JP2012206038A - Polymer coagulant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer coagulant capable of greatly improving the dehydrating treatment efficiency of sludge by forming firm coarse floc in a dehydrating treatment of hardly dehydrated organic sludge or the like.SOLUTION: The polymer coagulant contains a water-soluble polymer (A) formed by polymerizing monomers containing water-soluble unsaturated monomers (a) in the presence of at least one kind of living radical polymerization initiator (Iv) selected from a group consisting of the following (Iv1) and (Iv2). The (Iv1) is an organic tellurium compound represented by following general formula (1). The (Iv2) is a mixture of: a transition metal complex selected from a group consisting of ruthenium, palladium, copper, iron, molybdenum, rhodium and nickel; an organic halide selected from a group consisting of an organic iodide and an organic chloride; and a Lewis base selected from a group consisting of amine and phosphine. Formula (1): R4R3R2C-Te-R1.

Description

  The present invention relates to a polymer flocculant. More specifically, the present invention relates to a polymer flocculant having excellent dewatering performance of organic sludge.

Conventionally, for the dehydration of organic sludge such as sewage or human waste (hereinafter abbreviated as sewage sludge) or factory wastewater (hereinafter abbreviated as wastewater), polymethacryloyloxyethyltrimethylammonium chloride, acrylamide-acryloyloxyethyltrimethyl Cationic polymer flocculants such as ammonium chloride copolymer and polyamidine, and amphoteric polymer flocculants such as acrylamide-acrylic acid-acryloyloxyethyltrimethylammonium chloride copolymer are widely used.
In addition, nonionic polymer flocculants such as polyacrylamide and anionic polymer flocculants such as acrylamide-sodium acrylate copolymer are widely used for dewatering inorganic sludge such as wastewater.
Known methods for producing these polymer flocculants include an aqueous solution polymerization method, a thin film polymerization method, a reverse phase suspension polymerization method, a precipitation polymerization method, and an emulsion polymerization method.
Among these polymer flocculants, in recent years, especially regarding the dewatering of organic sludge, there is an increasing need for an increase in the dewatering treatment speed from the viewpoint of increasing the amount of generated sludge and making sludge properties difficult to dewater. Therefore, a polymer flocculant that forms stronger floc strength is desired. In addition, the polymer flocculants that can reduce the moisture content of dehydrated cakes due to soaring incineration costs when dewatered cakes are incinerated, and the tightness of landfill sites when dehydrated cakes are landfilled as they are, It is desired.
Recently, as a polymer flocculant for the purpose of improving these performances, for example, amphoteric compounds in which partial crosslinking is formed by adding and reacting with a crosslinking agent chemically bonded to a carboxylic acid group in the polymer during or after polymerization. A polymer flocculant (for example, see Patent Document 1), a product produced by adding a polyalkylene oxide compound having an azo group or a polyalkylene oxide compound having a photocleavable group during polymerization (for example, see Patent Document 2), polymerization Sometimes manufactured by adding a nitroxy radical (see, for example, Patent Document 3).

Japanese Patent No. 3305688 JP 2002-97236 A JP 2001-139606 A

However, currently used polymer flocculants have not yet reached a level that can sufficiently solve the above problems, and the disclosed polymer flocculants have a floc strength and a dehydrated cake moisture content. From the point of view, although it was improved somewhat, it was still insufficient.
An object of the present invention is to provide a polymer flocculant capable of forming a strong coarse floc in the dewatering treatment of hardly dewatering organic sludge and greatly improving the sludge dewatering efficiency.

The inventor of the present invention has arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention provides a monomer containing a water-soluble unsaturated monomer (a) in the presence of at least one living radical polymerization initiator (Iv) selected from the group consisting of the following (Iv1) and (Iv2): A polymer flocculant comprising a polymerized water-soluble polymer (A).
(Iv1) Organic tellurium compound represented by the following general formula (1) (Iv2) Complex of transition metal selected from the group consisting of ruthenium, palladium, copper, iron, molybdenum, rhodium and nickel, organic iodide and organic chlorinated compound Organic halides selected from the group consisting of, and mixtures of Lewis bases selected from the group consisting of aluminum and titanium

R ⁴ R ³ R ² C-Te-R ¹ (1)

[In the formula, R ¹ having 1 to 8 carbon atoms, an alkyl group, an aryl group, a substituted aryl group or an aromatic heterocyclic group; R ² and R ³ are H or an alkyl group having 1 to 8 carbon atoms; R ⁴ is An aryl group, substituted aryl group, aromatic heterocyclic group, acyl group, amide group, oxycarbonyl group or cyano group having 2 to 10 carbon atoms is represented. ]

The polymer flocculant of the present invention has the following effects.
(1) A strong coarse floc is formed in dewatering treatment of organic sludge and the like.
(2) Since the formed floc is not easily broken or redispersed, the stability and processing speed of the aggregation treatment can be remarkably increased.
(3) The moisture content of the cake after the dehydration step is low, and the amount of waste and incineration costs can be reduced.

[Water-soluble polymer (A)]
The water-soluble polymer (A) in the present invention comprises a water-soluble unsaturated monomer (a) containing 50 to 100 mol% of a cationic monomer (a1) represented by the following general formula [1] or [2]. And As (a), in addition to (a1), a nonionic monomer (a2) and / or an anionic monomer (a3) having one unsaturated group can be further contained as required.
In the following and below, a water-soluble unsaturated monomer or a water-soluble polymer means one having a solubility in water of 1 g / 100 g (20 ° C.) or more. It means that the solubility is less than 1 g / 100 g of water (20 ° C.).

^{_{CH 2 = C (R 5)}} CO-Q-X-NR 6 R 7 [1]
^{_{CH 2 = C (R 5)}} CO-Q-X-N + R 6 R 7 R 8 · Z - [2]

In the formulas [1] and [2], R ⁵ is H or a methyl group, R ⁶ and R ⁷ are carbon numbers (hereinafter abbreviated as C) 1 to 3 [flocculation performance (high floc strength, floc coarsening, dehydrated cake) In view of reducing the water content, etc., the same shall apply hereinafter), it preferably represents an alkyl group of 1-2]. R ⁸ represents H, C 1-7 alkyl or benzyl group. R ^{5 to} R ⁸ may be the same as or different from each other.
Z ⁻ represents an anion such as a halogen ion, a sulfate ion, a phosphate ion, or a nitrate ion.

Examples of (a1) to (a3) include the following.
(A1) Cationic monomer The following are included, and salts thereof [for example, inorganic acid (hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, etc.) salts, methyl chloride salts, dimethyl sulfate salts and benzyl chloride salts], and mixtures thereof. .
(A11) Nitrogen atom-containing (meth) acrylate [where (meth) acrylate represents acrylate or methacrylate. same as below. ]
C5-30, such as aminoalkyl (C2-3) (meth) acrylate, N, N-dialkyl (alkyl group is C1-2) aminoalkyl (C2-3) (meth) acrylate [N, N-dimethylaminoethyl and -Propyl (meth) acrylate, N, N-diethylaminoethyl and -propyl (meth) acrylate and the like], heterocycle-containing (meth) acrylate [N-morpholinoethyl (meth) acrylate and the like];
(A12) Nitrogen atom-containing (meth) acrylamide derivative C5-30, such as N, N-dialkyl (C1-2) aminoalkyl (C2-3) (meth) acrylamide [N, N-dimethylaminoethyl (meth) acrylamide, etc. ];
(A13) ethylenically unsaturated compound having amino group C5-30, such as vinylamine, vinylaniline, (meth) allylamine, p-aminostyrene, etc.];
(A14) Compound having amine imide group C5-30, such as 1,1,1-trimethylamine (meth) acrylimide, 1,1-dimethyl-1-ethylamine (meth) acrylimide, 1,1-dimethyl-1- ( 2'-Phenyl-2'-hydroxyethyl) amine (meth) acrylimide.

(A2) Nonionic monomer The following are mentioned, and these mixtures.
(A21) (Meth) acrylate C4 or more and number average molecular weight [hereinafter abbreviated as Mn. The measurement is based on a gel permeation chromatography (GPC) method under the conditions described later. ] 5,000 or less, for example, hydroxyl group-containing (meth) acrylate [eg, hydroxyethyl-, diethylene glycol mono-, polyethylene glycol (polymerization degree 3-50) mono- and polyglycerol (polymerization degree 1-10) mono (meth) acrylate] And alkyl acrylate (alkyl group is C1-2) ester (C4-5, such as methyl acrylate, ethyl acrylate);
(A22) (Meth) acrylamide and derivatives thereof C3-30, such as (meth) acrylamide, N-alkyl (C1-3) (meth) acrylamide [N-methyl and -isopropyl (meth) acrylamide etc.], N-alkylol (Meth) acrylamide [N-methylol (meth) acrylamide etc.];
(A23) Nitrogen-containing ethylenically unsaturated compounds other than (a1) C3-30, such as acrylonitrile, N-vinylformamide, N-vinyl-2-pyrrolidone, N-vinylimidazole, N-vinylsuccinimide, N-vinyl Carbazole and 2-cyanoethyl (meth) acrylate.

