to form redox systems.

Chain transfer agents such as t-dodecylmercaptan and carbon tetrachloride can also be used.

The emulsion polymerization temperature is appropriately selected depending on the type and composition of the unsaturated monomer, the type of polymerization catalyst, etc., but is usually θ~100.
℃ range. Furthermore, according to the method of the present invention, monomer (1) and/or monomer (2) are not hydrolyzed during polymerization, and even under harsh conditions at relatively high temperatures, monomer (1) and/or monomer (2) are not hydrolyzed during emulsification. Stability is not impaired in any way.

The amount of water during emulsion polymerization is usually 300 to 50 parts by weight per 100 parts by weight of the unsaturated monomer.

There are no particular restrictions on the unsaturated monomer, such as methyl (
meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dimethylamine ethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, etc. (meth)acrylic acid ester of: styrene,
Styrenic monomers such as vinyltoluene and α-methylstyrene: (meth)acrylonitrile and other unsaturated nitrile compounds: (meth)acrylamide: Vinyl acetate: (meth)
α of acrylic acid, maleic acid, fumaric acid, itacone, etc.
, β-monoethylenically unsaturated carboxylic acids, salts thereof, etc., or 1a selected from these, or two or more thereof can be used.

The amount of monomer (1) and/or monomer (2) to be used is desirably maintained within a range of 0.5 to 10 weight percent of all monomers. If the amount used is less than O.5Zit%, the stability during polymerization and the chemical stability of the resulting emulsion may decrease; on the other hand, if the amount exceeds 10, the resulting resin The physical properties of the emulsion film, especially the water resistance, may deteriorate.

It is not clear whether the method of the present invention has such excellent effects in some cases. However, the monomer used in the present invention +1
) and/or monomer (2) has an oxyalkylene group in the molecule and a hydroxyl group, phosphoric acid group, sulfonic acid group, or sulfuric acid group at the end, and other unsaturated monomers By copolymerizing with the copolymer, an oxyalkylene group, hydroxyl group, phosphoric acid group, sulfonic acid group, or sulfuric acid group is introduced into the terminal or side chain of the resulting copolymer, which stabilizes the dispersed particles of the copolymer. It is conceivable that the water resistance of the film is improved because the copolymers have the ability to change the copolymer and the compatibility between the copolymers is excellent.

According to the method of the present invention, it is possible to produce a resin emulsion with good stability during emulsification, and the obtained resin emulsion has excellent chemical stability and good film water resistance and adhesion. It exhibits excellent characteristics for paper processing, paints, fiber processing, adhesives, and mortar mixing.

EXAMPLES Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples. Incidentally, unless otherwise specified, "parts" in the examples refer to parts by weight, and "parts by weight" refer to parts by weight.

Example 1 3 parts of polyethylene glycol monoallyl ether (containing 10 ethylene oxide units on average per molecule), 1 part of acrylic rR, 56 parts of 2-ethylhexyl acrylate, 40 parts of styrene and 30 parts of deionized water A mixture of 13 parts of an aqueous solution of unsaturated monomer was prepared by stirring
0 parts were prepared.

A glass flask equipped with a stirrer, a thermometer, a dropping funnel, a nitrogen gas inlet, and a reflux condenser was charged with 70 parts of deionized water and 1 part of potassium persulfate, and after purging the inside of the reaction vessel with nitrogen, it was heated in a hot water bath. did.

While maintaining the liquid temperature at 80° C., the aqueous solution of the unsaturated monomer was added dropwise over 180 minutes to carry out emulsion polymerization. After further holding at 80°C for 120 minutes to complete polymerization, it was cooled to room temperature and 28% ammonia water was added to adjust the pH to 9.0.
Adjusted to. A resin emulsion with a solid content of 50.0% and a viscosity of 200 cps was obtained.

Example 2 3-allyloxy-2 prepared in a similar manner to Example 1
-3 parts of sodium hydroxypropanesulfonate, 1 part of acrylic acid, 56 parts of butyl acrylate, 10 parts of 2-ethylhexyl acrylate, 30 parts of methyl methacrylate
The same polymerization operation as in Example 1 was repeated using 130 parts of an aqueous solution of an unsaturated monomer consisting of 30 parts of deionized water and 30 parts of deionized water.
A resin emulsion of ps was obtained.

Example 3 3 parts of polyethylene glycol monoallyl ether (containing an average of 10 ethylene oxide units per molecule), 1 part of acrylic acid, and 2-ethylhexyl ac! prepared in the same manner as in Example 1. 130 parts of an aqueous unsaturated monomer liquid consisting of 56 parts of Jl/-t, 40 parts of styrene, 0.5 parts of polyoxyethylene nonylphenyl ether sulfate sodium salt (number of moles of ethylene oxide added: 4), and 30 parts of deionized water. Using 5 parts, the same polymerization operation as in Example 1 was repeated to obtain a pH of 9.0 and a solid content of 50.
- A resin emulsion of 2% 1 viscosity of 500 cps was obtained.

Example 4 3-allyloxy-2 prepared in the same manner as Example 1
-3 parts of sodium hydroxypropanesulfonate, 1 part of acrylic acid, 56 parts of butyl acrylate, 10 parts of 2-ethylhexyl acrylate, 30 parts of methyl methacrylate
parts, polyoxyethylene nonylphenyl ether sulfate ammonium salt (number of moles of ethylene oxide added: 4)
)0.51) Using 130.5 parts of an aqueous solution of unsaturated monomers consisting of 1S and 30 parts of deionized water, the same polymerization operation as in Example 1 was repeated to obtain a pH of 9.0 and solid content. 50.
A resin emulsion of 1% and a viscosity of 570 cps was obtained.

