JP3370966B2 - Polymer and its production method - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a polymer and the polymer. More specifically, the present invention relates to a polymerization method and a polymer obtained by radical polymerization in an aqueous solution, which has a narrow molecular weight distribution and produces a low molecular weight product.

[0002]

2. Description of the Related Art Conventionally, when radically polymerizable monomers are polymerized in an aqueous solution, as a method for controlling the molecular weight, in addition to changing the amount of the polymerization initiator, the polymerization temperature, the polymerization concentration, etc., a chain transfer agent such as an alkyl mercaptan is used. The method to use is known.

[0003]

However, in order to obtain a high molecular weight product, these methods have a problem that many low molecular weight products are inevitably produced and the molecular weight distribution is widened, which causes an adverse effect. The present invention provides a method for obtaining a polymer having a small molecular weight distribution by radical polymerization in an aqueous solution.

[0004]

The present inventors have found a method for obtaining a polymer having a narrow molecular weight distribution by using a specific chain transfer agent when polymerizing a radically polymerizable monomer in an aqueous solution, The present invention has been reached. That is, the present invention provides a method for producing a polymer by radically polymerizing at least one radically polymerizable monomer (a) which becomes water-soluble or becomes water-soluble by hydrolysis in the presence of water. And a radical copolymerizable compound (b) having a thioether group in the same molecule, the polymerization is carried out in the coexistence thereof; and the resulting polymer.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a compound represented by the following general formula (1) can be used as (b).

[0006]

[Chemical 2]

(In the formula, R ¹ is a hydrogen atom and has 1 to 4 carbon atoms.
Alkyl group, phenyl group, carboxyl group or salt-forming group thereof, or alkoxycarbonyl group having an alkoxy group having 1 to 12 carbon atoms; R ² is an alkyl group having 1 to 12 carbon atoms, aromatic having 6 to 12 carbon atoms A genus or araliphatic hydrocarbon group, an alkyl group is a carboxyalkyl group having 1 to 12 carbon atoms, an aminoalkyl group having 1 to 12 carbon atoms, or a hydroxyalkyl group having 1 to 12 carbon atoms. )

R ¹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms (for example, methyl, ethyl, propyl, butyl group, etc.), a phenyl group, a carboxyl group or a salt forming group thereof, or an alkoxy group having 1 carbon atom. To 12 alkoxycarbonyl groups (eg, methoxycarbonyl, ethoxycarbonyl, propylcarbonyl, n-butoxycarbonyl, 2-ethylhexyloxycarbonyl groups, etc.); R ²
Is an alkyl group having 1 to 12 carbon atoms (for example, methyl, ethyl, propyl, n-butyl, n-hexyl, 2-ethylhexyl, n-lauryl group, etc.), an aromatic or araliphatic group having 6 to 12 carbon atoms. Hydrocarbon group (eg, phenyl, benzyl, tolyl, xylyl, naphthyl, 2-phenylhexyl group, etc.), alkyl group having carboxyalkyl group having 1 to 12 carbon atoms (eg, carboxymethyl, carboxyethyl, carboxypropyl, carboxy) Hexyl, carboxydecyl group, etc.), aminoalkyl group having 1 to 12 carbon atoms (for example, 1-aminopropyl, 2-aminohexyl, 1-aminodecyl group, etc.) or 1 to 1 carbon atoms
2 hydroxyalkyl groups (2-hydroxyethyl, 2
-Hydroxypropyl, 1-hydroxyhexyl, 2-
A hydroxydecyl group, etc.). Examples of the salt-forming group include alkali metal salts (sodium salt, potassium salt, etc.),
Alkaline earth metal salt (calcium salt, magnesium salt, etc.), amine salt or ammonium [ammonium,
Tetraalkyl (C1-8) ammonium such as tetraoctylammonium] salt, organic amine {alkanolamine having 2-8 carbon atoms, polyalkylene (C1-8) polyamine (amino groups 2-10) or derivative thereof [C1-8 alkylated product, alkylene (C2-4) oxide adduct (1-30 mol)],
Lower alkylamines having 1 to 4 carbon atoms, etc.} salts.

Specific examples of such a compound (b) include, for example, t-butylallyl thioether, phenylallyl thioether, α- (carboxyethyl) thiomethyl-acrylic acid (salt), α- (2-carboxyethyl). Thiomethyl-styrene, α- (2-aminoethyl)
Thiomethylstyrene, α- (2-hydroxyethyl) thiomethyl-acrylic acid, α- (2-carboxyethyl)
Thiomethyl-ethyl acrylate, β-carboxyethylthio-methallyl, β-phenylthio-methallyl, β-
(T-butyl) thio-methallyl and the like can be mentioned. Of these, preferred are compounds having a hydrophilic group such as a carboxyl group, a hydroxyl group or an amino group in R ¹ and / or R ² . These compounds may be used alone or in combination of two or more.

The amount of the compound (b) used is that of the radical-polymerizable monomer [the radical-polymerizable monomer (a) which becomes water-soluble or becomes water-soluble by hydrolysis and other radical-polymerizable monomer (a3) capable of copolymerization]. Based on mass
Usually 0.001-1 mass%, preferably 0.005-
It is 0.3% by mass. The amount of compound (b) used is 0.00
When it is 1% or more, the effect of using (b), that is, the molecular weight distribution becomes narrow, and the production of low molecular weight products is small. On the other hand, 1
When it is at most%, the polymerization rate and the polymerization rate of the radically polymerizable monomer will be sufficient, and the productivity will be good. When the solubility of the compound (b) in the aqueous polymerization liquid is low, it is possible to carry out the polymerization by dissolving or dispersing it in the aqueous polymerization liquid in combination with a surfactant and the like. In addition, regarding the synthesis method of these compounds, for example, Macromolecule
s, 24, 3690 (1991).

