JP2001323003A - Polymer and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymerization method for producing a polymer by a radical polymerization by which the polymer having a narrow molecular weight distribution and containing small amounts of low molecular products is provided, and further to provide the polymer. SOLUTION: This polymerization method is characterized in that when polymerizing a radical-polymerizable monomer, a specific tertiary phosphine is used as a chain transfer agent. The polymer is also provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing a radical polymer and a polymer thereof. More specifically, the present invention relates to a polymerization method in which the molecular weight distribution of a polymer obtained by radical polymerization in the presence of water is narrow and the production of a low molecular weight product is small, and a polymer obtained.

[0002]

2. Description of the Related Art Conventionally, when a radical polymerizable monomer is polymerized in an aqueous solution, as a method of controlling the molecular weight, a chain transfer agent such as an alkyl mercaptan may be used in addition to changing the amount of a polymerization initiator, a polymerization temperature, a polymerization concentration and the like. The methods used are known.

[0003]

However, in these methods, when a high molecular weight product is to be obtained, a large number of low molecular weight products are inevitably generated and the molecular weight distribution is widened, thereby causing a problem that adverse effects occur. An object of the present invention is to provide a method for obtaining a polymer having a small molecular weight distribution by radical polymerization in the presence of water.

[0004]

Means for Solving the Problems 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 a radical polymerizable monomer is polymerized in the presence of water. Reached the present invention. That is, the present invention relates to a method for producing a polymer by radically polymerizing one or more radically polymerizable monomers (a) which become water-soluble and / or water-soluble by hydrolysis. A method for producing a polymer, characterized in that polymerization is carried out in the presence of a polymerization initiator (c) and water; and a polymer thereof.

[0005]

DETAILED DESCRIPTION OF THE INVENTION In the present invention, a water-soluble radically polymerizable monomer (a1) and / or a water-soluble radically polymerizable monomer (a2) is used as the radically polymerizable monomer (a). it can.

Water-soluble radically polymerizable monomer (a1)
Include at least one acid group and / or a salt-forming group thereof (a carboxylic acid (salt) group, a sulfonic acid (salt) group, a sulfuric acid (salt) group, a phosphoric acid (salt) group, etc.), a hydroxyl group, an amide group, Examples include radical polymerizable monomers having a hydrophilic group such as an amino group and a quaternary ammonium base, and can be classified into anionic, nonionic, and cationic monomers. In the above, as the (salt) group, sodium salts, potassium salts, ammonium salts, amine salts (salts of alkylamines such as methylamine and trimethylamine; salts of alkanolamines such as diethanolamine and triethanolamine) and the like can be used.

(I) Anionic or radically polymerizable monomers that become anionic (i-1) Examples of the monomer having a carboxylic acid group include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, and cinnamic acid. Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, itaconic acid and the like; monoalkyl (1-8 carbon atoms) esters of unsaturated dicarboxylic acids (above) such as monobutyl maleate and monobutyl fumarate Carboxyl-containing vinyl monomers such as esters, ethyl carbitol monoester of maleic acid, ethyl carbitol monoester of fumaric acid, monobutyl citraconic acid, glycol monoester itaconate, and combinations of two or more of these. No.

(I-2) Examples of the radically polymerizable monomer having a sulfonic acid group include aliphatic or aromatic vinyl sulfonic acids having 2 to 30 carbon atoms, for example, vinyl sulfonic acid,
(Meth) allylsulfonic acid; styrenesulfonic 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-dimethylethanesulfonic acid, 3- (meth) acryloxyethanesulfonic acid, 2- (meth) acrylamide-
2-methylpropanesulfonic acid, 3- (meth) acrylamide-2-hydroxypropanesulfonic acid]; alkyl (C3-18) (meth) allyl sulfosuccinate, and the like.

(I-3) As a radical polymerizable monomer having a sulfuric ester, hydroxyalkyl (having 2 to 2 carbon atoms)
6) Sulfated ester of (meth) acrylate [sulfated ester of hydroxyethyl (meth) acrylate and the like]; poly (n = 2 to 30) oxyalkylene (having 2 to 4 carbon atoms: may be single, random, or block) mono Sulfated ester of (meth) acrylate [poly (n = 5
15) Sulfuric acid ester of oxypropylene monomethacrylate] and the following general formulas (1), (2),
Compounds represented by (3) are exemplified. General formula

[0010]

Embedded image

[0011]

Embedded image

[0012]

Embedded image

[In the formulas (1) to (3), R is a group having 1 to 1 carbon atoms.
R 'represents an alkyl group having 1 to 15 carbon atoms which may be substituted with a fluorine atom, A represents an alkylene group having 2 to 4 carbon atoms, and Ar represents a benzene ring. n represents an integer of 1 to 50. When n is plural, each A may be the same or different, and if different, it may be random or block. ]

(I-4) Examples of the radical polymerizable monomer having a phosphoric acid group include, for example, a phosphoric acid monoester of a hydroxyalkyl (meth) acrylate (for example, hydroxyethyl (meth) acrylate). Monophosphate, etc.], a phosphoric diester of hydroxyalkyl (meth) acrylate (2-6 carbon atoms) [for example, phenyl-
2-acryloyloxyethyl phosphate etc.], alkyl (meth) acrylate (C2-C6) phosphonic acids [for example, 2-acryloyloxyethyl phosphonic acid etc.] and the like. (i-5) Salts of the above (i-1) to (i-4). Examples of the salt include the same ones as described in the above [(a1)].