In addition, the measurement conditions of Mn by GPC method in this invention are as follows, The weight average molecular weight (henceforth Mw) mentioned later can also be measured similarly.
<GPC measurement conditions>
GPC model: HLC-8120GPC, manufactured by Tosoh Corporation Column: 2 TSKgel GMHXL + TSKgel Multipore
HXL-M [all manufactured by Tosoh Corporation]
Measurement temperature: 40 ° C
Eluent: Tetrahydrofuran solution injection volume: 100 μl
Detection apparatus: Refractive index detector reference material: Standard polystyrene (TSK standard POLYSTYRENE),
Made by Tosoh Corporation

(A3) Anionic monomer The following, these salts [alkali metal (lithium, sodium, potassium, etc., the same shall apply hereinafter) salt, alkaline earth metal (magnesium, calcium, etc., the same shall apply hereinafter) salt, ammonium salt and amine (C1-20) salts and the like], and mixtures thereof.
(A31) unsaturated carboxylic acid C3-30, such as (meth) acrylic acid, (anhydrous) maleic acid, fumaric acid, (anhydrous) itaconic acid, vinylbenzoic acid, allyl acetic acid;
(A32) Unsaturated sulfonic acid C2-20 aliphatic unsaturated sulfonic acid (such as vinyl sulfonic acid), C6-20 aromatic unsaturated sulfonic acid (such as styrene sulfonic acid), sulfonic acid group-containing (meth) acrylate [ Sulfoalkyl (C2-20) (meth) acrylate [2- (meth) acryloyloxyethane, -propane and -butanesulfonic acid, 3- (meth) acryloyloxypropanesulfonic acid, 4- (meth) acryloyloxybutanesulfonic acid 2- (meth) acryloyloxy-2,2-dimethylethanesulfonic acid, p- (meth) acryloyloxymethylbenzenesulfonic acid, etc.], sulfonic acid group-containing (meth) acrylamide [2- (meth) acryloylaminoethanesulfone Acid, 2- and 3- (meth) acryloylaminoprop Sulfonic acid, 2- and 4- (meth) acryloylaminobutanesulfonic acid, 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid, p- (meth) acryloylaminomethylbenzenesulfonic acid, etc.], alkyl ( C1-20) (meth) allylsulfosuccinic acid ester [methyl (meth) allylsulfosuccinic acid ester and the like] and the like;
(A33) (Meth) acryloyl polyoxyalkylene (alkylene group is C1-6) sulfate ester (meth) acryloyl polyoxyethylene (polymerization degree 2-50) sulfate ester and the like.

  Among (a), from the viewpoint of increasing the molecular weight of the water-soluble polymer (A), (a12) and (a13) among the cationic monomers, (a21) and (a22) among the nonionic monomers, Of the anionic monomers (a31), (a32), more preferably (a12), (a13), (a21), (a22), (a31), and (a32) containing a sulfonic acid group ( (Meth) acrylate and sulfonic acid group-containing (meth) acrylamide, particularly preferred are (a12), (a13), (a21), (a31), and (a32) sulfonic acid group-containing (meth) acrylate and sulfone. Acid group-containing (meth) acrylamide, most preferably (meth) acrylamide of (a12), acrylonitrile of (a13), N-vinyl Formamide, N, N-dimethylaminoethyl (meth) acrylate in (a21) and salts thereof (the foregoing), (meth) acrylic acid in (a31), (anhydrous) maleic acid, (anhydrous) Itaconic acid and alkali metal salts thereof, (a32) 2- (meth) acryloyloxyethanesulfonic acid, 2- and 3- (meth) acryloyloxypropanesulfonic acid, 2- (meth) acryloylamino-2, 2-dimethylethanesulfonic acid and alkali metal salts thereof. Moreover, these (a) can be arbitrarily mixed and copolymerized.

  The content (mol%) of the cationic monomer (a1) in the water-soluble unsaturated monomer (a) is preferably 50 to 100 mol%, more preferably 70 to 100% from the viewpoint of aggregation performance.

As a monomer constituting the water-soluble polymer (A), a water-insoluble monomer (x) and a cross-linkable monomer (y) are used in combination with the water-soluble unsaturated monomer (a) as necessary, as long as the effects of the present invention are not impaired. can do.
Examples of the water-insoluble monomer (x) include the following (x1) to (x5) and mixtures thereof.
(X1) (Meth) acrylate of C6-23 (meth) acrylate of aliphatic or alicyclic alcohol (C3-20) [propyl-, butyl-, lauryl-, octadecyl- and cyclohexyl (meth) acrylate etc.] and epoxy Group (C4-20) -containing (meth) acrylate [glycidyl (meth) acrylate and the like];

(X2) Unsaturated carboxylic acid of [monoalkoxy (C1-20)-, monocycloalkoxy (C3-12)-or monophenoxy] polypropylene glycol (polypropylene glycol is hereinafter abbreviated as PPG) (degree of polymerization 2-50) Monoester Monool (C1-20) or monohydric phenol (C6-20) propylene oxide (hereinafter abbreviated as PO) adduct (meth) acrylate ester [ω-methoxy PPG mono (meth) acrylate, ω-ethoxy PPG mono (meth) acrylate, ω-propoxy PPG mono (meth) acrylate, ω-butoxy PPG mono (meth) acrylate, ω-cyclohexyl PPG mono (meth) acrylate, ω-phenoxy PPG mono (meth) acrylate, etc.] and diol (C2-20) or Valence phenol (meth) acrylic acid ester [.omega.-hydroxyethyl (poly) oxypropylene mono (meth) acrylate] of the PO adduct of (C6-20) or the like;

(X3) C2-30 unsaturated hydrocarbon ethylene, nonene, styrene, 1-methylstyrene and the like;
(X4) carboxylic acid (C2-30) ester (such as vinyl acetate) of unsaturated alcohol [C2-4, for example, vinyl alcohol, (meth) allyl alcohol];
(X5) A halogen-containing monomer (C2-30, such as vinyl chloride).

In addition, as the crosslinkable monomer (y), the following (y1) to (y5) having two or more unsaturated groups, salts thereof [for example, for basic monomers, inorganic acids (hydrochloric acid, Hydrobromic acid, hydroiodic acid, sulfuric acid, sulfurous acid, phosphoric acid, nitric acid, etc.) salt, methyl chloride salt, dimethyl sulfate salt, benzyl chloride salt, etc., for acidic monomers, alkali metal salts, alkaline earth metal salts, Amines (C1-20, such as methylamine, ethylamine, cyclohexylamine) salts], and mixtures thereof.
(Y1) Bispoly (2-4 or more) (meth) acrylamide C5-30, such as N, N′-methylenebis (meth) acrylamide;
(Y2) poly (2-4 or more) (meth) acrylates C8-30, such as ethylene glycol di (meth) acrylate, pentaerythritol [poly (2-4)] (meth) acrylate;

(Y3) Vinyl group (2 to 20 or more) -containing monomer C4 or more and Mn 6,000 or less, such as divinylamine, polyvalent (2 to 5 or more) amine [C2 or more and Mn 3,000 or less, such as ethylenediamine , Polyethyleneimine (C4 or more and Mn3,000 or less)] poly (2-20) vinylamine, divinyl ether, polyhydric alcohol [C2 or more and Mn3,000 or less, such as alkylene (C2-6 or more) glycol [ethylene Glycol, propylene glycol, 1,6-hexanediol (hereinafter abbreviated as EG, PG, 1,6-HD, respectively)], polyoxyalkylene [Mn 2,000 to 3,000, such as polyethylene glycol (hereinafter referred to as PEG) (Abbreviation) (Molecular weight 106 or more and Mn 3,000 Lower), PPG (molecular weight 134 to Mn 3,000), polyoxyethylene (molecular weight 106 to Mn 3,000) / polyoxypropylene (molecular weight 134 to Mn 3,000) block copolymer], trimethylolethane, Tri (methylolpropane), (poly) (2-50) glycerin, pentaerythritol, sorbitol (hereinafter abbreviated as TME, TMP, GR, PE, SO, respectively), starch] poly (2-20) vinyl ether, and the like;

(Y4) Allyl group (2 to 20 or more) -containing monomer C6 or more and Mn 3,000 or less, for example, di (meth) allylamine, N-alkyl (C1-20) di (meth) allylamine, polyvalent amine (above Poly (2-20) (meth) allylamine, di (meth) allyl ether, poly (2-20) (meth) allyl ether of polyhydric alcohol (above), poly (2-20) ( (Meth) allyloxyalkanes (C1-20) (tetraallyloxyethane and the like);
(Y5) Epoxy group-containing monomer C8 or more and Mn 6,000 or less, for example, EG diglycidyl ether, PEG diglycidyl ether, GR triglycidyl ether.

  The content of each monomer based on the total number of moles of the monomers (a), (x) and (y) constituting the water-soluble polymer (A) is preferably from 50 to 100 moles from the viewpoint of aggregation performance. %, More preferably 70 to 100 mol%; (x) is usually 40 mol% or less, preferably 0.1 to 20 mol% from the viewpoint of the aggregation performance and the solubility of the polymer flocculant in water, Preferably, 0.5 to 10 mol%; Moreover, although (y) depends on the polymerizability or reactivity of (y), it is usually 5 mol% or less. From the viewpoint of solubility, it is preferably 0.001 to 1 mol%, more preferably 0.01 to 0.5 mol%.

(A) is a known aqueous solution polymerization (for example, adiabatic polymerization, thin film polymerization, spray polymerization, etc. described in JP-A-55-133413) or a known reversed-phase suspension polymerization (for example, Japanese Patent Publication No. 54-30710). Various polymerization methods including those described in JP-A-56-26909, JP-A-1-5808), photopolymerization (for example, those described in JP-B-6-804), precipitation polymerization (for example, And those produced by reverse-phase emulsion polymerization (for example, those described in JP-A-58-197398) and the like] and a radical polymerization initiator.
Among the polymerization methods, the aqueous solution polymerization method is preferable from the industrial viewpoint that it is not necessary to use an organic solvent or the like. Hereinafter, the method using the living radical polymerization initiator (Iv) or (Iv) and other radical polymerization initiator (Iz) may be referred to as a radical polymerization method.