In the present invention, the radically polymerizable monomer (a) is a water-soluble radically polymerizable monomer (a).
1) or the radical-polymerizable monomer (a2) which becomes water-soluble by hydrolysis can be used. As the water-soluble radically polymerizable monomer (a1), at least one acid group and / or its salt-forming group [carboxylic acid (salt) group, sulfonic acid (salt) group, sulfuric acid (salt) group, phosphoric acid (salt) Group, etc.], a hydroxyl group, an amide group, an amino group, a radical polymerizable monomer having a hydrophilic group such as a quaternary ammonium salt group.
It can be classified into anionic, nonionic and cationic monomers.

(I) Anionic or anionic monomer (i-1) Examples of the monomer having a carboxylic acid group include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, cinnamic acid; Dicarboxylic acids, such as maleic acid, fumaric acid, citraconic acid, itaconic acid, etc .; Monoalkyl (C1-8) esters of unsaturated dicarboxylic acids (above), such as maleic acid monobutyl ester, fumaric acid monobutyl ester, maleic acid. Examples thereof include carboxyl group-containing vinyl monomers such as ethyl carbitol monoester of acid, ethyl carbitol monoester of fumaric acid, citraconic acid monobutyl ester and itaconic acid glycol monoester, and a combination of two or more thereof.

(I-2) As the monomer having a sulfonic acid group, an aliphatic or aromatic vinyl sulfonic acid having 2 to 30 carbon atoms such as vinyl sulfonic acid, (meth) allyl sulfonic acid; styrene sulfonic acid, α- Methylstyrene sulfonic acid; (meth) acrylalkyl sulfonic acids [(meth) acryloxypropyl sulfonic acid, 2-hydroxy-3- (meth) acryloxypropyl sulfonic acid, 2- (meth) acryloylamino-2,2-dimethyl Ethanesulfonic acid, 3- (meth) acryloxyethanesulfonic acid, 2- (meth) acrylamido-2-methylpropanesulfonic acid, 3- (meth) acrylamide-2
-Hydroxypropanesulfonic acid]; alkyl (C3-18) (meth) allylsulfosuccinic acid ester and the like.

(I-3) Sulfuric acid ester-containing monomers include hydroxyalkyl (carbon number 2 to 6) (meth) acrylate sulfuric acid ester compounds [hydroxyethyl (meth) acrylate sulfuric acid ester compounds and the like]; poly (n =
2-30) Oxyalkylene (carbon number 2-4: single, random, or block) mono (meth) acrylate sulfate ester [poly (n = 5-15) oxypropylene monomethacrylate sulfate ester compound, etc.]; The compound etc. which are shown by the following general formula (I), (II), (III) are mentioned.

[0015]

[Chemical 3]

[In the formulas (I) to (III), R is 1 carbon atom.
To 15 alkyl groups, R'represents an alkyl group having 1 to 15 carbon atoms which may be substituted by a fluorine atom, A represents an alkylene group having 2 to 4 carbon atoms, and n is the same or different. May be present, and when different, it may be random or block, Ar represents a benzene ring, and n is 1
Indicates an integer of -50. ]

(I-4) Examples of the monomer having a phosphoric acid group include, for example, phosphoric acid monoesters of hydroxyalkyl (meth) acrylate (having 2 to 6 carbon atoms) [eg, monoethyl phosphate of hydroxyethyl (meth) acrylate, etc. ], A phosphoric acid diester of hydroxyalkyl (meth) acrylate (having 2 to 6 carbon atoms) [for example, phenyl-2-acryloyloxyethyl phosphate, etc.], an alkyl (meth) acrylate (having 2 to 6 carbon atoms) phosphonic acids [for example, ,
2-acryloyloxyethylphosphonic acid, etc.] and the like. (i-5) The salts of (i-1) to (ii-4) above can be mentioned. As the salt, the same salts as those mentioned above (at R ¹ ) can be mentioned.

(Ii) Nonionic monomer (ii-1) Examples of the monomer having a hydroxyl group include monoethylenically unsaturated alcohols [eg (meth) allyl alcohol]; divalent to hexavalent or higher. Unsaturated ester or ether [eg, alkylene glycol having 2 to 20 carbon atoms, glycerin, polyalkylene (2 to 4 carbon atoms) glycol (molecular weight 106 to 2000), etc.] such as hydroxyethyl (meth ) Acrylate, hydroxypropyl (meth) acrylate, triethylene glycol (meth) acrylate, poly-oxyethylene-oxypropylene (random or block) glycol mono (meth) allyl ether (the terminal hydroxyl group is etherified or esterified, Etc.] etc. It

(Ii-2) Examples of the monomer having an amide group include (meth) acrylamide, N-alkyl (C 1-8) (meth) acrylamide [eg N
-Methyl acrylamide, etc.], N, N-dialkyl (C 1-8) acrylamide [eg, N, N-dimethyl acrylamide, N, N-di-n- or i-propyl acrylamide, etc.], N-hydroxyalkyl ( (C1-8) (meth) acrylamide [eg N
-Methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, etc.]; N, N-dihydroxyalkyl (C1-8) (meth) acrylamide [eg, N, N-dihydroxyethyl (meth) acrylamide] , Vinyl lactams [eg, N-vinylpyrrolidone, etc.] and the like.