(Ii) Nonionic monomers (ii-1) Examples of the radical polymerizable monomer having a hydroxyl group include monoethylenically unsaturated alcohols (eg, (meth) allyl alcohol and the like); divalent to hexavalent Or a monoethylenically unsaturated ester or ether of a polyol (for example, alkylene glycol having 2 to 20 carbon atoms, glycerin, polyalkylene (2 to 4 carbon atoms) glycol (molecular weight: 106 to 2,000), etc.) Ethyl (meth) acrylate, hydroxypropyl (meth) acrylate, triethylene glycol (meth) acrylate, poly-oxyethylene-oxypropylene (random or block) glycol mono (meth) allyl ether (terminal hydroxyl group is etherified or esterified May be) And the like.

(Ii-2) Examples of the radical polymerizable monomer having an amide group include (meth) acrylamide and N
-Alkyl (C1-8) (meth) acrylamide [for example, N-methylacrylamide and the like], N, N-
Dialkyl (C1-8) acrylamide [for example,
N, N-dimethylacrylamide, N, N-di-n- or i-propylacrylamide, etc.], N-hydroxyalkyl (C1-8) (meth) acrylamide [for example, N-methylol (meth) acrylamide, N
-Hydroxyethyl (meth) acrylamide and the like];
N, N-dihydroxyalkyl (C1-8) (meth) acrylamide [eg, N, N-dihydroxyethyl (meth) acrylamide], vinyl lactams [eg, N-vinylpyrrolidone] and the like.

(Iii) Cationic or cationic radical polymerizable monomer (iii-1) As the radical polymerizable monomer having an amino group, monoethylenically unsaturated mono- or di-carboxylic acid amino group-containing ester For example, dialkyl (C1-8) aminoalkyl (C2-10) (meth) acrylate, dihydroxyalkyl (C1-8) aminoalkyl (C2-10) ester, morpholinoalkyl (C1 To 8) esters and the like [for example, dimethylaminoethyl (meth) acrylate, diethylamino (meth) acrylate, morpholinoethyl (meth) acrylate, dimethylaminoethyl fumarate, etc.];
Amino group-containing amides of monoethylenically unsaturated mono- or di-carboxylic acids, such as monoalkyl (C2-C1)
0) (meth) acrylamide and the like [for example, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide and the like]; heterocyclic vinyl compound [for example, 2-vinylpyridine, 4-vinylpyridine,
Vinylpyridines such as N-vinylpyridine, N-vinylimidazole, etc.]; diallylamine and the like.

(Iii-2) Examples of the radical polymerizable monomer having a quaternary ammonium group include a quaternary product of a tertiary amino group-containing radical polymerizable monomer (the tertiary amino group-containing radical polymerizable monomer having 1 carbon atom). To 8 using a quaternizing agent such as methyl chloride, dimethyl sulfate, benzyl chloride and dimethyl carbonate.
Graded), for example, trimethylaminoethyl (meth) acrylate chloride, methyldiethylaminoethyl (meth) acrylate / methosulfate, trimethylaminoethyl (meth) acrylamide chloride, diethylbenzylaminoethyl (meth) acrylamide chloride and the like Is mentioned.

The radically polymerizable monomer (a2) which becomes water-soluble by hydrolysis includes at least one hydrolyzable group [acid anhydride group, lower alkyl (C1-3) ester group, nitrile group, etc.] And a radical polymerizable monomer having the formula: Examples of the radical polymerizable monomer having an acid anhydride group include, for example, a radical polymerizable monomer having 4 to 20 carbon atoms such as maleic anhydride, itaconic anhydride, and citraconic anhydride; as the radical polymerizable monomer having an ester group, For example, lower alkyl (C 1-3) ester of monoethylenically unsaturated carboxylic acid [eg, methyl (meth) acrylate, ethyl (meth) acrylate], ester of monoethylenically unsaturated alcohol [eg, Vinyl acetate, (meth) allyl acetate, etc.]. Examples of the radical polymerizable monomer having a nitrile group include (meth) acrylonitrile and the like. The hydrolysis of (a2) may be performed during or after polymerization, and usually forms a salt by hydrolysis to become water-soluble. Examples of the salt include the same salts as those described in the above (a1). Of these, preferred are water-soluble radically polymerizable monomers (a
1). More preferred are carboxylic acids (salts)
It is a radical polymerizable monomer having a group, a sulfonic acid (salt) group, and an amide group, and particularly preferably (meth) acrylic acid (salt) and (meth) acrylamide. These radical polymerizable monomers (a) may be used alone or in combination of two or more as necessary.