[Living radical polymerization initiator (Iv)]
The living radical polymerization initiator (Iv) in the present invention is at least one living radical polymerization initiator selected from the group consisting of the following (Iv1) and (Iv2).

[Organic Tellurium Compound (Iv1) Represented by General Formula (1)]
(Iv1) in the present invention is an organic tellurium compound represented by the following general formula (1).

R ⁴ R ³ R ² C-Te-R ¹ (1)

In the formula, R ¹ represents a C1-20 alkyl group, aryl group, substituted aryl group or aromatic heterocyclic group. When C of R ¹ exceeds 20, the solubility of (Iv1) in water is deteriorated, the living radical polymerizability is reduced, and the aggregation performance of the resulting water-soluble polymer is deteriorated.
R ² and R ³ represents H or C1~8 alkyl group. When C of R ² and R ³ exceeds 8, the solubility in water is deteriorated, the living radical polymerizability is lowered, and the aggregation performance of the obtained water-soluble polymer is deteriorated.
R ⁴ represents a C1-20 aryl group, substituted aryl group, aromatic heterocyclic group, acyl group, amide group, oxycarbonyl group or cyano group. When C of R ⁴ exceeds 20, the polymerization rate decreases.

As the alkyl group in R ¹ , C1-8, such as methyl group, ethyl group, n- and i-propyl group, cyclopropyl group, n-, sec- and ter-butyl group, cyclobutyl group, n-pentyl group, Examples thereof include linear, branched and cyclic alkyl groups such as n-hexyl group, n-heptyl group and n-octyl group. Of these, C1-4 linear and branched alkyl groups are preferred from the viewpoint of increasing the molecular weight of (A), and methyl, ethyl and n-butyl groups are more preferred.
As an aryl group, C6-10, for example, a phenyl group, a naphthyl group is mentioned. Of these, a phenyl group is preferred from the viewpoint of increasing the molecular weight of (A).

Examples of the substituted aryl group include C7-20, for example, a phenyl group having a substituent, a naphthyl group, and the like. The substituent of the substituted aryl group, for example a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a nitro group, a cyano group, a carbonyl-containing group represented by -COR ^a (R a is a C1-8, alkyl group, aryl Group, alkoxy group or aryloxy group), sulfonyl group, and trifluoromethyl group. The number of these substituents is preferably 1 to 2 from the viewpoint of increasing the molecular weight of (A), and in the case of 2, the para position or the ortho position is preferable from the same viewpoint.
Among the substituted aryl groups, a trifluoromethyl-substituted phenyl group is preferable from the viewpoint of increasing the molecular weight.
Moreover, as an aromatic heterocyclic group, C4-10, for example, a pyridyl group, a pyrrole group, a furyl group, and a thienyl group are mentioned.

Examples of the C1-8 alkyl group represented by R ² and R ³ include the same alkyl groups as those described above for R ¹ .

Among the groups represented by R ⁴ , examples of the aryl group, substituted aryl group, and aromatic heterocyclic group include the same groups as those represented by R ¹ above.
Examples of the acyl group include a formyl group, an acetyl group, and a benzoyl group.
Examples of the amide group include carboxylic acid amide (acetamide, malonamide, succinamide, maleamide, benzamide, 2-fluamide, etc.), thioamide (thioacetamide, hexanedithioamide, thiobenzamide, methanethiosulfonamide, etc.), selenoamide (selenoacetamide, hexane) And di-selenoamide, selenobenzamide, methaneselenosulfonamide, etc.), N-substituted amides (N-methylacetamide, benzanilide, cyclohexanecarboxanilide, 2,4′-dichloroacetanilide, etc.).

As the oxycarbonyl group, a group represented by -COOR ^b (R ^b is H, a C1-8 alkyl group or an aryl group), for example, a carboxyl group, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, n-, Examples thereof include a sec- and ter-butoxycarbonyl group, an n-pentoxycarbonyl group, and a phenoxycarbonyl group. Among these, a methoxycarbonyl group and an ethoxycarbonyl group are preferable from the viewpoint of increasing the molecular weight of (A).

Of the groups represented by R ⁴ , aryl groups, substituted aryl groups, oxycarbonyl groups, and cyano groups are preferable from the viewpoint of living radical polymerizability, and more preferable are phenyl groups and halogen atom substitutions (particularly 1 to 5 groups). Substituted) phenyl group, trifluoromethyl-substituted phenyl group, methoxycarbonyl group, ethoxycarbonyl group.

Formula (1) an organic tellurium compound represented by preferred as (Iv1) is, R ¹ is an alkyl group or a phenyl group C1 -4, R ² and R ³ are H or an alkyl group C1 -4 , R ⁴ is a C6-20 (substituted) aryl group or oxycarbonyl group, more preferably R ¹ is a C1-4 alkyl group or phenyl group, and R ² and R ³ are H or alkyl C1 -4, R ⁴ is (substituted) phenyl group C6-20, those which are methoxycarbonyl group or ethoxycarbonyl group.
Specific examples of (Iv1) include (methylterranylmethyl) benzene, (methylterranylmethyl) naphthalene, ethyl-2-methyl-2-methylterranyl-propionate, ethyl-2-methyl-2-n-butylterranyl-propionate. Can be illustrated.

[(Iv2) transition metal complexes selected from the group consisting of iron, molybdenum, ruthenium, palladium, copper, rhodium and nickel, organic halides selected from the group consisting of organic iodides and organic chlorides, and aluminum and titanium A mixture of Lewis bases selected from the group consisting of
The metal constituting the transition metal complex in (Iv2) is an element of Group 6 to 11 of the periodic table (according to the periodic table described in “Basic Manual I Revised 4th Edition” edited by the Chemical Society of Japan (1993)). Which is a transition metal selected from the group consisting of ruthenium, palladium, copper, iron, molybdenum, rhodium and nickel, of which iron and molybdenum are preferred.

As a specific example of the complex in which the transition metal is iron, iron (II) [in the following, (II) represents an ionic valence of 2. ] Acetate, dicarbonylcyclopentadienyl iodoiron, iron (II) acetylacetonate, iron (II) phthalocyanine, 1,1'-diacetylferrocene, 1,1'-dimethylferrocene, dicarbonylcyclopentadienyl iron dimer , Dicyclopentadienyl iron, tricarbonyl (cyclooctatetraene) iron and the like, and dicarbonylcyclopentadienyl iron dimer is preferable from the viewpoint of increasing the molecular weight of the water-soluble polymer (A).

  Specific examples of the complex in which the transition metal is molybdenum include molybdenum hexacarbonyl, molybdenum (II) acetate dimer, [1,1′-bis (diphenylphosphino) ferrocene] tetracarbonylmolybdenum, [1,2-bis (diphenyl). Phosphino) ethane] tetracarbonylmolybdenum, (bicyclo [2.2.1] hepta-2,5-diene) tetracarbonylmolybdenum, (propylcyclopentadienyl) molybdenum tricarbonyl dimer, cis-tetracarbonylbis (piperidine) Molybdenum, cyclopentadienyl molybdenum tricarbonyl halide, cyclopentadienyl molybdenum tricarbonyl dimer, dicarbonyl (pentamethylcyclopentadienyl) molybdenum dimer, methylcyclopentadiene Le molybdenum tricarbonyl dimer, triamine molybdenum tricarbonyl, tricarbonyl (cycloheptatriene) molybdenum and the like, cyclopentadienyl molybdenum tricarbonyl dimer are preferable from the viewpoint of molecular weight of the water-soluble polymer (A).

  As the preferred ligand when the transition metal is ruthenium, palladium, copper, rhodium or nickel other than iron or molybdenum, triphenylphosphine, tributylphosphine, cyclooctadiene, norbornadiene, benzene, cyclopentadiene, bipyridine, Salicylidene, triphenyl phosphite, diphenylphosphinoethane, phenanthroline, halogen, hydrogen, carbon monoxide and the like can be mentioned.

  Accordingly, specific examples of complexes in which the transition metal is, for example, ruthenium include dichlorotris (triphenylphosphine) ruthenium (II), dichlorotris (tributylphosphine) ruthenium (II), dichloro (cyclooctadiene) ruthenium (II), Dichlorobenzene ruthenium (II), dichloro-p-cymene ruthenium (II), dichloro (norbornadiene) ruthenium (II), cis-dichlorobis (2,2′-bipyridine) ruthenium (II), dichlorotris (1,10-phenanthroline) ) Ruthenium (II), carbonyl chlorohydridotris (triphenylphosphine) ruthenium (II) and the like.

The organic halide constituting (Iv2) is an organic halide selected from the group consisting of organic iodides and organic chlorinated compounds.
Organic iodides produced by addition reaction of hydrogen iodide with alkenes [vinyl esters (vinyl acetate, etc.), (meth) acrylates [methyl (meth) acrylate, ethyl (meth) acrylate, etc.], etc.]] Products, iodomethane, iodoethane, iodopropane, iodobutane, diiodomethane, 1,2-diiodoethane, iodoform, chloroiodomethane, iodoacetonitrile, iodoacetic acid, ethyl iodoacetate, 1,6-diiodohexane, iodoacetamide and the like.
Of these, from the viewpoint of increasing the molecular weight of the water-soluble polymer (A), a product obtained by addition reaction of hydrogen iodide and alkene and ethyl iodoacetate are preferable.