(Iii) Cationic or cationic monomer (iii-1) The amino group-containing monomer is an amino group-containing ester of monoethylenically unsaturated mono- or di-carboxylic acid, for example, dialkyl (carbon number). 1-8) Aminoalkyl (C2-10) (meth) acrylate, dihydroxyalkyl (C1-8) aminoalkyl (C2-10) ester, morpholinoalkyl (C1-8) ester, etc. For example, dimethylaminoethyl (meth) acrylate, diethylamino (meth) acrylate, morpholinoethyl (meth) acrylate,
Dimethylaminoethyl fumarate, etc.]; Amino group-containing amide of monoethylenically unsaturated mono- or di-carboxylic acid, for example, monoalkyl (having 2 to 10 carbon atoms) (meth)
Acrylamide [eg, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, etc.]; Heterocyclic vinyl compound [eg, 2
-Vinylpyridine, 4-vinylpyridine, vinylpyridines such as N-vinylpyridine, N-vinylimidazole and the like]; diallylamine and the like.

(Iii-2) As the monomer having a quaternary ammonium group, a quaternized product of a vinyl monomer containing a tertiary amino group (the vinyl monomer containing a tertiary amino group is alkylated with 1 to 8 carbon atoms). Agents such as methyl chloride, dimethylsulfate, benzyl chloride, dimethyl carbonate and the like quaternized with a quaternizing agent), for example, trimethylaminoethyl (meth) acrylate chloride, methyldiethylaminoethyl (meth) acrylate meth Sulfate, trimethylaminoethyl (meth)
Examples thereof include acrylamide chloride and diethylbenzylaminoethyl (meth) acrylamide chloride.

The radical-polymerizable monomer (a2) which becomes water-soluble by hydrolysis is at least one hydrolyzable group [an acid anhydride group, a lower alkyl (C1-C3) ester group, a nitrile group, etc.]. And a monomer having Examples of the monomer having an acid anhydride group include monomers having 4 to 20 carbon atoms such as maleic anhydride, itaconic anhydride, and citraconic anhydride, and examples of the monomer having an ester group include monoethylenically unsaturated carboxylic acid. Lower alkyl (C1-C3) esters [eg, methyl (meth) acrylate, ethyl (meth) acrylate], esters of monoethylenically unsaturated alcohols [eg, vinyl acetate, (meth) allyl acetate, etc.] Can be mentioned. Examples of the nitrile group-containing monomer include (meth) acrylonitrile. The hydrolysis of these (a2) may be carried out during the polymerization or after the polymerization, and usually the hydrolysis forms a salt to render it water-soluble. Examples of the salt include the same salts as those described above for the salt-forming group. Among these, the water-soluble radically polymerizable monomer (a1) is preferable. More preferred are monomers having a carboxylic acid (salt) group, a sulfonic acid (salt) group, and an amide group, and particularly preferred are (meth) acrylic acid (salt) and (meth) acrylamide. These radically polymerizable monomers (a) may be used alone, or if necessary, two or more kinds may be used in combination.

Further, other monomers copolymerizable with the above (a1) and (a2) can be used in combination for polymerization.
Other copolymerizable monomers (a3) include, but are not limited to, hydrophobic monomers (a3-1) and crosslinkable monomers (a3-2).

Examples of (a3-1) include the following monomers (i) to (iv). (I) Aromatic ethylenically unsaturated monomer: styrene, α
-Styrenes such as methylstyrene, vinyltoluene and hydroxystyrene; halogen-substituted styrenes such as vinylnaphthalene and dichlorostyrene; (ii) C2-C20 aliphatic ethylenically unsaturated monomers: alkenes [ Ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, etc.]; alkadiene [butadiene, isoprene, etc.], etc .; (iii) alicyclic ethylenically unsaturated monomer having 5 to 15 carbon atoms: Monoethylenically unsaturated monomers [pinene, limonene, indene, etc.]; Polyethylenically unsaturated monomers [cyclopentadiene, bicyclopentadiene, ethylidene norbornene, etc.], etc .;

(Iv) (Meth) acrylic acid ester having an alkyl group having 4 to 50 carbon atoms: n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate , Heptadecyl (meth) acrylate, eicosyl (meth) acrylate and the like; (a3-1)
The blending amount of the monomer is 0 to 5 relative to the monomer of (a).
It is 0% by weight, preferably 0 to 25% by weight.

Examples of (a3-2) include the following crosslinking agents having two or more radical double bonds.
Terminal divinyl compound [(divinylbenzene, 1,5-hexadiene-3-yne, hexatriene, divinyl ether, divinyl sulfone, etc.]; allyl compound [diallyl phthalate, 2,6-diacrylphenol, diallylcarbinol, tetraary] Roxyethane, pentaerythritol triallyl ether, etc.]; bis (meth) acrylamide [N, N'-methylenebisacrylamide, etc.];
Poly (meth) acrylate [(poly) alkylene (having 2 carbon atoms) of polyhydric alcohol (2 to 10 valences or more)
To 6) glycol (degree of polymerization = 2 to 30) di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, sorbitol hexa (meth) acrylate, etc.] Etc. and one or more of these in combination. (A3-2)
The amount of the monomer used is the radical polymerizable monomer (a)
0.001 to 20% by mass, preferably 0.01 to 10% by mass, particularly preferably 0.01
Is about 5% by mass.

In the present invention, the radically polymerizable monomer is radically polymerized in the presence of water. The polymerization concentration, that is, the concentration of all monomers in the polymerization liquid is usually 20 to 45% by mass, preferably 25 to 45% by mass, based on the total mass of the polymerization liquid.
40% by mass, particularly preferably 25 to 35% by mass.
When the concentration of all the monomers is 20% by mass or more, the concentration is sufficient for use after polymerization, which is efficient. On the other hand, 4
When the content is 5% by mass or less, the molecular weight of the obtained polymer does not decrease, and side reactions such as self-crosslinking do not occur and the molecular weight distribution becomes narrow, which is suitable for the purpose of the present invention. The total amount of water is 80 ~
There are 30. When the amount of water is 80% by mass or less, the concentration is sufficient for use after the polymerization, which is efficient. When it is 30% or more, the molecular weight of the obtained polymer does not decrease, and side reactions such as self-crosslinking do not occur and the molecular weight distribution becomes narrow, which is suitable for the purpose of the present invention.