The polymerization can be carried out in combination with other radically polymerizable monomers (a3) copolymerizable with the above (a1) and (a2). (A3) includes, but is not limited to, a hydrophobic radically polymerizable monomer (a3-1) and a crosslinkable radically polymerizable monomer (a3-2).

Examples of (a3-1) include the following radically polymerizable monomers (i) to (iv). (I) Aromatic ethylenic monomers having 8 to 20 carbon atoms: styrenes such as styrene, α-methylstyrene, vinyltoluene, and hydroxystyrene; halogen-substituted styrenes such as vinylnaphthalenes and dichlorostyrene; ii) an aliphatic ethylenic monomer having 2 to 20 carbon atoms: alkene [ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene;
Dodecene, octadecene, etc.]; alkadienes [butadiene, isoprene, etc.] etc .; (iii) alicyclic ethylenic monomers having 5 to 15 carbon atoms:
Monoethylenically unsaturated monomers [pinene, limonene, indene, etc.]; polyethylene-based vinyl polymerizable monomers [cyclopentadiene, bicyclopentadiene, ethylidene norbornene, etc.];

(Iv) (meth) acrylate 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)
Is from 0 to 50% by weight, and preferably from 0 to 25% by weight, based on (a).

Examples of (a3-2) include the following crosslinkable radical polymerizable monomers having two or more double bonds. Terminal divinyl compound [(divinylbenzene, 1,5-hexadiene-3-yne, hexatriene, divinyl ether, divinylsulfone, etc.); Allyl compound [diallyl phthalate, 2,6-diacrylphenol, diallyl carbinol, tetraali Roxyethane, pentaerythritol triallyl ether, etc.]; bis (meth) acrylamide [N, N′-methylenebisacrylamide, etc.]; poly (meth) acrylate of polyhydric alcohol (2 to 10 or more) [(poly) Alkylene (C2-6) glycol (degree of polymerization = 2-3)
0) di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol tri (meth)
Acrylate, pentaerythritol tetra (meth) acrylate, sorbitol hexa (meth) acrylate, etc.], and one or a combination of two or more of these. In addition, depending on the type of (a) used, a crosslinkable radical polymerizable monomer having a vinylic double bond and a functional group capable of reacting with (a) [eg, glycidyl (meth) acrylate] Etc. of the present invention (a3-
It can be suitably used as 2).

The amount of (a3-2) used is usually 0.001 to 20% by mass, preferably 0.01 to 10% by mass, particularly preferably 0.01 to 5% by mass, based on the mass of (a). %.

In the present invention, the tertiary phosphine (b)
Is not particularly limited, but is preferably a tertiary phosphine compound having 1 to 4 phosphorus atoms and 3 to 54 carbon atoms from the viewpoint of control of polymerizability, and examples thereof include the following. 1) aromatic phosphine (8-54 carbon atoms) an aryl group containing phosphine diethyl phenyl phosphine, triphenyl phosphine (hereinafter PPh _3), diethyl naphthyl phosphine, ortho - phenylenebis (diphenylphosphine), ortho - phenylenebis (dimethylphosphine ), Ortho-
Phenylenebis (diethylphosphine), ortho-phenylenebis (ethylphenylphosphine), 1,2-bis (diphenylphosphino) ethane, 1,2-bis (ethylphenylphosphino) ethane, 1,2-bis (diphenylphosphine) Fino) methane (hereinafter dppm), 1,2-
Bis (ethylphenylphosphino) methane, 1,2-bis (ethylnaphthylphosphino) methane, tris (diphenylphosphinoethyl) phosphine, tris (ethylphenylphosphinoethyl) phosphine, diethyltolylphosphine, diethylxylylphosphine, Diethyl-p- (2-ethylhexyl) phenylphosphine,
1,2-bis (ethyltolylphosphino) methane,
2-bis (ethylxylylphosphino) methane and 1,
2-bis (ethyl-p- (2-ethylhexyl) phenylphosphino) methane and the like; aralkyl group-containing phosphine diethylbenzylphosphine, diethyl-2-phenylhexylphosphine, 1,2-bis (ethylbenzylphosphino) methane and the like;

2) Aliphatic phosphines (3 to 5 carbon atoms)
4) Trimethylphosphine, triethylphosphine, tri-
n-butylphosphine, 1,2-bis (dimethylphosphino) methane, 1,2-bis (diethylphosphino) methane, 1,2-bis (dimethylphosphino) ethane,
1,2-bis (diethylphosphino) ethane, 1,2-
Bis (ethyl-2-ethylhexylphosphino) methane, tris (diethylphosphinoethyl) phosphine and tris (dimethylphosphinoethyl) phosphine;
And the like.

Of these, more preferred are aromatic phosphines, particularly preferred are aryl group-containing phosphines, and most preferred are PPh ₃ and dpp.
m, 1,2-bis (ethyltolylphosphino) methane.