The Lewis base constituting (Iv2) functions as an activator for activating the above transition metal complex.
The Lewis base includes trialkylamines [C3-20, such as triethylamine, tri (n- and i-propyl) amine, tri (i-, sec- and ter-butyl) amine, tri (n-pentyl) amine, Di (n-butyl) ethylamine, di (i-propyl) ethylamine]; tri (cyclo) alkyl or triarylphosphine [C3-20, such as trimethylphosphine, triethylphosphine, tri (n- and i-propyl) phosphine, tri (I- and ter-butyl) phosphine, tri (n-pentyl) phosphine, di (n-butyl) ethylphosphine, di (i-propyl) ethylphosphine, tricyclopentylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzyl Hosphy , Tri (o-tolyl) phosphine, trimesitylphosphine phosphine], and the like. Of these, triethylamine is preferred from the viewpoint of living radical polymerizability. These can be used alone or in combination of two or more.

  The ratio (molar ratio) of other components to 1 mol of the organic halide in (Iv2) is preferably 0.05 to 3, more preferably 0.1 from the viewpoint of narrowing the polymerization rate and molecular weight distribution of the transition metal complex. ˜1; The Lewis base is preferably 0.05 to 5, more preferably 0.1 to 3, from the same viewpoint.

  (Iv2) is usually prepared by mixing a transition metal complex, an organic halide and a Lewis base immediately before use. If necessary, polymerization is started by adding each component separately to the monomer for polymerization. You may make it function as an agent.

The living radical polymerization initiator (Iv) in the present invention is at least one living radical polymerization initiator selected from the group consisting of (Iv1) and (Iv2), and (Iv) is only (Iv1), (Iv2) ) And (Iv1) / (Iv2) in combination, but only (Iv1) or (Iv2) is preferred from the viewpoint of increasing the molecular weight.
The weight ratio when (Iv1) / (Iv2) is used in combination is preferably 5/95 to 99/1, more preferably 30/70 to 70/30, from the viewpoint of increasing the molecular weight.

  The content of (Iv) based on the total weight of the monomers constituting (A) is preferably 0.001 to 1%, more preferably 0.005 to 0.5%, from the viewpoint of high molecular weight and aggregation performance. Particularly preferred is 0.01 to 0.1%, and most preferred is 0.02 to 0.05%.

In the present invention, (Iv) can be used in combination with an ordinary radical polymerization initiator (Iz) other than (Iv) as long as it does not inhibit the effects of the present invention.
Examples of (Iz) include various compounds such as azo compounds [water-soluble compounds [azobisamidinopropane (salt), azobiscyanovaleric acid (salt), etc.]] and oil-soluble compounds [azobiscyanovaleronitrile, azo Bisisobutyronitrile, azobiscyclohexanecarbonitrile, etc.]] and peroxides [water-soluble [peracetic acid, ter-butyl peroxide, hydrogen peroxide, ammonium persulfate, sodium persulfate, potassium persulfate, etc.] and Oil-soluble ones [benzoyl peroxide, cumene hydroxy peroxide, etc.].
Examples of the salt in the azo compound include inorganic acid (hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, etc.) salts, alkali metal (lithium, sodium, potassium, etc.) salts, ammonium salts, and the like.
The above peroxide may be used as a redox initiator in combination with a reducing agent. Examples of the reducing agent include bisulfites (sodium bisulfite, potassium bisulfite, ammonium bisulfite, etc.), reducing metal salts [iron sulfate (II ), Etc.], amine complexes of transition metal salts [pentamethylenehexamine complexes of cobalt (III) chloride, diethylenetriamine complexes of copper (II) chloride, etc.], organic reducing agents [ascorbic acid, tertiary amine [dimethylaminobenzoic acid ( Salt), dimethylaminoethanol and the like]. Further, the azo compound, peroxide and redox initiator may be used alone or in combination of two or more.
Of these, azo compounds are preferred from the viewpoint of not deactivating (Iv).
Although (Iz) is usually contained in the aqueous phase of the polymerization system, depending on the polymerization method, it may be present in either the aqueous phase (or dispersed phase) and / or the oil phase (or continuous phase).

  The amount of (Iz) used based on the total weight of the monomers constituting (A) is preferably 0.001 to 1%, more preferably 0.005 to 0.5%, from the viewpoint of obtaining an optimum molecular weight. Particularly preferred is 0.01 to 0.1%, and most preferred is 0.02 to 0.05%.

In the polymerization in the present invention, a chain transfer agent (f) can be used.
Examples of (f) include those having a chain transfer constant of 0.01 to 100, preferably 0.05 to 50, particularly preferably 0.1 to 10.
The definition of the chain transfer constant is as follows: “Handbook of Polymer Handbook (4th edition)” edited by J. Brandrup and EE Immag, published by J. Brandrup and EH Immergut, Polymer Handbook fourth edition, JOHN WILEY & SONS), pages 97-98.
The chain transfer constant in the present invention is measured using a general method described in “Experimental Methods for Polymer Synthesis” [Chemical Doujin Co., Ltd., published in 1993] and the like. It shall be a chain transfer constant.

  As (f), a compound having one or more amino groups in the molecule [C0-60, such as ammonia, methylamine, dimethylamine, triethylamine, n- and i-propanolamine], Compounds having one or more thiol groups (described later) and (hypo) phosphorous acid compounds [phosphorous acid, hypophosphorous acid, and salts thereof [alkali metal (sodium, potassium, etc.) salts, etc.], And derivatives thereof, etc.]. Among these, compounds having one or more thiol groups in the molecule and (hypo) phosphite compounds are preferable from the viewpoint of molecular weight control.

Examples of the compound having one or more thiol groups in the molecule include the following compounds, salts thereof [alkali metal salts, alkaline earth metal salts, ammonium salts, amines (C1-20, such as methylamine, ethanol Amine) salts, inorganic acid (hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, etc.) salts, and the like], and mixtures thereof.
(1) Monovalent thiol Aliphatic thiol (C1-20, such as methanethiol, ethanethiol, propanethiol, n-octanethiol, n-dodecanethiol, hexadecanethiol, n-octadecanethiol, 2-mercaptoethanol, mercaptoacetic acid, 3-mercaptopropionic acid, 1-thioglycerol, thioglycolic acid monoethanolamine, thiomaleic acid, mercaptosuccinic acid, cysteine, cysteamine), alicyclic-containing thiol (C5-20, such as cyclopentanethiol, cyclohexanethiol), aromatic ring Containing thiols (C6-12, such as benzenethiol, thiosalicylic acid, thiocresol, thiolenol, thionaphthol) and araliphatic thiols (C7-20, such as α-toluenethiol). It is.

(2) Polyvalent thiol dithiol [aliphatic dithiol (C2-40, such as ethanedithiol, diethylenedithiol, triethylenedithiol, n-, i- and sec-propanedithiol, 1,3- and 1,4-butanedithiol, 1,6-hexanedithiol, neopentanedithiol, triethyleneglycoldithiol), alicyclic dithiol (C5-20, such as cyclopentanedithiol, cyclohexanedithiol), aromatic dithiol (C6-16, such as benzenedithiol, biphenyldithiol) And araliphatic dithiols (C8-20, such as xylene dithiols).

  Of the above (f), those having high water solubility are preferred from the viewpoint of reducing the water-insoluble content of the polymer flocculant, and the water / n-decane partition coefficient is preferably 10/90 to 100/0. The ratio is preferably 20/80 to 100/0, particularly preferably 50/50 to 100/0. The water / n-decane partition coefficient here is the same measurement method as the water / 1-octanol partition coefficient (JIS Z7260-107) defined in Japanese Industrial Standard (JIS), and 1-octanol is converted to n-decane. It can measure by substituting.

  The amount of (f) used is preferably 0.0001%, more preferably 0.001%, based on the total weight of the monomers constituting (A), from the viewpoint of reducing the water-insoluble content of the polymer flocculant. The upper limit is preferably 0.01%, most preferably 0.05%, and the upper limit is preferably 10%, more preferably 5%, particularly preferably 3%, and most preferably 1% from the viewpoint of increasing the molecular weight.

In the case of the reverse phase suspension polymerization method among the methods for producing the water-soluble polymer (A), it can be produced, for example, by the following method.
That is, after the hydrophobic dispersion medium (b) and the dispersant (c) are charged into a polymerization tank and adjusted to a predetermined polymerization temperature (usually 20 to 100 ° C., preferably 30 to 80 ° C.) while heating as necessary. The inside of the tank is sufficiently replaced with an inert gas (for example, nitrogen).
On the other hand, a water-soluble unsaturated monomer (a), a living radical polymerization initiator (Iv), and, if necessary, a chain transfer agent (f), a water-insoluble unsaturated monomer (x) and / or a crosslinkable monomer (y) were added. After preparing an aqueous monomer solution and sufficiently substituting with an inert gas, it is put into a polymerization tank under stirring and polymerized while being suspended.
The method for charging the monomer aqueous solution may be either batch charging or dropping. In this case, the monomer aqueous solution may be a uniform aqueous solution of (a), (Iv) and (x) and / or (y) to be added if necessary. It may be dropped simultaneously or separately. Examples of the method of replacing the monomer aqueous solution with an inert gas include a method of bubbling and supplying an inert gas to the monomer aqueous solution, a method of blending an inert gas with a static mixer or the like in a dropping line, and the like. From the viewpoint of properties, a method of blending an inert gas with a static mixer is preferred.
Here, the “hydrophobic dispersion medium” means a dispersion medium having a solubility in water (g / 100 g of water, 20 ° C.) of less than 1 g.