Example 5 1 part of polyethylene glycol monoallyl ether (containing an average of 35 ethylene oxide units per molecule) prepared in the same manner as in Example 1, 2 parts of sodium 3-allyloxy-2-hydroxypronosulfonate,
The same polymerization procedure as in Example 1 was repeated using 130 parts of an aqueous solution of an unsaturated monomer consisting of 2 parts of methacrylic acid, 65 parts of butyl acrylate, 30 parts of methyl methacrylate, and 30 parts of deionized water to obtain PH9. , 0, solid content 50.
A resin emulsion with a coefficient of 0 and a viscosity of 230 cps was obtained.

Comparative Example 1 1 part, 2 parts of acrylic acid prepared in the same manner as in Example 1
-ethylhexyl aqueous IJL'-) 59 parts, styrene 4
0 parts, polyoxyethylene nonylphenyl ether sulfate ester sodium salt (number of moles of ethylene oxide added: 4
) Using 130:5 parts of an aqueous solution of an unsaturated monomer consisting of parts o, s and 30 parts of deionized water, the same polymerization procedure as in Example 1 was repeated to obtain a polymer with a pH of 9.0 and a solid state. min 48.5
%, a resin emulsion with a viscosity of 200 cps was obtained.
A large amount of agglomerates were generated during polymerization.

Comparative Example 2 1 part of acrylic acid, 2 parts of acrylic acid prepared in the same manner as in Example 1
-Ethylhexyl acrylate 56IIS, styrene 4
0 parts, polyoxyethylene nonyl phenol ether sulfate sodium 9m salt (number of moles of ethylene oxide added: 4
) Using 130.5 parts of an aqueous solution of an unsaturated monomer consisting of 3.5 parts of deionized water and 30 parts of deionized water, the same polymerization procedure as in Example 1 was repeated to obtain a polymer with a pH of 9.0 and a solid state. min 48.8
%, a resin emulsion with a viscosity of 1000 cps'
4.

Comparative Example 3 1 part of acrylic acid, 2 parts of acrylic acid prepared in the same manner as in Example 1
-56 parts of ethylhexyl acrylate, 40 parts of styrene, polyoxyethylene nonylphenyl ether sulfate ester sodium salt (number of moles of ethylene oxide added: 4)
Same as in Example 1, using 130.5 parts of an aqueous solution of an unsaturated monomer consisting of 0.5 parts, 3 parts of polyoxyethylene nonyl femol ether (number of moles of ethylene oxide added: 20), and 30 parts of deionized water. Reversing the polymerization operation of P
A resin emulsion with H9.0, solid content 49.1%, and viscosity 600 cps was obtained.

Example 6 Table 1 shows the evaluation results regarding the physical properties of the resin emulsions obtained in Examples 1 to 5 and Comparative Examples 1 to 3 and their stability during emulsion polymerization.

Chapter 1 Table It was expressed in terms of hatred towards monomers.

The resulting residue was washed with water, dried at 105-1) 0°C for 5 minutes, weighed, and expressed as the ratio of the residue to the solid content of the resin emulsion used.

Note 3) After accurately weighing the weight of the resin emulsion film using an applicator on a Teflon plate (the weight of the film before immersion in water), it was immersed in deionized water at 20°C for 24 hours.

The film after immersion in water for 24 hours was taken out, the surface was gently wiped with F paper, the weight of the film after immersion in water was accurately weighed, and the water absorption rate was determined using the following formula.

Claims (1)

[Claims] 1. When producing a resin emulsion by emulsion polymerization of one or more unsaturated monomers, the following monomer (1)
and/or a method for producing a resin emulsion, which comprises copolymerizing monomer (2). (Note) Monomer (1) has a general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (However, in the formula, R_1 represents hydrogen or a methyl group, m represents an integer from 1 to 100, and R_2 represents an alkylene group having 2 to 4 carbon atoms, and the -(OR_2)-_m portion may be randomly bonded with different repeating structural units.) Quantity. Monomer (2) has the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (II) (However, in the formula, p represents an integer from 1 to 4, and q and r each independently represent 0 or 1 to 100. Represents an integer, R_3 and R_4 each independently have 2 to 4 carbon atoms.
represents an alkylene group, -(OR_3)-_q and -
(OR_4)-_r may be randomly bonded with different repeating structural units, and Y and Z each independently represent a hydroxyl group, an alkoxyl group having 1 to 4 carbon atoms, or a monovalent phosphoric acid group. groups (including monovalent metals, divalent metals, salts of ammonia or organic amines, or mono- or diesters of alkyl groups having 1 to 4 carbon atoms), monovalent sulfonic acid groups (however, monovalent metals, salts of divalent metals, ammonia or organic amines, or esters of alkyl groups having 1 to 4 carbon atoms), or monovalent sulfate groups (however, salts of monovalent metals, divalent metals, ammonia or organic amines or [2] Y and Z together represent a divalent phosphate, a divalent sulfonic acid group, or a divalent sulfate group. represent. ) Allyl ether monomer represented by