The polymerization method in the present invention may be a conventionally known method, for example, a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, a reverse phase suspension polymerization method, a thin film polymerization method, a spray polymerization method and the like. Can be mentioned. Examples of the polymerization control method include an adiabatic polymerization method and a temperature control polymerization method. In addition to the method of initiating polymerization by heat, a method of initiating polymerization by irradiating with radiation, electron beam, ultraviolet ray or the like can be adopted. A solution polymerization method using a radical initiator is preferable, and an aqueous solution polymerization method is particularly preferable because it is not necessary to use an organic solvent or the like and is advantageous in terms of production cost.

As the polymerization initiator used in the polymerization using the radical polymerization initiator, conventionally known initiators can be used, and examples thereof include azo compounds [azobisisobutyronitrile, azobiscyanovaleric acid and the like. Salt, 2,
2'-azobis (2-amidinopropane) hydrochloride, 2,2'-azobis (2-methyl-N- (2-
Hydroxyethyl) propionamide, etc.], inorganic peroxide [hydrogen peroxide, ammonium persulfate, potassium persulfate, sodium persulfate, etc.], organic peroxide [benzoyl peroxide, di-t-butyl peroxide, cumene hydroper] Oxide, succinic acid peroxide, di (2-ethoxyethyl) peroxydicarbonate, etc.] and redox catalysts [alkali metal sulfite or bisulfite, ammonium sulfite, ammonium bisulfite, ferric chloride, ferric sulfate] , A combination of a reducing agent such as ascorbic acid and an oxidizing agent such as an alkali metal persulfate, ammonium persulfate, hydrogen peroxide, or an organic peroxide]
Etc. These initiators may be used alone or in combination of two or more. The amount of the radical polymerization initiator used is usually 0.0005 to 5% by mass, preferably 0.001 to 2% by mass, based on the mass of the radically polymerizable monomer (a).

A chain transfer agent other than (b) may be used in combination with (b), and examples thereof include thiols (n-lauryl mercaptan, mercaptoethanol, mercaptopropanol, triethyleneglycoldiene). Mercaptans, etc., thiolic acids (thioglycolic acid, thiomalic acid, etc.), secondary alcohols (isopropanol, etc.), amines (dibutylamine, etc.), hypophosphites (sodium hypophosphite, etc.), etc. Can
The amount of the chain transfer agent other than (b) is preferably 0.001 to 1 mass% with respect to the total amount of the monomers.

In the present invention, the polymerization conditions are not particularly limited, and for example, the polymerization initiation temperature can be variously changed depending on the kind of the catalyst used, but it is usually 0 to 100 ° C., preferably 5 to 80 ° C. The polymerization is preferably aqueous solution polymerization, but if necessary, it may be carried out in the coexistence of water and an organic solvent. Examples of the solvent include alcohol solvents (methanol, ethanol, etc.), ketone solvents (acetone,
Examples thereof include methyl ethyl ketone), amide solvents (N, N-dimethylformamide, etc.), sulfoxide solvents (dimethyl sulfoxide, etc.), and mixtures of two or more thereof, and the amount of solvent relative to water is usually on a mass basis. It is 40% or less, preferably 30% or less. When a suspension polymerization method, a reverse phase suspension polymerization method or an emulsion polymerization method is adopted as the polymerization method, the polymerization is carried out in the presence of a conventionally known dispersant or surfactant, if necessary. In the case of the reverse phase suspension polymerization method, polymerization is carried out using a conventionally known hydrocarbon solvent such as xylene, normal hexane, and normal heptane.

In the present invention, if necessary, known additives such as surfactants, preservatives, fungicides, antibacterial agents and antioxidants can be added at any stage (before, during and after polymerization) of the production method of the present invention. Agents, ultraviolet absorbers, colorants (pigments, dyes), fragrances, deodorants, inorganic powders, organic fibrous substances, dispersion peptizers, builders, leveling agents, plasticizers, etc. can be added. Although the amount varies depending on the use, it is preferably 50% by mass or less based on the mass of the obtained polymer.

As the surfactant, anionic surfactant, nonionic surfactant, cationic surfactant, amphoteric surfactant, such as US
The thing described in the specification of P4331447 is mentioned, and these 1 type (s) or 2 or more types may be used together. Examples of the anionic surfactant include hydrocarbon ether carboxylic acids having 8 to 24 carbon atoms or salts thereof, [polyoxyethylene (polymerization degree = 1 to 100) sodium lauryl ether acetate, polyoxyethylene (polymerization degree = 1 to 1). 100) disodium lauryl sulfosuccinate, etc.], a hydrocarbon-based sulfuric acid ester salt having 8 to 24 carbon atoms [sodium lauryl sulfate,
Polyoxyethylene (degree of polymerization = 1-100) sodium lauryl sulfate, polyoxyethylene (degree of polymerization = 1-10)
0) triethanolamine lauryl sulfate, polyoxyethylene (degree of polymerization = 1 to 100) sodium coconut oil fatty acid monoethanolamide sulfate,], and hydrocarbon sulfonate having 8 to 24 carbon atoms [sodium dodecylbenzenesulfonate, etc.] And hydrocarbon phosphate ester salts having 8 to 24 carbon atoms [sodium lauryl phosphate, polyoxyethylene (polymerization degree = 1 to 100) sodium lauryl ether phosphate, etc.], fatty acid salts [sodium laurate, triethanol laurate Amine, etc.], acylated amino acid salt [sodium coconut oil fatty acid methyl taurine, sodium coconut oil fatty acid sarcosine sodium, coconut oil fatty acid sarcosine triethanolamine, N-coconut oil fatty acid acyl-L-glutamic acid triethanolamine, N-coconut oil fatty acid acyl -L-glutamine Sodium, lauroyl methyl -
β-alanine sodium, etc.] and others [sulfooxysuccinic acid polyoxyethylene (polymerization degree = 1 to 100) lauroyl ethanolamide disodium etc.] and the like.