Among the production methods of the water-soluble polymer (A), the hydrophobic dispersion medium (b) used in the reverse phase suspension polymerization method or the reverse phase emulsion polymerization includes the following hydrocarbons, ketones, ethers, esters and mixtures thereof. Can be mentioned.
(1) Hydrocarbon aliphatic (C5-12, such as n-hexane, n-heptane, n-octane, n-nonane, n-decane), alicyclic ring (C5-12, such as cyclopentane, cyclohexane, cycloheptane) , Methylcyclohexane, cyclooctane, decalin) and aromatic ring-containing hydrocarbons (C6-12, such as benzene, toluene, xylene, ethylbenzene) and the like];
(2) Ketone Aliphatic (C3-10, such as methyl-n-propylketone, diethylketone, methylisobutylketone), alicyclic ring-containing (C5-10, such as cyclopentanone, cyclohexanone) and aromatic ring-containing ketone (C8- 13, for example, acetophenone, benzophenone) and the like];
(3) Ethers Aliphatic (C4-8, eg di-n-propyl ether, di-n-butyl ether, diethylene glycol dimethyl ether), cyclic (C4-18, eg tetrahydropyrine) and aromatic ring-containing ethers (C7-12, eg Anisole) etc.] etc .;
(4) Esters Aliphatic (C3-10, eg n-butyl acetate, isobutyl acetate), alicyclic (C7-12, eg cyclohexyl acetate, methyl cyclohexanecarboxylate) and aromatic ring containing esters (C8-13, eg benzoic) Acid methyl, ethyl benzoate, n-butyl benzoate, benzyl acetate, dimethyl phthalate, diethyl phthalate, di-n-butyl phthalate) and the like.

  Of these, aliphatic and alicyclic hydrocarbons are preferred from the viewpoint of handling during production of (A) and temperature control during polymerization, and more preferred are n-hexane, n-heptane, and n-octane. , N-nonane, n-decane, cyclohexane and methylcyclohexane.

  The amount of the hydrophobic dispersion medium (b) used in reverse phase suspension polymerization is preferably 25%, more preferably 40%, particularly preferably, based on the total weight of the aqueous monomer solution from the viewpoint of the viscosity of the dispersion. 65%, and the upper limit is preferably 1,000% from the viewpoint of dispersion stability, more preferably 400%, particularly preferably 200%; in reverse emulsion polymerization, based on the total weight of the monomer aqueous solution from the viewpoint of emulsion viscosity. The preferable lower limit is 20%, more preferably 30%, particularly preferably 40%, and the preferable upper limit is 80%, more preferably 70%, particularly preferably 60% from the viewpoint of emulsion stability.

Further, as the dispersing agent (c) used in the reverse phase suspension polymerization method, the particle diameter of the dispersed particles and the angle of repose of the dried particles after the dispersed particles are dehydrated and dried, that is, the powder fluidity are controlled. Various oil-soluble substances intended to be used are mentioned.
HLB (Hydrophile-Lipophile Balance) of (c) is preferably from 1 to 8, more preferably from the viewpoint of dispersion stability of reversed phase suspension particles, particle size and angle of repose control of dry particles (A) described later. 2 to 7, particularly preferably 3 to 5.
Here, HLB represents a balance between hydrophilicity and lipophilicity, and is obtained from the following formula [“Synthesis of surfactants and their applications”, page 501, published by Takashi Shoten in 1957; “New surfactants” “Introduction”, pp. 197-198, published by Sanyo Chemical Industries, Ltd., 1992, etc.].

HLB = 10 × (inorganic / organic)

In the above formula, the value in () represents the inorganic to organic ratio of the organic compound, and the ratio can be calculated from the values described in the above documents.

  (C) includes a low molecular weight dispersant (c1) having an Mw of less than 5,000 (more preferably from 100 to 3,000, particularly preferably from 100 to 1,000), and an Mw of 5,000 or more (more preferably 7,000 to 1,000,000, particularly preferably 10,000 to 100,000) of the polymer dispersant (c2). The (c2) has a glass transition temperature (Tg) of 60 to 100 ° C.

  (C1) includes fatty acid (C10-30) esters of polyhydric (2-8 or more) alcohols [sucrose fatty acid esters (C22-120, such as sucrose distearate, sucrose tristearate), sorbitan fatty acid esters (C16-120, such as sorbitan monostearate, sorbitan monooleate), (poly) glycerin fatty acid ester (C12-120, such as glycerin monostearate), PEG fatty acid ester [Mw 100-4,500, such as PEG (Mw 100-4) , 500) mono- and distearate], etc.], alkyl (C1-30) allyl ether and the like.

  Of the above (c1), a fatty acid ester of a polyhydric alcohol is preferred, and a fatty acid ester of a polyhydric alcohol is more preferred from the viewpoint of prevention of polymer particle adhesion to the polymerization apparatus during the production of (A) and an angle of repose of the polymer particles after drying. Sugar fatty acid ester and sorbitan fatty acid ester.

(C2) includes a copolymer of an alkene and an α, β-unsaturated polyvalent carboxylic acid (anhydride) or a derivative thereof [for example, 1-olefin (C11-100) / (anhydrous) maleic acid copolymer, And its amine reaction product], long chain alkyl group (C12-50) -containing (meth) acrylate (co) polymer, modified (amino, carboxy, epoxy, hydroxy, mercapto, fatty acid ester or fatty acid amide modified, etc.) organopolysiloxane , Cellulose ether (for example, ethyl cellulose, ethyl hydroxyethyl cellulose), (maleic anhydride modified) ethylene / vinyl acetate copolymer, and the like.
The above (maleic anhydride modified) ethylene / vinyl acetate copolymer is a copolymer of ethylene and / or maleic anhydride modified ethylene and vinyl acetate, and ethylene / vinyl acetate copolymer modified with maleic anhydride. Etc. are included.

Examples of the ethylene / vinyl acetate copolymer modified with maleic anhydride include those obtained by adding maleic anhydride to the ethylene / vinyl acetate copolymer. The weight ratio is preferably 2/98 to 30/70, more preferably 5/95 to 20/80, from the viewpoint of dispersion stability of the reversed-phase suspended particles and adjustment of the molecular weight of the reaction product.
(Maleic anhydride modified) The copolymerization ratio (weight ratio) in the copolymer of ethylene and vinyl acetate is preferably from the viewpoint of solubility in the hydrophobic dispersion medium (b) and dispersion stability of the reversed-phase suspension particles. Is 50/50 to 95/5, more preferably 70/30 to 90/10.

  Among the above (c2), from the viewpoint of preventing the polymer particles from adhering to the polymerization apparatus during the production of (A) and the angle of repose of the dried particles of the polymer flocculant after drying, alkene and α, β-insoluble are preferable. A copolymer with a saturated polyvalent carboxylic acid (anhydride) or a derivative thereof, a modified organopolysiloxane, and a (maleic anhydride-modified) ethylene / vinyl acetate copolymer.

  The dispersant (c) is preferably 60 to 100 ° C., more preferably 65 to 95 ° C., particularly from the viewpoint of the powder flowability of (A) and the solubility in the hydrophobic dispersion medium (b) during polymerization. Preferably, it contains a dispersant [for example, the above (c2)] having a Tg of 67 to 92 ° C, most preferably 70 to 90 ° C. The Tg is measured using a differential scanning calorimeter (DSC) according to the method for measuring the transition temperature of JIS K7121-1987 plastic.

  The melting point of (c) is preferably 25 to 100 ° C., more preferably 30 to 80 ° C. from the viewpoint of powder flowability of (A) and solubility in the hydrophobic dispersion medium (b) during polymerization. Especially preferably, it is 40-70 degreeC. The melting point is measured using a melting point measuring device according to the JIS K0064-1992, 3.2 melting point test method.

In using the dispersant (c), it is preferable to use (c1) and (c2) in combination from the viewpoints of dispersion stability of reversed-phase suspended particles, angle of repose of dry particles, and particle size distribution. The ratio [(c1) / (c2)] is preferably 70/30 to 1/99, more preferably 50/50 to 5/95, from the same viewpoint.
When (c1) and (c2) are used in combination, a preferred combination from the viewpoint of the particle size distribution of the dry particles is a combination of a fatty acid ester of a polyhydric alcohol and a maleic anhydride-modified ethylene / vinyl acetate copolymer, more preferably PEG. A combination of a fatty acid ester and a maleic anhydride-modified ethylene / vinyl acetate copolymer.

  The amount of (c) used is based on the weight of the hydrophobic dispersion medium (b), the stability of the reversed phase suspended particles, the prevention of polymer particle adhesion to the apparatus during polymerization, the angle of repose of the dried particles after polymerization, and From the viewpoint of particle diameter control, it is preferably 0.01 to 20%, more preferably 0.03 to 10%, and particularly preferably 0.05 to 5%.

  The monomer concentration in the aqueous monomer solution in the living radical polymerization method is usually 1% based on the total weight of the aqueous monomer solution in aqueous solution polymerization, preferably 5%, more preferably 10%, particularly preferably from an industrial viewpoint. 15%, most preferably 20%, upper limit is usually 80%, preferably 75%, more preferably 70%, particularly preferably 65%, most preferably 60% from the viewpoint of temperature control during polymerization; In polymerization, the lower limit is usually 30%, preferably 40% from the same viewpoint as described above, more preferably 45%, particularly preferably 50%, most preferably 55%, and the upper limit is usually 90%, from the same viewpoint as described above. Preferably 85%, more preferably 80%, particularly preferably 78%, most preferably 75%; 10%, preferably 20% from the same viewpoint as described above, more preferably 30%, particularly preferably 40%, most preferably 55%, the upper limit is usually 90%, preferably 80% from the same viewpoint as above, more Preferably it is 75%, particularly preferably 70%, most preferably 65%.