The amount of the compound (b) used is usually 0.001 to 20% by mass, preferably 0.005 to 1% by mass based on the mass of the radical polymerizable monomers [(a) and (a3)].
0 mass%, particularly preferably 0.01 to 5 mass%.
When the amount of the compound (b) used is 0.001% by mass or more,
The effect of using (b) is remarkable, that is, the molecular weight distribution is narrow, and the generation of low molecular weight products is small. On the other hand, when the content is 20% by mass or less, the polymerization rate and the polymerization rate of the radical polymerizable monomer are sufficient, and the productivity is good. When the solubility of the compound (b) in the aqueous polymerization solution is low, the polymerization can be carried out by dissolving or dispersing the compound (b) in the aqueous polymerization solution together with a surfactant or the like.

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 radically polymerizable monomers in the polymerization solution is usually 20 to 70% by mass, preferably 25 to 40% by mass, particularly preferably 25 to 35% by mass, based on the total mass of the polymerization solution.
% By mass. The concentration of all radically polymerizable monomers is 20
When the amount is at least mass%, the concentration is sufficient for use after polymerization, which is efficient. On the other hand, when the content is 45% by mass or less,
The molecular weight of the obtained polymer is not reduced, and a side reaction such as self-crosslinking does not occur. The amount of water is usually from 80 to 30% by mass, preferably from 60 to 75% by mass, more preferably from 65 to 75% by mass of the whole. When the amount of water is 80% by mass or less, the concentration is sufficient for use after the polymerization, which is efficient. When the content is 30% by mass or more, the molecular weight of the obtained polymer does not decrease,
In addition, side reactions such as self-crosslinking do not occur, and the molecular weight distribution becomes narrow, which meets the object of the present invention.

As the polymerization initiator (c) used in the polymerization using the polymerization initiator, conventionally known initiators can be used, for example, an azo initiator, a peroxide initiator,
Redox initiators, organic halogen compound initiators and the like can be mentioned. Specifically, azo-based initiators include azobisisobutyronitrile, azobiscyanovaleric acid and salts thereof, 2,2′-azobis (2-amidinopropane) hydrochloride, 2,2′-azobis (2- Methyl-N
-(2-hydroxyethyl) propionamide and the like; peroxide-based initiators include inorganic peroxides such as hydrogen peroxide, ammonium persulfate, potassium persulfate, and sodium persulfate; organic peroxides such as benzoyl peroxide; Di-t-butyl peroxide, cumene hydroperoxide, succinic peroxide, di (2-ethoxyethyl) peroxydicarbonate, etc .; redox-based initiators include alkali metal sulfites or bisulfites, Ammonium sulfate, ammonium bisulfite, ferric chloride,
Examples include a combination of a reducing agent such as ferric sulfate and ascorbic acid and an oxidizing agent such as an alkali metal persulfate, ammonium persulfate, hydrogen peroxide, and an organic peroxide.

The halogen of the organic halogen compound initiator includes fluorine, chlorine, bromine and iodine. The organic halogen compound is not particularly limited, but preferably has a halogen number of 1 selected from the group consisting of alkyl halides, alkyl phenyl ketones, alkyl carboxylic acids, and alkyl esters of halogenated alkyl carboxylic acids. -10 or more, carbon number 1-1
5 or more organohalogen compounds. More preferably, tetrachloromethane, trichlorobromomethane, trichloroiodomethane, dichloromethylphenylketone, 1-bromo-1-methylethylcarboxylic acid, 1-bromo-1-methylethylcarboxylic acid having 1 to 8 carbon atoms in the alkyl group Acid alkyl esters (eg, 1-bromo-1)
-Methylethyl carboxylate, ethyl 1-bromo-1-methylethylcarboxylate, octyl 1-bromo-1-methylethylcarboxylate, lauryl 1-bromo-1-methylethylcarboxylate). Particularly preferably, dichloromethyl phenyl ketone, alkyl group having 1 to 8 carbon atoms
1-bromo-1-methylethyl carboxylic acid alkyl ester. These initiators may be used alone or in combination of two or more.

In (c), the amount of the azo-based initiator, peroxide-based initiator and redox-based initiator used is usually 0.000 based on the mass of the radically polymerizable monomer (a).
It is 5 to 1% by mass, preferably 0.01 to 0.5% by mass. When the amount of these initiators is 0.0005% by mass or more, the effect of using (b) is remarkable,
A polymer having a narrow molecular weight distribution and low generation of low molecular weight products can be obtained. On the other hand, when the content is 1% by mass or less, the polymerization rate and the polymerization rate of the radical polymerizable monomer are sufficient, and the productivity is good. The amount of the organic halogen compound initiator to be used is usually 0.0005 to 10% by mass, preferably 0.001 to 10% by mass, based on the mass of the radically polymerizable monomer (a).
The content is 5% by mass, particularly preferably 0.005 to 3% by mass. The amount of the organic halogen compound initiator used is 0.0005.
When the content is not less than mass%, the effect of using (b) is remarkable,
That is, a polymer having a narrow molecular weight distribution and low generation of low molecular weight products can be obtained. On the other hand, when the content is 10% by mass or less, the polymerization rate and the polymerization rate of the radical polymerizable monomer are sufficient, and the productivity is good.