Specific examples of the nonionic surfactant include aliphatic alcohols (C8 to C24) alkylene oxide (C2 to C8) adducts (degree of polymerization = 1 to 1).
100) [lauryl alcohol ethylene oxide addition (degree of polymerization = 20), oleyl alcohol ethylene oxide addition (degree of polymerization = 10), McCo alcohol ethylene oxide addition (degree of polymerization = 35), etc.], polyoxyalkylene (number of carbon atoms 2-8, degree of polymerization = 1-100)
Higher fatty acid (C8-24) ester [polyethylene glycol monostearate (degree of polymerization = 20), polyethylene glycol distearate (degree of polymerization = 30)
Etc.], polyhydric (divalent to 10 valent or higher) alcohol fatty acid (C8 to C24) ester [glyceryl monostearate, ethylene glycol monostearate, sorbitan lauric acid (mono / di) ester, sorbitan palmitic acid (Mono / di) ester, sorbitan stearic acid (mono / di) ester, sorbitan oleic acid (mono / di) ester, sorbitan coconut oil (mono / di)
Esters, etc.], polyoxyalkylenes (C2-8,
Degree of polymerization = 1 to 100) Polyhydric (divalent to 10 or higher) alcohol Higher fatty acid (C8 to C24) ester [polyoxyethylene (degree of polymerization = 10) sorbitan lauric acid (mono / di) ester, Polyoxyethylene (degree of polymerization = 20) sorbitan palmitic acid (mono / di) ester, polyoxyethylene (degree of polymerization = 15) sorbitan stearic acid (mono / di) ester, polyoxyethylene (degree of polymerization = 10) sorbitan oleic acid (Mono / di)
Ester, polyoxyethylene (degree of polymerization = 25) lauric acid (mono / di) ester, polyoxyethylene (degree of polymerization = 50) stearic acid (mono / di) ester, polyoxyethylene (degree of polymerization = 18) oleic acid ( (Mono / di)
Ester, sorbitan, polyoxyethylene (polymerization degree = 50) dioleic acid methyl glucoside, etc.], fatty acid alkanolamide [1: 1 type coconut oil fatty acid diethanolamide, 1: 1 type lauric acid diethanolamide],
Polyoxyalkylene (C2-8, degree of polymerization = 1-1)
00) alkyl (having 1 to 22 carbon atoms) phenyl ether (polyoxyethylene (degree of polymerization = 20) nonylphenyl ether, etc.), polyoxyalkylene (having 2 to 8 carbon atoms,
Degree of Polymerization = 1 to 100) Alkyl (C8 to C24) Amino Ether and Alkyl (C8 to C24) Dialkyl (C1 to C6) Amine Oxide [Lauryl Dimethyl Amine Oxide, etc.], Polydimethylsiloxane Polyoxyethylene Addition product, polyoxyethylene / polyoxypropylene block polymer (weight average molecular weight = 150 to 1)
0000) and the like.

As the cationic surfactant, a quaternary ammonium salt type [stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, distearyldimethylammonium chloride, lanolin fatty acid aminopropylethyldimethylammonium ethylsulfate, etc.], an amine salt type Stearic acid diethylaminoethylamide lactate, dilaurylamine hydrochloride, oleylamine lactate, etc.] and the like. Examples of the amphoteric surfactant include betaine-type amphoteric surfactants [coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-
Hydroxyethyl imidazolinium betaine, lauryl hydroxysulfobetaine, lauroylamidoethyl hydroxyethyl carboxymethyl betaine hydroxypropyl sodium phosphate, etc.], and an amino acid type amphoteric surfactant [sodium β-lauryl aminopropionate etc.] can be mentioned.

As the antioxidant, triethylene glycol-bis- [3- (3-t-butyl-5-methyl-4) is used.
-Hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-) Butyl-4-hydroxyphenylpropionate, 3,5-di-t-butyl-
Examples thereof include hindered phenolic antioxidants such as 4-hydroxybenzylphosphonate-diethyl ester; amine antioxidants such as n-butylamine, triethylamine, diethylaminomethylmethacrylate and the like.

As the ultraviolet absorber, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2-
(3,5-di-t-butyl-2-hydroxyphenyl)
Benzotriazole, 2- (3,5-di-t-butyl-
Benzotriazole-based UV absorbers such as 2-hydroxyphenyl) -5-chlorobenzotriazole and 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole; 2- (4,6-diphenyl- 1, 3,
5-triazin-2-yl) -5-[(hexyl) oxy] -phenol and other triazine-based UV absorbers; 2-
Benzophenone-based UV absorbers such as hydroxy-4-n-octyloxybenzophenone; 2-ethoxy-2 '
-Anilide oxalic acid-based UV absorbers such as ethyloxalic acid bisanilide.