The pH of the aqueous monomer solution is not particularly limited, but from the viewpoint of increasing the molecular weight, the preferable lower limit is 1.5, more preferably 2, particularly preferably 2.5, and the preferable upper limit is 9, more preferably from the viewpoint of preventing hydrolysis. Is 8, particularly preferably 7.5.
The pH adjuster used for pH adjustment is not particularly limited, and when the monomer aqueous solution is alkaline, inorganic acid (sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, etc.), inorganic solid acidic substance (acidic sodium phosphate, acidic bladder) Glass, ammonium chloride, ammonium sulfate, ammonium sulfate, sulfamic acid, etc.) and organic acids (C2-20, such as oxalic acid, succinic acid, malic acid). When the aqueous monomer solution is acidic, an inorganic alkaline substance (sodium hydroxide) , Potassium hydroxide, ammonia and the like) and organic alkaline substances (guanidine and the like).
In addition, pH here is the value measured at room temperature (20 degreeC) using the stock solution of monomer aqueous solution using a pH meter [For example, brand name "LAB pH meter-M-12", Horiba Ltd.]. is there.

  In aqueous solution polymerization, the lower limit of the polymerization temperature is usually −10 ° C., preferably 0 ° C., more preferably 5 ° C., particularly preferably 10 from the viewpoint of obtaining an optimum molecular weight as the water-soluble (co) polymer (A). The upper limit is usually 130 ° C (under pressure), preferably 100 ° C, more preferably 95 ° C, particularly preferably 90 ° C, and most preferably 85 ° C. Further, during the polymerization, the temperature may be adjusted by appropriately heating and cooling so as to keep the predetermined temperature constant (for example, the predetermined polymerization temperature ± 5 ° C.), or adiabatic polymerization may be performed in a glass heat insulating container or the like. .

The polymerization temperature in the photopolymerization is preferably 0 ° C. at the lower limit, preferably 5 ° C., more preferably 10 ° C., particularly preferably 15 ° C., most preferably 20 ° C., upper limit from the viewpoint of obtaining the optimum molecular weight as (A). Is usually 100 ° C., preferably 95 ° C., more preferably 90 ° C., particularly preferably 80 ° C., most preferably 70 ° C. from the same viewpoint as described above.
Further, during the polymerization, the temperature may be adjusted by appropriately heating and cooling so as to keep the predetermined polymerization temperature constant (for example, the predetermined polymerization temperature ± 5 ° C), or the polymerization may be performed at a relatively low temperature (for example, 15 to 35 ° C). It may be started and heated (for example, 55 to 80 ° C.) after polymerization for a certain time (for example, 1 to 3 hours).

The lower limit of the polymerization temperature in the reverse phase suspension polymerization is usually 10 ° C., preferably 20 ° C., more preferably 30 ° C., particularly preferably 40 ° C., most preferably 50 ° C. from the viewpoint of obtaining an optimum molecular weight as (A). The upper limit is usually 95 ° C., preferably 90 ° C., more preferably 80 ° C., particularly preferably 70 ° C., and most preferably 60 ° C. from the same viewpoint as described above.
Further, during polymerization, it is preferable to adjust by appropriately heating and cooling so that the predetermined polymerization temperature is kept constant (for example, predetermined polymerization temperature ± 5 ° C.). In order to keep the polymerization temperature constant, the monomer may be dropped continuously or intermittently under stirring of a dispersion medium whose temperature has been adjusted to a predetermined polymerization temperature in advance. The dropping time at that time varies depending on the monomer concentration and the amount of heat generated by the polymerization reaction, but is usually 0.5 to 20 hours, preferably 1 to 10 hours.

The lower limit of the polymerization temperature in the inverse emulsion polymerization is usually 0 ° C., preferably 5 ° C., more preferably 10 ° C., particularly preferably 15 ° C., most preferably 20 ° C. from the viewpoint of obtaining an optimal molecular weight as (A). The upper limit is usually 95 ° C., preferably 90 ° C., more preferably 80 ° C., particularly preferably 70 ° C., and most preferably 55 ° C. from the same viewpoint as described above.
Further, during the polymerization, the temperature may be adjusted by appropriately heating and cooling so as to keep the predetermined polymerization temperature constant (for example, the predetermined polymerization temperature ± 5 ° C), or the polymerization may be performed at a relatively low temperature (for example, 15 to 35 ° C). It may be started and heated after polymerization for a certain time (for example, 1 to 3 hours), and may be set to 55 to 80 ° C., for example.

Pressure during polymerization [kPa (absolute pressure), only numerical values are shown below. ] Is not particularly limited, but is usually performed under atmospheric pressure or reduced pressure. From the viewpoint of controlling the molecular weight distribution, it is preferable to set the pressure at which the hydrophobic dispersion medium (b) boils at the polymerization temperature.
The preferable lower limit of the pressure is 5, more preferably 10, particularly preferably 15, and the preferable upper limit is 500, more preferably 300, particularly preferably 150.

The end point of the reaction can be confirmed at the time when the heat generation due to the polymerization disappears, but the polymerization time is usually 1 to 24 hours from the time when the start of the polymerization is confirmed by the heat generation, preferably 2 to 12 from the standpoint of reducing residual monomers and from an industrial viewpoint. It's time.
In the case of reverse phase suspension polymerization, when the monomer is added dropwise, it is preferable to carry out the polymerization for the above time after completion of the addition.
The monomer concentration, monomer aqueous solution pH, polymerization temperature, polymerization pressure, and polymerization time can be appropriately adjusted depending on the monomer composition, polymerization method, initiator type, and the like.

  The water-soluble polymer (A) in the present invention may be further modified. As the polymer modification method, for example, when (meth) acrylamide having a hydrolyzable functional group in the molecule is used as the water-soluble unsaturated monomer (a), a caustic alkali (sodium hydroxide, hydroxide) is used during or after the polymerization. Potassium etc.) or alkali carbonate (sodium carbonate, potassium carbonate, etc.) is added, and the amide group of (a) is partially hydrolyzed to introduce a carboxyl group (see JP-A-56-16505 etc.) ); Formaldehyde, dialkylamine (C1-12) and halogenated (chlorine, bromine, iodine, etc.) alkylated (C1-12) (methyl chloride, ethyl chloride, etc.) are added, and a cationic group is partially introduced by the Mannich reaction. Obtained by hydrolysis of nitrile groups such as acrylonitrile and vinylformamide A method of forming an amidine ring in a molecule by a ring-closing reaction with an amino group (see JP-A-5-192513, etc.); and a method of adding a crosslinkable monomer (y) after polymerization to cause a crosslinking reaction (patent) No. 3305688) and the like.

  The water-containing gel obtained by polymerization [consisting of water-soluble polymer (A) and water] is shredded as necessary, and further dehydrated and dried to obtain a powdery polymer flocculant of the present invention. Can do.

The intrinsic viscosity (hereinafter sometimes referred to as η) of (A) (measured value in a 1N-NaNO ₃ aqueous solution at 30 ° C., unit is dl / g, the same shall apply hereinafter) is usually 1 to 40, the aggregation performance and the aggregation rate. From the viewpoint, it is preferably 2 to 38, more preferably 4 to 35, and most preferably 5 to 30.

In addition, the string length (mm) of the 0.4% by weight aqueous solution of (A) is a non-ionic and anionic polymer flocculant described later from the viewpoint of increasing the molecular weight necessary for aggregation and reducing the moisture content of the dehydrated cake. To preferably 20 to 200, more preferably 40 to 150, and for cationic and amphoteric polymer flocculants, from the same viewpoint, it is preferably 5 to 100, more preferably 6 to 80.
The yarn length has a correlation with the molecular weight (or intrinsic viscosity; the same applies hereinafter) and the molecular weight distribution, and the larger the molecular weight and the wider the molecular weight distribution, the larger the yarn length. Further, at the same molecular weight, the shorter the spine length, the sharper the molecular weight distribution.

Here, the yarn length L (mm) can be measured by the following procedure using a yarn measuring device [manufactured by Kyowa Interface Science Co., Ltd.].
Take 0.80 g of water-soluble polymer particles (in terms of solid content) in a 300 ml glass beaker, quickly add ion-exchanged water so that the total weight of the polymer and ion-exchanged water is 200.0 g, and use a glass rod or the like. The polymer is stirred until it swells and is uniformly dispersed (about 1 minute). At this time, care is taken so that the polymer does not remain. Then, after covering with a transparent resin film and allowing to stand at room temperature (about 20 ° C.) for about 20 hours, stirring with a plate-like PVC stirring blade (diameter 5 cm, height 2 cm, thickness 0.2 cm) A jar tester equipped with a stick is set and stirred at 120 rpm for 1 hour to prepare a 0.4 wt% aqueous solution of the measurement sample. After adjusting the temperature of the measurement sample to 25 ± 2 ° C., a glass spheroid (hereinafter referred to as a glass sphere) (short diameter 7 mm, long diameter 11 mm, long diameter) attached to the lower end of the hanging thread of the spinnability measuring instrument. Is suspended so that the upper end of the major axis of the glass sphere is located immediately below the liquid surface of the measurement sample, and held for 15 seconds, then the glass sphere is pulled up at a speed of 16 mm / second, and the yarn of the polymer aqueous solution is cut. Measure the distance from the liquid level to the lower end of the glass bulb. The immersion position of the glass sphere in the measurement sample is changed, the measurement is repeated 10 times, the average value is calculated, and the value is set as the yarn length (mm).