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 reversed-phase suspension polymerization method, a thin film polymerization method, a spray polymerization method and the like. No. Examples of the polymerization control method include an adiabatic polymerization method and a temperature-controlled polymerization method. In addition to the method of initiating polymerization with the radical polymerization initiator (c), radiation, electron beam,
A method of irradiating ultraviolet rays or the like to start polymerization may be employed. A solution polymerization method using the initiator (c) is preferred, and an aqueous solution polymerization method is particularly preferred because it does not require the use of an organic solvent or the like and is advantageous in terms of production cost. Further, a chain transfer agent may be used in combination. Examples of such a compound include thiols (n-laurylmercaptan,
Mercaptoethanol, mercaptopropanol, triethylene glycol dimercaptan, etc.), thiolic acids (thioglycolic acid, thiomalic acid, etc.), secondary alcohols (isopropanol, etc.), amines (dibutylamine, etc.), hypophosphites ( Sodium hypophosphite etc.), and the amount of the chain transfer agent is preferably 0.001 to 1% by mass based on the total amount of the radical polymerizable monomers.
It is.

In the present invention, the polymerization conditions are not particularly limited. For example, the polymerization initiation temperature can be variously changed depending on the type of the catalyst used, but is usually 0 to 100 ° C., preferably 5 to 80 ° C. The polymerization method is preferably an aqueous solution polymerization method, but may be carried out in the presence of water and a water-soluble organic solvent if necessary. In this case, the amount of the solvent with respect to water is usually 40% or less, preferably 30% or less on a mass basis. When a suspension polymerization method, a reversed phase suspension polymerization method or an emulsion polymerization method is used as the polymerization method, the polymerization is carried out, if necessary, in the presence of a conventionally known dispersant or surfactant. In the case of the reversed-phase suspension polymerization method, polymerization is performed using a conventionally known hydrocarbon solvent such as xylene, normal hexane, and normal heptane.

In the present invention, known additives such as surfactants, preservatives, fungicides, antibacterial agents, and antioxidants may be used at any stage (before, during and after polymerization) of the process of the present invention, if necessary. Agents, ultraviolet absorbers, colorants (pigments, dyes), fragrances, deodorants, inorganic powders, organic fibrous materials, dispersed deflocculants, builders, leveling agents, plasticizers, etc. The amount varies depending on the application, but is preferably 50% by mass or less based on the mass of the obtained polymer.

Examples of the surfactant include an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant such as US
P43331447, and one or more of these may be used in combination. Examples of the anionic surfactant include a hydrocarbon ether carboxylic acid having 8 to 24 carbon atoms or a salt thereof, [polyoxyethylene (degree of polymerization = 1 to 100) sodium lauryl ether acetate, polyoxyethylene (degree of polymerization = 1 to 1). 100) disodium lauryl sulfosuccinate etc.], a hydrocarbon sulfate 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 (polymerization degree = 1-100) coconut oil fatty acid monoethanolamide sodium sulfate, etc., and a hydrocarbon sulfonate having 8 to 24 carbon atoms [sodium dodecylbenzene sulfonate] And hydrocarbon phosphate ester salts having 8 to 24 carbon atoms [sodium lauryl phosphate, polyoxyethylene (degree of polymerization = 1 to 100), sodium lauryl ether phosphate, etc.], and fatty acid salts [sodium laurate, triethanol laurate] Amines], acylated amino acid salts [coconut fatty acid methyltaurine sodium, coconut fatty acid sarcosine sodium, coconut fatty acid sarcosine triethanolamine, N-coconut fatty acid acyl-L-glutamic acid triethanolamine, N-coconut fatty acid acyl -L-glutamine Sodium, lauroyl methyl -
[beta] -alanine sodium, etc.], and other [polyoxyethylene sulfosuccinate (degree of polymerization = 1 to 100) disodium lauroylethanolamide].

As the nonionic surfactant, specifically, for example, an aliphatic alcohol (8 to 24 carbon atoms) alkylene oxide (2 to 8 carbon atoms) adduct (degree of polymerization = 1 to 1)
100) [lauryl alcohol ethylene oxide addition (polymerization degree = 20), oleyl alcohol ethylene oxide addition (polymerization degree = 10), Macko alcohol ethylene oxide addition (polymerization degree = 35), etc.], polyoxyalkylene (carbon number) 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 (8 to 24 carbon atoms) esters [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 (C 2-8,
Polyhydric (divalent to divalent 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, polyoxyethylene (degree of polymerization = 50) methyl dioleate glucoside, etc.), fatty acid alkanolamide [1: 1 coconut oil fatty acid diethanolamide, 1: 1
Lauric acid diethanolamide, etc.], polyoxyalkylene (C2-8, polymerization degree = 1-100) alkyl (C1-2-22) phenyl ether (polyoxyethylene (polymerization degree = 20) nonylphenyl ether, etc.) , Polyoxyalkylene (2-8 carbon atoms, degree of polymerization = 1-10
0) alkyl (8-24 carbon atoms) amino ether and alkyl (8-24 carbon atoms) dialkyl (1 carbon atoms)
6) Amine oxides such as lauryl dimethylamine oxide, polydimethylsiloxane polyoxyethylene adducts, and polyoxyethylene / polyoxypropylene block polymers (weight average molecular weight = 150 to 10,000).