As the inorganic powder, calcium carbonate, kaolin, talc, mica, bentonite, clay, sericite, asbestos, glass fiber, carbon fiber, glass powder, glass balloon, silas balloon, coal powder, metal powder, ceramic powder, Zeolite, slate powder and the like can be mentioned. The morphology may be arbitrary, and the average particle size is preferably 0.1 micron to 1 mm. Examples of the pigment include carbon black, titanium oxide, red iron oxide, red lead,
Examples include para red and navy blue.

The organic fibrous materials include natural fibers [cellulosic materials (cotton, sawdust, straw, etc. and others, grass charcoal, wool, etc.]), artificial fibers (cellulosics such as rayon, acetate, etc.), synthetic fibers ( Polyamide, polyester, acrylic, etc.), pulp [mechanical pulp (ground wood pulp, asplund method ground wood pulp, etc.),
Chemical pulp (sulfurous acid pulp, soda pulp, sulfate pulp, nitric acid pulp, chlorine pulp, etc.), semi-chemical pulp, recycled pulp (for example, mechanical crushing or crushing of paper once made from pulp, or waste paper machine Recycled waste paper pulp, which is a mechanically crushed or crushed product, and the like.

The polymer obtained by the method of the present invention has a low molecular weight and a narrow molecular weight distribution. A wide range of molecular weight distribution and many low molecular weight products are less harmful, and the value of a polymer obtained by polymerizing a radical-polymerizable monomer in an aqueous solution is improved. The weight average molecular weight of the polymer is naturally 3,000 to 2,000,000, although it naturally varies depending on the polymerization conditions, application and the like. It is preferably 10,000 to 1,000,000, and particularly preferably 20,000 to 800,000.

When the weight average molecular weight of the polymer is relatively small (it is difficult to draw a clear line, but usually 1,0
The weight average molecular weight can be measured by the following GPC method. The molecular weight distribution can be determined by the shape of the GPC chart or the area of the chart when the GPC method is used. Both ends of the peak of the GPC chart correspond to high molecular weight or low molecular weight. Polymer GPC
, Where M is the peak top molecular weight, M × 0.
The content of a low molecular weight substance of 2 or less and a high molecular weight substance of M × 2.0 or more is preferably 2% or less and 5% or less, more preferably 1% or less, respectively, in terms of the area on the GPC chart. It is 4% or less, particularly preferably 0.8% or less and 3% or less, respectively.

When the molecular weight is larger than the above, the accuracy of measurement becomes a problem in the GPC method, and different measuring methods are adopted. For example, it can be measured by the following intrinsic viscosity. When the measurement by the GPC method is difficult, the molecular weight distribution can be judged by the spinnability. . The smaller the string length, the smaller the molecular weight distribution. The string length depends on the intrinsic viscosity, but the value of the string length / intrinsic viscosity is preferably 7 or less, more preferably 6 or less, and particularly preferably 5 or less.

The obtained polymer has various properties depending on the type and amount of the radical-polymerizable monomer used, the molecular weight, etc., and can be used for various purposes. It can be obtained in liquid form at room temperature, from viscous to solid. When the polymer obtained as an example is, for example, (i) a water-soluble polymer or a water-dispersible polymer; a polymer for an aqueous paint,
Water-based coating agent, photoresist, sizing agent, conductive agent, antistatic agent for fiber, antifouling agent for fiber, binder for resin processing, non-woven fabric binder, binder for plastic reinforcing fiber, binder for magnetic tape, binder for resin concrete, etc. Dyeing paste, adhesive, thickener for civil engineering,
Primer, pigment dispersant, dispersant for pesticide granules, dispersant for pulverized coal, dispersant for cement, scale inhibitor, compatibilizer, drainage / yield improver, binder for printing ink,
Flocculants, dye fixing agents, chelating polymers, hair setting polymers, etc. (ii) Water-insoluble polymers; water-absorbing resins, oil-absorbing resins, polymers for increasing crude oil production, gelling agents, plasticizers, plastic kneading, antistatic It is useful as an agent, a sealing agent, an elastomer, an electrophotographic toner binder, a binder for printing inks, a binder for magnetic tapes, a lubricant dispersant for lubricating oils, a pour point depressant, and a filler.

The optimum molecular weight of the polymer or a numerical value related thereto is described for the dispersant and the aggregating agent as a representative of the above-mentioned applications, and test examples are described in Examples, but the applications are not limited thereto. For example, a suitable intrinsic viscosity for a flocculant is preferably 15-25 dl / g, more preferably 18-22 for nonionic or anionic flocculants.
dl / g, and in the case of a cationic flocculant, it is preferably 3 to 15 dl / g, more preferably 5 to 13 dl / g. The thread length suitable for the coagulant is preferably 80 to 120 mm, more preferably 80 to 100 mm in the case of nonionic or anionic coagulant, and preferably 5 to 90 mm, more preferably 5 in the case of cationic coagulant. ~ 80
mm.

The peak top molecular weight M of GPC suitable for various dispersants is preferably 3,000 to 20,000, more preferably 5,000 to 15,000.
The content of the low molecular weight substance of M × 0.2 or less and the high molecular weight substance of M × 2.0 or more is preferably 1% or less and 4% or less, respectively, in the area on the GPC chart, and more preferably, respectively. 0.9% or less, 3.5% or less,
Particularly preferably, they are 0.8% or less and 3% or less, respectively.