Usually, the string length has a correlation with the molecular weight (or intrinsic viscosity, the same shall apply hereinafter) or the molecular weight distribution, and becomes larger as the molecular weight is larger or the molecular weight distribution is wider. In addition, when comparing different water-soluble polymers, if the water-insoluble content is less than 0.1% by weight and the molecular weight is the same (difference in intrinsic viscosity is within ± 5%), It can be determined that the shorter the yarn length, the sharper the molecular weight distribution and the better the agglomeration performance.
In the relationship between the yarn length, the molecular weight (intrinsic viscosity) and the aggregation performance, the present invention determines the ratio (L / η) of the yarn length L (mm) and the intrinsic viscosity η (dl / g) in (A). It has been found for the first time that excellent agglomeration performance is exhibited by setting the specific range. That is, the (L / η) is preferably 1 to 8, more preferably 1.5 to 7, particularly preferably 2 to 5, from the viewpoint of increasing the molecular weight necessary for aggregation and reducing the moisture content of the dehydrated cake. .
The ratio (L / η) is increased by reducing the use amount of the living radical polymerization initiator (Iv) based on the total weight of the monomers constituting (A), and the use amount of (Iv) By increasing the value, it can be made smaller and within the above range.

[Polymer flocculant]
The polymer flocculant of the present invention contains the water-soluble polymer (A).
Generally, in sewage sludge, the size of suspended particles is relatively large, and the surface of suspended particles in water has a negative charge, so that the polymer flocculant for dehydration is cationic or amphoteric. Polymer flocculants and mixtures thereof are preferred.
In wastewater, in order to treat soluble organic matter and the like, an inorganic flocculant is often added first, and in that case, the suspended particle surface is covered with the inorganic flocculant and has a positive charge. As the polymer flocculant for the coagulation sedimentation treatment, anionic or nonionic and mixtures thereof are preferable.
For the tertiary recovery of petroleum, those having a relatively large molecular weight are used, and anionic or nonionic and mixtures thereof are preferred.
Cationic or amphoteric polymer flocculants and mixtures thereof are preferred for improving drainage yield or enhancing paper strength in the papermaking process.

  Here, the cationic polymer flocculant is a polymer flocculant having a cationic group in the molecule, that is, a polymer flocculant exhibiting a cationic property when dissolved in water, and an amphoteric polymer flocculant and Is a polymer flocculant having a cationic group and an anionic group in the molecule, that is, a polymer flocculant exhibiting cationic and anionic properties when dissolved in water. About the cationic or anionic evaluation method of these polymer flocculants in water, it can obtain | require as a colloid equivalent value (meq / g). That is, the cationic group equivalent value in the cationic flocculant can be determined as the cation colloid equivalent value, and the cationic group equivalent value and the anionic group equivalent value in the amphoteric flocculant are the cationic colloid equivalent value and the anionic colloid respectively. It can be determined as an equivalent value.

When the polymer flocculant of the present invention is a cationic polymer flocculant, the preferable lower limit of the cation colloid equivalent value (meq / g) in the flocculant is 0.1, more preferably 0.8. 5, more preferably 1.0, particularly preferably 1.5, most preferably 2.0, and from the viewpoint of agglomeration performance, a preferable upper limit is 7.0, more preferably 6.0, still more preferably 5.5, especially Preferably it is 5.2, most preferably 5.0.
When the polymer flocculant of the present invention is an amphoteric polymer flocculant, the lower limit of the cation colloid equivalent value (meq / g) in the flocculant is preferably 0.1, more preferably 0.8. 5, more preferably 1.0, particularly preferably 1.5, most preferably 2.0, and from the viewpoint of agglomeration performance, a preferable upper limit is 7.0, more preferably 6.0, still more preferably 5.5, especially Preferably, it is 5.2, and most preferably 5.0; the anion colloid equivalent value (meq / g) is preferably -13.0, more preferably -10.0, more preferably from the viewpoint of aggregation performance. −8.0, particularly preferably −5.0, most preferably −3.0, and the upper limit is preferably −0.05, more preferably −0.1, still more preferably −0.3, from the viewpoint of aggregation performance. Especially preferred -0.5, and most preferably -1.0.

The colloid equivalent value can be determined by the colloid titration method shown below. The subsequent measurement is performed at room temperature (about 20 ° C.).
(1) Preparation of measurement sample (50 ppm aqueous solution of polymer flocculant) Weigh accurately 0.2 g of sample (in terms of solid content), put it in a 200 ml Erlenmeyer flask, and total weight (total of sample and ion-exchanged water) After adding ion-exchanged water so that the weight becomes 100 g, the mixture is stirred for 3 hours with a magnetic stirrer (a cylindrical magnet having a length of 40 mm and a diameter of 5 mm, a rotational speed of 1,000 rpm) to completely dissolve it. Prepare a 2% by weight polymer flocculant solution. Take 10 ml of the prepared solution in a 500 ml beaker, add ion exchange water so that the total weight (total weight of solution 10 ml and ion exchange water) is 400 g, and again magnetic stirrer (1,000 to 1,200 rpm). Then, stir for 30 minutes to obtain a uniform measurement sample.
The solid content of the polymer flocculant was weighed (W1) in a petri dish (diameter: 100 mm, depth: 10 mm) and dried at 105 ± 5 ° C. for 90 minutes in a circulating drier. This is a value calculated from the following equation, assuming that the remaining weight after (W2).

Solid content (% by weight) = (W2) × 100 / (W1)

(2) Measurement of cation colloid equivalent value 100 g of a measurement sample is placed in a 200 ml conical beaker, and a 0.5 wt% aqueous sulfuric acid solution is gradually added while stirring with a magnetic stirrer (500 rpm) to adjust to pH 3. Next, add 2-3 drops of toluidine blue indicator (TB indicator) and titrate with N / 400 potassium potassium sulfate (N / 400 PVSK) reagent. The titration rate is 2 ml / min, and the end point is the time when the measurement sample changes color from blue to reddish purple and the reddish purple color is maintained for 30 seconds.
(3) Measurement of anion colloid equivalent value 100 g of a measurement sample was placed in a 200 ml conical beaker, 0.5 ml of an N / 10 sodium hydroxide aqueous solution was added while stirring with a magnetic stirrer (500 rpm), and further N / 200 methyl glycol chitosan. After adding 5 ml of an aqueous solution, the mixture is stirred for 5 minutes (pH about 10.5 at that time). Add 2-3 drops of TB indicator and titrate in the same manner as in (2) above.

(4) Blank test The same operation as (2) and (3) is performed except that 100 g of ion-exchanged water is used instead of the measurement sample.
(5) Calculation method Colloidal equivalent value (meq / g) = (1/2) × (Titration of sample-titration of blank test)
× (N / 400 PVSK titer)

  The polymer flocculant of the present invention is an antifoaming agent, a chelating agent, a pH adjuster, a surfactant, an antiblocking agent, an antioxidant, an ultraviolet absorber, and an antifoaming agent, as long as the effects of the present invention are not impaired. An additive selected from the group consisting of preservatives can be used in combination.

The method for adding the polymer flocculant of the present invention to sewage sludge, waste water or the like (hereinafter abbreviated as sewage sludge or the like) is not particularly limited, and is described in, for example, Japanese Patent No. 1311340 or Japanese Patent No. 2038341. A method is mentioned.
The amount of the polymer flocculant used in the present invention varies depending on the type of sewage sludge, the content of suspended particles, the molecular weight of the polymer flocculant, etc., but is not particularly limited, and the weight of evaporation residue in sewage sludge etc. (Hereinafter abbreviated as TS), usually from 0.01 to 10%, preferably from the viewpoint of agglomeration performance, the lower limit is 0.1%, more preferably 0.5%, particularly preferably 1%, from the viewpoint of processing costs Therefore, the preferable upper limit is 5%, more preferably 3%, and particularly preferably 2%.

As a method of using the polymer flocculant of the present invention, it is preferable to add it to sewage sludge after making it into an aqueous solution from the viewpoint of sufficient flocculation performance, but the polymer flocculant is added directly to sewage sludge etc. in a solid state. You can also The concentration when the polymer flocculant is used as an aqueous solution is preferably 0.05 to 1% by weight from the viewpoint of handling and dissolution rate.
The method for dissolving the polymer flocculant is not particularly limited. For example, a predetermined amount of the polymer flocculant is gradually added while stirring the water weighed in advance using a stirring device such as a jar tester, A method of dissolving for several hours (about 2 to 4 hours) can be employed. When the powdery polymer flocculant is dissolved in water, a method of adding a predetermined amount of the polymer flocculant at a stretch is undesirably caused by the fact that it becomes difficult to completely dissolve in water.

  When the polymer flocculant of the present invention is used for the third recovery of petroleum, it is usually used as an aqueous solution. The concentration (% by weight) of the aqueous polymer solution is usually 0.001 to 3%, preferably from 0.005 to 1%, more preferably from 0.01 to 0.5 from the viewpoint of the thickening effect and the viscosity capable of being fed. %.