Examples of the cationic surfactant include quaternary ammonium salt type [stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, distearyldimethylammonium chloride, aminopropylethyldimethylammonium ethyl lanolin sulfate fatty acid], amine salt type [ Stearic acid diethylaminoethylamide lactate, dilaurylamine hydrochloride, oleylamine lactate, etc.]. Examples of the amphoteric surfactant include betaine-type amphoteric surfactants [coconut fatty acid amidopropyldimethylaminoacetic acid betaine, lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-
Hydroxyethylimidazolinium betaine, laurylhydroxysulfobetaine, lauroylamidoethylhydroxyethylcarboxymethylbetaine, sodium hydroxypropyl phosphate, etc.], amphoteric surfactant of amino acid type [sodium β-laurylaminopropionate, etc.]
Is mentioned.

As the antioxidant, triethylene glycol-bis- [3- (3-tert-butyl-5-methyl-4)
-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-
Hindered phenol-based antioxidants such as 4-hydroxybenzylphosphonate-diethyl ester; and amine-based antioxidants such as n-butylamine, triethylamine and diethylaminomethyl methacrylate.

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

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

Examples of the organic fibrous materials include natural fibers (cellulose-based (cotton, sawdust, straw, etc.), peat, wool, etc.), artificial fibers (cellulose-based such as rayon, acetate, etc.), synthetic fibers ( Polyamide, polyester, acrylic, etc.), pulp (mechanical pulp (crushed wood pulp from logs, asplund crushed wood pulp, etc.), chemical pulp (sulfite pulp, soda pulp, sulfate pulp, nitrate pulp, chlorine pulp, etc.), semi-chemical pulp And recycled pulp (for example, mechanically crushed or pulverized paper made from pulp once, or recycled pulp or the like which is mechanically crushed or pulverized waste paper).

The polymer obtained by the method of the present invention has a low molecular weight and a narrow molecular weight distribution. Therefore, there is little adverse effect due to a wide molecular weight distribution and a large number of low molecular weight products, and the value of the obtained polymer is improved. The weight average molecular weight of the polymer naturally varies depending on polymerization conditions, applications, and the like, but is usually 3,000 to 2,000,000. It is preferably from 10,000 to 1,000,000, and particularly preferably from 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,
The weight average molecular weight can be measured by the gel permeation chromatography method (GPC method) described below. For molecular weight distribution, see GP
In the case of the C method, it can be determined from the shape of the GPC chart and the area of the chart. Both ends of the peak of the GPC chart correspond to high molecular weight or low molecular weight. In the GPC chart of the polymer, assuming that the peak top molecular weight is M, M ×
The content of the low molecular weight compound of 0.2 or less and the high molecular weight material of M × 2.0 or more are preferably 2% or less and 5% or less, respectively, in the area on the GPC chart. It is more preferably 1% or less and 4% or less, respectively, and particularly preferably 0.8% or less and 3% or less, respectively.

If the molecular weight is higher than the above, it is difficult to perform accurate measurement by the GPC method, so a different measurement method is employed. For example, it can be measured by the intrinsic viscosity described below. In addition, the molecular weight distribution can be determined based on the spinning length described later. The smaller the spinning length, the smaller the molecular weight distribution. Although the spinning length varies depending on the intrinsic viscosity, the value of the spinning length / intrinsic viscosity is preferably 7 or less, more preferably 6 or less, and particularly preferably 5 or less.

The properties of the obtained polymer vary greatly depending on the kind, amount, molecular weight and the like of the radical polymerizable monomer used, and can be used for various applications. Forms can be obtained from liquid, viscous to solid at room temperature.
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, an aqueous coating agent, a photoresist, a sizing agent, a conductive agent, an antistatic agent for a fiber, an anti-fiber for a fiber Soil processing agents, resin processing binders, non-woven fabric binders, plastic reinforcing fiber binders, magnetic tape binders, resin concrete binders, dye pastes, adhesives, civil engineering thickeners, primers, pigment dispersants, pesticide granules Dispersant, pulverized coal dispersant, cement dispersant, scale inhibitor, compatibilizer, drainage / retention improver, binder for printing ink, flocculant, dye fixing agent, chelate polymer, polymer for hair setting, etc. (Ii) water-insoluble polymer: water-absorbing resin, oil-absorbing resin, polymer for increasing crude oil production, gelling agent, plasticizer, plastic They crowded antistatic agents, sealing agents, elastomers, electrophotographic toner binder, the printing ink binder, a binder for a magnetic tape, a lubricating oil detergent-dispersants, pour point depressants useful for the fillers, and the like.

For the above-mentioned applications, the optimum molecular weight of the polymer or a numerical value related thereto is described for the dispersant and the flocculant. Test examples are described in Examples, but the application is not limited thereto. For example, the intrinsic viscosity suitable for a flocculant is preferably 15 to 35 dl / g for nonionic or anionic flocculants, more preferably 18 to 30 dl / g.
dl / g, and preferably 3 to 20 dl / g, more preferably 5 to 15 dl / g in the case of a cationic flocculant. The thread length suitable for the flocculant is preferably 50 to 120 mm, more preferably 50 to 100 mm for a nonionic or anionic flocculant, and preferably 5 to 90 mm, more preferably for a cationic flocculant. 5-80
mm.