The following measured values are based on the following method. (Measurement of molecular weight by GPC method) The methods for measuring the peak top molecular weight by GPC and calculating the contents of low molecular weight substances and high molecular weight substances are as follows. The peak top molecular weight, the content of the low molecular weight material and the content of the high molecular weight material are the values when completely neutralized with sodium hydroxide. << GPC measurement conditions >> Model: Waters510 (Japan Waters
Limited) Column: TSK gel G5000pwXL TSK gel G3000pwXL (both manufactured by Tosoh Corporation) Column temperature: 40 ° C Detector: RI solvent: 0.5% sodium acetate / water / methanol (volume ratio 70/30) Flow speed : 1.0 ml / min Sample concentration: 0.25% by mass Injection amount: 200 μl Standard: Polyoxyethylene glycol (manufactured by Tosoh Corporation; TSK STANDARDPOL
YETHYLENE OXIDE) Data processing device: SC-8010 (manufactured by Tosoh Corporation)

<< Method of Calculating Content of Low Molecular Weight Material and High Molecular Weight Material >> Based on the peak top molecular weight M, calculation was carried out by the following method. Low molecular weight product: The ratio (%) of the area of the portion having a molecular weight of M × 0.2 or less to the total peak area (retention time, for example, a peak appearing by 20 minutes) was calculated using a data processor. High molecular weight product: the molecular weight is M × 2.
The area ratio (%) of 0 or more portions was calculated using a data processing device. The GPC chart is based on the retention time.

<< Distribution Conditions by GPC >> Dispersants of Examples and Comparative Examples were obtained by using the following devices and mixing or mixing preparative products. The peak top molecular weight, the content of low molecular weight substances and the content of high molecular weight substances were measured by the GPC. Machine type: Fleip C type liquid chromatographic fractionation device (manufactured by Soken Chemical Co., Ltd.) Column: TSK gel G3000pw TSK gel G5000pw (both manufactured by Tosoh Corporation) Column temperature: 20 to 30 ° C. Detector: RI Solvent: 0. 5% sodium acetate / water / methanol (volume ratio 70/30) Flow rate: 30 ml / min Sample concentration: 2 mass% Injection volume: 50 ml Standard: Polyoxyethylene glycol (Tosoh Corporation; TSK STANDARDPOL
(YETHYLENE OXIDE)

[0049]

The present invention will be further described below with reference to examples, but the present invention is not limited thereto. Unless otherwise specified, all parts are by weight. Example 1 540 parts of water was charged into a pressure resistant reactor, which was replaced with nitrogen and then sealed, and the temperature was raised to 100 ° C. 77 parts of acrylic acid with stirring,
A homogeneous mixture of 228 parts of acrylic acid, 1.5 parts of α- (2-carboxyethyl) thiomethyl-acrylic acid and 0.7 part of ferrous chloride (tetrahydrate), and 6% sodium persulfate.
50 parts of aqueous solution, from separate containers for 3 hours, 1
After the lapse of time, the solution was added dropwise over 2 hours and 3.5 hours. After finishing the dropping, add 3 parts of 35% hydrogen peroxide aqueous solution, and add 1 part at the same temperature.
After maintaining for a period of time to confirm that the polymerization rate was 99.9 or more, it was neutralized with 350 parts of a 48% aqueous sodium hydroxide solution to obtain an aqueous sodium polyacrylate solution. Table 1 shows the peak top molecular weight, low molecular weight substance content, and high molecular weight substance content of sodium polyacrylate.

Example 2 Acrylic acid / methacrylic acid = 5 instead of acrylic acid
An aqueous sodium salt solution of a copolymer of acrylic acid and methacrylic acid was obtained in the same manner as in Example 1 except that 0/50 (molar ratio) was used and 322 parts of a 48% aqueous sodium hydroxide solution was used. Table 1 shows the peak top molecular weight, low molecular weight substance content and high molecular weight substance content of the copolymer. Comparative Example 1 A polymer (Comparative Example 1) was obtained in the same manner as in Example 1 except that the same amount of n-lauryl mercaptan was used as the chain transfer agent. Table 1 shows the peak top molecular weight, low molecular weight content and high molecular weight content of the polymer.

[0051]

[Table 1]

Test Example 1 (wet pulverization and dispersion test of heavy calcium carbonate) 25 parts of water and 0.6 parts of the polymers of Examples 1 and 2 and Comparative Example 1 (in terms of solid content) were uniformly dissolved. 75 parts of coarsely ground ore of calcium bicarbonate was added to the aqueous solution, and the mixture was stirred and dispersed for 30 minutes using a sand grinder. Immediately after the preparation of the obtained 75 wt% calcium carbonate aqueous slurry, and 25
The viscosity after standing for 7 days at 25 ° C using a BL viscometer,
The measurement was performed under the condition of 60 rpm. Table 2 shows the test results.

[0053]

[Table 2]

Test Example 2 (Dispersion of Sachin White) Using the polymers of Examples 1 and 2 and Comparative Example 1, 200 g of Sachin white cake containing 71% of water was used as a dispersant to obtain 1.74 g of a polymer aqueous solution (solid). Then, the viscosity of the slurry was measured with a BL type viscometer at 25 ° C. and 60 rpm. Table 3 shows the test results.

[0055]

[Table 3]

It can be seen that the polymers of Examples 1 and 2 have better dispersibility of calcium carbonate and satin white than the polymer of Comparative Example 1. Example 3 80 parts of acrylamide, α- (2-carboxyethyl)
1.1 parts of thiomethyl-styrene and 280 parts of ion-exchanged water were charged into an adiabatic reaction vessel, and nitrogen was vigorously blown into the solution at 20 ° C. for 20 minutes. Then, sequentially, 0.1 part of 10% aqueous solution of azobisamidinopropane hydrochloride, 0.02 part of 10% aqueous solution of hydrogen peroxide, and 0.01% aqueous solution of 10% sodium bisulfite.
Parts were added. After the addition, blowing of nitrogen was stopped. About 1
The liquid temperature started to rise after 0 minutes, and the system gradually thickened and became a gel-like polymer. After 7 hours, the gel was shredded, dried with hot air at 75 ° C. for 5 hours, and then pulverized to obtain a powdery polymer. Table 4 shows the intrinsic viscosity and the string length of the polymer.

Example 4 Instead of 80 parts of acrylamide, 60 parts of acrylamide were used.
Parts, sodium acrylate 20 parts, and α- (2-carboxyethyl) thiomethyl-styrene 1.1 parts 2.5 parts
A powdery polymer was obtained in the same manner as in Example 3 except that part of the polymer was used. Table 4 shows the intrinsic viscosity and the string length of the polymer. Comparative Example 2 A powdery polymer was obtained in the same manner as in Example 3, except that 1.1 parts of α- (2-carboxyethyl) thiomethyl-styrene was used and the same amount of n-lauryl mercaptan was used. Table 4 shows the intrinsic viscosity and the string length of the polymer.

The intrinsic viscosity and the yarn length of Examples 3 to 4 and Comparative Example 2 were measured according to the following measuring methods. (Measurement Method of Intrinsic Viscosity) Intrinsic viscosity is a value measured using a Canon Fenske viscometer at 25 ° C. with a 1N aqueous solution of sodium nitrate. The intrinsic viscosity of the polymer is the value obtained by extrapolating the concentration to 0 in the graph in which the horizontal axis represents the viscosity at several concentrations of the dilute polymer solution and the vertical axis represents the viscosity. (Measurement method of spinnability) The spinnability was obtained by dissolving a polymer in ion-exchanged water to prepare a 0.2% aqueous solution, and attaching a glass ball having a diameter of 7 mm to a depth of 11 mm, and the glass ball was spun at a speed of 16 mm / sec. It is a value measured at 25 ° C. until the polymer aqueous solution is cut off when pulled up.

[0059]

[Table 4]

Performance Evaluation Example 1 (Test as Flocculant) Using the polymers obtained in Examples 3 to 4 and Comparative Example 2, K gravel washing plant wastewater (suspension substance 0.35%, pH 6.0) was used. A sedimentation test was conducted. The test results are shown in Table 5. In the coagulation / sedimentation test, 300 ml of waste water was put into a 300 ml graduated cylinder (sedimentation tube) with a stopper, and 0.1% of the polymer (solid content conversion) was added to this.
A predetermined amount of ion exchange aqueous solution was added at room temperature. Next, this settling tube was turned over 10 times to mix the waste water and the polymer aqueous solution to form flocs, and then the settling tube was left standing to measure the sedimentation velocity at the interface of the floc layer. Settling speed is m / h
It is represented by r.

[0061]

[Table 5]

It can be seen that the polymers of Examples 3 to 4 can obtain a high coagulation rate with a low addition amount as compared with the polymer of Comparative Example 2.

[0063]

INDUSTRIAL APPLICABILITY In radical polymerization in an aqueous solution, the polymer obtained by the production method of the present invention has few low molecular weight products and has a narrow molecular weight distribution. Therefore, the adverse effects caused by the presence of a low molecular weight substance are reduced, and the polymer of the present invention is a useful polymer.

─────────────────────────────────────────────────── ─── Continuation of the front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08F 2/00-2/60 C08F 228/04

Claims (8)

(57) [Claims] 1. A method for producing a polymer by radically polymerizing one or more radical-polymerizable monomers (a) which are water-soluble or water-soluble by hydrolysis, wherein a (substituted) allyl group and a thioether group are the same molecule. A method for producing a polymer, which comprises polymerizing in the presence of a radical copolymerizable compound (b) contained therein and water. 2. The method according to claim 1, wherein (b) is a compound represented by the following general formula (1). [Chemical 1] (In the formula, R ¹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, a carboxyl group or a salt-forming group thereof, or an alkoxycarbonyl group having an alkoxy group having 1 to 12 carbon atoms; R ² is An alkyl group having 1 to 12 carbon atoms,
An aromatic or araliphatic hydrocarbon group having 6 to 12 carbon atoms, a carboxyalkyl group having 1 to 12 carbon atoms in an alkyl group, an aminoalkyl group having 1 to 12 carbon atoms, or 1 carbon atom
~ 12 hydroxyalkyl groups. ) 3. (a) comprises a carboxylic acid (salt) group, a sulfonic acid (salt) group, a sulfuric acid (salt) group, a phosphoric acid (salt) group, a hydroxyl group, an amide group, an amino group and a quaternary ammonium salt group. Water-soluble radically polymerizable monomer (a1) selected from the group
And / or the method for producing a polymer according to claim 1 or 2, which is a radical-polymerizable monomer (a2) selected from the group consisting of an acid anhydride group, a lower alkyl ester group, and a nitrile group, which becomes water-soluble by hydrolysis. 4. The method according to claim 1, which is obtained by further copolymerizing (a) with another radical copolymerizable monomer (a3).
4. The method for producing a polymer according to any one of 3 above. 5. The method for producing a polymer according to claim 4, wherein (a3) is a hydrophobic monomer and a crosslinkable monomer. 6. The amount of (b) is 0.001 to 1% by mass based on the total mass of (a) and (a3).
5. The method for producing a polymer according to any one of 5 to 5. 7. A polymer obtained by the method according to any one of claims 1 to 6, wherein the weight average molecular weight of the polymer is 1
20,000 to 1,000,000, and G of the polymer
When the peak top molecular weight of the molecular weight measurement chart by the PC method is M, low molecular weight substances of M × 0.2 or less and M ×
A polymer having a content of 2.0 or more high molecular weight substances in an area on a GPC chart of 2% or less and 5% or less, respectively. 8. A polymer obtained by the process according to claim 1, wherein the polymer has a string length / intrinsic viscosity of 7 or less.