The peak top molecular weight M of GPC suitable for various dispersants is preferably from 3,000 to 30,000, more preferably from 5,000 to 25,000.
The content of a low molecular weight substance of M × 0.2 or less and a high molecular weight substance of M × 2.0 or more are preferably 1% or less and 4% or less, more preferably, respectively, in the area on the GPC chart. 0.9% or less, 3.5% or less,
Particularly preferably, they are respectively 0.8% or less and 3% or less.

The following measurement values are obtained by the following method. (Molecular Weight Measurement by GPC Method) The method of measuring the peak top molecular weight by GPC and calculating the contents of low molecular weight substances and high molecular weight substances is as follows. The content of the peak top molecular weight, the low molecular weight substance and the high molecular weight substance are all values assuming complete neutralization with sodium hydroxide. << GPC measurement conditions >> Model: Waters 510 (manufactured by Nippon 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 rate: 1.0 ml / min Sample concentration: 0.25 mass% Injection volume: 200 μl Standard: polyoxyethylene glycol (Tosoh Corporation; TSK STANDARD POLYETHYLENE OXIDE) Data processing Apparatus: SC-8010 (manufactured by Tosoh Corporation)

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

[0051]

The present invention will be further described below with reference to examples, but the present invention is not limited to these examples. Hereinafter, unless otherwise specified, parts are parts by mass. Example 1 A pressure-resistant reaction vessel was charged with 540 parts of water, replaced with nitrogen, sealed, and heated to 90 ° C. 77 parts of acrylic acid under stirring,
228 parts of acrylic acid, n-lauryl mercaptan
5 parts, a homogenous mixture of 4 parts of triphenylphosphine (PPh ₃ ) and 0.7 part of ferrous chloride (tetrahydrate), and 50 parts of a 6% aqueous solution of sodium persulfate were placed in separate containers for 5 parts each. After 1 hour, the solution was dropped over 4 hours and 6.0 hours. After completion of the dropwise addition, 3 parts of a 35% aqueous hydrogen peroxide solution were added, and the mixture was maintained at the same temperature for 3 hours to confirm a polymerization rate of 99.9% or more. An aqueous sodium solution was obtained. Table 1 shows the peak top molecular weight, low molecular weight content, and high molecular weight content of sodium polyacrylate.

Example 2 In place of acrylic acid, acrylic acid / methacrylic acid = 50
/ 50 (molar ratio) and a sodium salt aqueous solution of a copolymer of acrylic acid and methacrylic acid was obtained in the same manner as in Example 1 except that 32.2 parts of a 48% aqueous sodium hydroxide solution was used. Table 1 shows the peak top molecular weight, low molecular weight content, and high molecular weight content of the copolymer.

Example 3 An aqueous solution of sodium acrylate was obtained in the same manner as in Example 1 except that 1,2-bis (diphenylphosphino) methane (dppm) was used instead of PPh ₃ . Table 1 shows the peak top molecular weight, low molecular weight content, and high molecular weight content of the copolymer.

Example 4 An aqueous solution of sodium acrylate was obtained in the same manner as in Example 1 except that 1,2-bis (ethyltolylphosphino) methane was used instead of PPh ₃ . Table 1 shows the peak top molecular weight, low molecular weight content, and high molecular weight content of the copolymer.

Comparative Example 1 A polymer (Comparative Example 1) was obtained in the same manner as in Example 1 except that PPh ₃ was not used. Table 1 shows the peak top molecular weight, low molecular weight content, and high molecular weight content of the polymer.

[0056]

[Table 1]

Test Example 1 (Wet pulverization and dispersion test of heavy calcium carbonate) Each of 25 parts of water and 0.6 part (in terms of solid content) of the polymer of Examples 1 to 4 and Comparative Example 1 were uniformly dissolved. 75 parts of coarse ore of calcium bicarbonate was added to the aqueous solution, and the mixture was stirred and dispersed using a sand grinder for 30 minutes. Immediately after the production of the obtained 75% by weight aqueous calcium carbonate slurry, and 30% by weight.
The viscosity after standing at 8 ° C. for 8 days was measured using a BL viscometer at 25 ° C.
The measurement was performed under the condition of 60 rpm. Table 2 shows the test results.

[0058]

[Table 2]

Test Example 2 (Dispersion of Satin White) Using the polymers of Examples 1 to 4 and Comparative Example 1, 1.74 g of a polymer aqueous solution (solids) as a dispersant was added to 200 g of a satin white cake containing 71% water. After the addition, the slurry was uniformly dispersed, and the viscosity of the slurry was measured with a BL viscometer at 35 ° C. and 60 rpm. Table 3 shows the test results.

[0060]

[Table 3]

The polymers of Examples 1 to 4 have better dispersibility of calcium carbonate and satin white than the polymer of Comparative Example 1.

Example 5 80 parts of acrylamide, 1.5 parts of PPh _{3 and} 280 parts of ion-exchanged water were charged in an adiabatic reaction vessel, and nitrogen was vigorously blown into the liquid at 5 ° C. for 20 minutes. Then, 10 parts of an aqueous solution of azobisamidinopropane hydrochloride 10%, hydrogen peroxide 1
2 parts of a 0% aqueous solution and 1 part of a 10% aqueous sodium bisulfite solution were added. After the addition, the blowing of nitrogen was stopped. After about 10 minutes, the temperature of the solution began to rise, and the system gradually thickened and became a gel-like polymer. After 24 hours, the gel was shredded, dried with hot air at 70 ° C. for 10 hours, and then pulverized to obtain a powdery polymer.
Table 4 shows the intrinsic viscosity and the thread length of the polymer.

Example 6 Acrylamide 60 was used in place of 80 parts of acrylamide.
Example 5 except that 20 parts by weight of sodium acrylate were used.
A powdery polymer was obtained in the same manner as described above. Table 4 shows the intrinsic viscosity and the thread length of the polymer.

Comparative Example 2 A powdery polymer was obtained in the same manner as in Example 5 except that PPh ₃ was not used. Table 4 shows the intrinsic viscosity and the thread length of the polymer.

The intrinsic viscosities and string lengths of Examples 5 and 6 and Comparative Example 2 were measured according to the following measuring methods. (Measurement Method of Intrinsic Viscosity) The intrinsic viscosity is a value measured with a 1N aqueous sodium nitrate solution at 20 ° C. using a Cannon-Fenske viscometer. The value obtained by extrapolating the concentration to zero in a graph in which the viscosities at several concentrations of the polymer dilute solution are plotted on the horizontal axis and the ordinate is the viscosity is the intrinsic viscosity of the polymer. (Measurement method of string length) The string length is obtained by dissolving a polymer in ion-exchanged water to form a 0.2% aqueous solution, attaching a glass ball having a diameter of 7 mm to a depth of 15 mm, and removing the glass ball at a speed of 16 mm / sec. It is a value measured at 22 ° C. at the time of pulling up, until the polymer aqueous solution breaks.

[0066]

[Table 4]

Performance Evaluation Example 1 (Test as Flocculant) Using the polymers obtained in Examples 5 and 6 and Comparative Example 2, K gravel washing wastewater (suspended matter 0.35%, pH 6.0) was used. A coagulation test was performed. Table 5 shows the test results. In the coagulation test, 500 ml of waste water was placed in a 500 ml measuring cylinder with a stopper (sedimentation tube), and a predetermined amount of a 0.1% (solid content converted) ion exchange aqueous solution of a polymer was added thereto at room temperature. Next, the sedimentation tube was turned 45 times to mix the wastewater and the aqueous polymer solution to form flocs. After that, the sedimentation tube was allowed to stand, and the sedimentation velocity at the interface of the floc layer was measured. Sedimentation velocity is m
/ Hr.

[0068]

[Table 5]

It can be seen that the polymers of Examples 5 and 6 can obtain a higher sedimentation rate with a lower addition amount than the polymer of Comparative Example 2.

[0070]

In the radical polymerization in an aqueous solution, the polymer obtained by the production method of the present invention has a low molecular weight product and a narrow molecular weight distribution. Accordingly, the harmful effects particularly due to the presence of low molecular weight substances are reduced, and the polymer of the present invention is a useful polymer.

Claims (8)

[Claims] 1. A method for producing a polymer by radically polymerizing one or more radically polymerizable monomers (a) which become water-soluble and / or water-soluble by hydrolysis, comprising the steps of: producing a tertiary phosphine (b); A method for producing a polymer, comprising conducting polymerization in the presence of a polymerization initiator (c) and water. 2. The method according to claim 1, wherein (b) is an aromatic phosphine. 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 base. A water-soluble radical polymerizable monomer (a1) having a hydrophilic group selected from the group and / or a radical having a group which becomes water-soluble by hydrolysis selected from the group consisting of an acid anhydride group, a lower alkyl ester group and a nitrile group; 3. The method for producing a polymer according to claim 1, which is a polymerizable monomer (a2). 4. The composition according to claim 1, which is obtained by further copolymerizing (a) with another radical copolymerizable monomer (a3).
3. The method for producing a polymer according to any one of 3. 5. The method according to claim 4, wherein (a3) is a hydrophobic radically polymerizable monomer and / or a crosslinkable radically polymerizable monomer. 6. The amount of (b) is 0.001 to 1% by mass based on the total mass of (a) and (a3).
A method for producing a polymer according to any one of claims 1 to 5. 7. A polymer obtained by the method according to claim 1, wherein the polymer has a weight average molecular weight of 10,000 to 1,000,000. Assuming that the peak top molecular weight of the molecular weight measurement chart by the GPC method is M, a low molecular weight compound of M × 0.2 or less and M
A polymer having a content of a high molecular weight substance of × 2.0 or more in an area on a GPC chart of 2% or less and 5% or less, respectively. 8. The polymer obtained by the production method according to claim 1, wherein the spinning length / intrinsic viscosity of the polymer is 7 or less.