When the polymer flocculant of the present invention is applied to sewage sludge, etc., if the sewage sludge is organic sludge or anaerobic bacteria-treated sludge, inorganic and / or organic coagulation is performed from the viewpoint of charge neutralization of the sludge particles. It is preferable to use an agent in combination.
Inorganic coagulants include sulfuric acid band, polyaluminum chloride, ferric chloride, ferric sulfate, polyiron sulfate, slaked lime, etc .; organic coagulants include aniline-formaldehyde polycondensate hydrochloride, polyvinylbenzyltrimethylammonium chloride , Dimethyldi (meth) allyl ammonium chloride, (meth) allylamine or di (meth) allylamine-maleic acid copolymer, (meth) allylamine or di (meth) allylamine-citraconic acid copolymer, (meth) allylamine or di ( Examples include (meth) allylamine-itaconic acid, (meth) allylamine, di (meth) allylamine-fumaric acid copolymer, and the like.
When an inorganic and / or organic coagulant is used in combination, sewage sludge is treated with a mixture obtained by adding these to the polymer flocculant of the present invention in advance, or an inorganic coagulant and / or an organic coagulant is preliminarily applied to the sewage sludge. After the primary agglomeration is added, the polymer flocculant of the present invention may be added and treated, but the latter method is preferred from the viewpoint of floc strength.

The amount used when using an inorganic coagulant and / or an organic coagulant varies depending on the type of sewage sludge, the size of suspended particles, the type of coagulant used, etc., but there is no particular limitation. Based on TS, the inorganic coagulant is usually 20% or less, preferably 0.5% from the viewpoint of setting performance, more preferably 1%, particularly preferably 1.5%, and the upper limit preferable from the viewpoint of setting performance. 10%, more preferably 5%, and particularly preferably 3%. In the case of an organic coagulant, it is usually 1% or less, and a preferable lower limit from the viewpoint of setting performance is 0.01%, more preferably 0.025%, particularly preferably. The upper limit is preferably 0.5%, more preferably 0.2%, and particularly preferably 0.15% from the viewpoint of setting performance of 0.05%.

When the polymer flocculant of the present invention is added, the pH of sewage sludge and the like may be adjusted in advance. The pH adjustment range is usually from 3 to 8, the lower limit preferable from the viewpoint of hydrolysis prevention is 3.5, more preferably 4, particularly preferably 4.5, and the upper limit preferable from the viewpoint of solubility is 7, more preferably 6. Particularly preferred is 5.5.
The pH adjustment method is not particularly limited, and an acidic substance such as inorganic acid (sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, etc.) or an alkaline substance such as caustic alkali (sodium hydroxide, potassium hydroxide, etc.) is used. The method to use is mentioned. In addition, the pH can be adjusted by adding the inorganic or organic coagulant to sewage sludge or the like in advance.

  In addition, as a dehydration method (solid-liquid separation method) of floc formed by adding the polymer flocculant of the present invention to sewage sludge, centrifugal dehydration, filter press dehydration, belt press dehydration, screw press dehydration and capillary dehydration Various dehydration methods such as these can be applied. Among these, screw press dewatering and belt press dewatering are preferable from the viewpoint of high floc strength, which is the specific aggregation performance of the polymer flocculant of the present invention.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In addition, the part in an Example represents a weight part and% represents weight%.

The composition, symbols, etc. of the raw materials used in the examples and comparative examples are as follows.
(1) Water-soluble unsaturated monomer (a)
(A1-1): Methyl chloride salt of N, N-dimethylaminoethyl methacrylate
80% aqueous solution of (DAMQ) (a1-2): methyl chloride salt of N, N-dimethylaminoethyl acrylate
(DAAQ) 70% aqueous solution (a2-1): Acrylamide (AAM) 50% aqueous solution (a3-1): Acrylic acid (2) Chain transfer agent (f)
(F-1): 1-thioglycerol (f-2): mercaptoacetic acid (f-3): cysteamine hydrochloride (3) living radical polymerization initiator (Iv)
(Iv1-1) Ethyl-2-methyl-2-n-butylterranyl-propionate (Iv2-1) cyclopentadienylmolybdenum tricarbonyl dimer /
Iodoethyl acetate / triethylamine = 0.5 / 1 / 0.5 (molar ratio)
(4) radical polymerization initiator (Iz)
(Iz-1): 10% aqueous solution of azobisamidinopropane hydrochloride

The solid content and the weight average particle size of the polymer flocculant were evaluated by the above methods, and the other items were evaluated by the following methods.
TS in sewage sludge and the like, suspended solids (SS), and organic content (loss on ignition) were performed according to the analysis method described in “Sewage test method” (Japan Sewerage Association, 1984 version).

(1) Water solubility A stirring bar equipped with two plate-shaped PVC stirring blades (diameter: 5 cm, height: 2 cm, thickness: 0.2 cm) continuously up and down in a cross shape is a jar tester [model number “ “JMD-6HS-A”, manufactured by Miyamoto Riken Kogyo Co., Ltd., and so on. ] Is used. A 500 ml beaker containing 499 g of ion-exchanged water is set here and stirred at a water temperature of 25 ° C. and 200 rpm. The total amount of 1 g (solid content) of the polymer flocculant weighed in the petri dish was poured into ion-exchanged water under stirring, and the dissolution state 60 minutes after the addition was visually observed, and water solubility was observed according to the following criteria. Evaluated.
<Evaluation criteria>
◎ No occurrence of undissolved, undissolved residue ○ No occurrence of undisturbed, very little undissolved △ Distinct occurrence, slightly more undissolved × Many occurrences of undissolved, undissolved

(2) Flock particle size (mm)
Put 200 ml of sludge in a 300 ml beaker and set in the same stirring device as in (1) above. The rotation speed of the jar tester was set to 300 rpm, and while the sludge was gradually stirred, an aqueous solution of a polymer flocculant having a predetermined concentration was added by a predetermined method and stirred for 30 seconds. The diameter (mm) is visually observed. Subsequently, the rotational speed is changed to 650 rpm, and the mixture is further stirred for 30 seconds, and then the stirring is stopped and the particle diameter (mm) of the formed floc is again visually observed.

(3) Flock strength The floc particle sizes at the rotation speeds of 300 rpm and 650 rpm in the above (2) are compared, and the floc strength is evaluated according to the following criteria from the change in the floc particle size.
<Evaluation criteria>
◎ Very strong (no change in particle size)
○ Strong (partially subdivided)
△ Slightly weak (partially subdivided)
× Weak (Overall segmentation)

(4) 10 seconds behind liquid volume, 60 seconds behind liquid volume (ml)
T-1189 nylon filter cloth (Shikishima Canvas Co., Ltd., circular shape, diameter 9 cm), Nutsche funnel, and measuring cylinder are set using a measuring cylinder capable of measuring 300 ml. All the sludge after the floc particle size test of (2) above is filtered at once on the Nutsche filtration surface, and the amount of filtrate that has passed from 10 seconds to 60 seconds after the addition is measured using a stopwatch. To do.

(5) Filter cloth peelability A part of the filtered sludge is removed with a spatula and subjected to a dehydration test (1 kg / cm ² , 60 seconds) using a press filter tester, and the dehydrated cake adhered to the filter cloth after the test is removed. The peelability of the dehydrated cake when peeled with a spatula is evaluated according to the following criteria.
<Evaluation criteria>
A: Very easy to peel off (no deposit on the filter cloth)
○: Easy to peel off (Slight deposits on filter cloth)
△: Slightly difficult to peel off (There are deposits on the filter cloth, and there are deposits slightly inside the filter cloth.)
×: Hard to peel off (There are many deposits even inside the filter cloth)

(6) Dehydrated cake moisture content (wt%)
About 3 g of the dehydrated cake after the filter cloth peelability test of the above (5) was weighed (W3) in a petri dish, dried in a circulating drier at 105 ± 5 ° C. for 8 hours, and then left on the petri dish. Taking the weight of the dry cake as (W4), the moisture content of the cake is calculated from the following equation.

Dehydrated cake moisture content (% by weight) = [(W3) − (W4)] × 100 / (W3)

Example 1 [Production of polymer flocculant (P-1)]
(A-2), (a-3) and ion-exchanged water were added to a 3 L reaction vessel equipped with a stirrer based on Table 1, and mixed and stirred until the inside of the system became a homogeneous solution. While stirring, the pH (20 ° C.) of the aqueous monomer solution was adjusted to 3.3 using sulfuric acid while monitoring with a pH meter.
Next, the solution temperature was adjusted to 5 ° C. in a constant temperature water bath at 0 ° C., and the system was sufficiently substituted with nitrogen (purity 99.999% or more) (gas phase oxygen concentration of about 5 ppm). Then, about the raw material liquid mixture which added radical polymerization initiator (d-1), (d-3), (d-4), (d-5) and the chain transfer agent (f-1) based on Table 1 The polymerization was started at a solution temperature of 5 ° C., and the temperature of the solution rose due to the heat generated by the polymerization, and reached 85 ° C. after about 3 hours. When the temperature reached 70 ° C., the reaction vessel was placed in a constant temperature bath at 90 ° C. and kept at 80 to 90 ° C. for 10 hours to complete the polymerization. During the polymerization, the content became highly viscous and stirring became difficult, so stirring was stopped halfway.
Thereafter, the obtained hydrogel was taken out, mixed and kneaded by a meat chopper machine [model number “12VR-400K”, manufactured by ROYAL Co., Ltd., mesh opening 6 mm], and further minced into 80 ° C. After drying with hot air for 2 hours, the mixture was pulverized with a juicer mixer to obtain 99 parts of powdered water-soluble resin particles (P-1) (yield 92%, solid content 96%). The evaluation results are shown in Table 1.

Examples 2 to 6, Comparative Examples 1 to 3 [Production of polymer flocculants (P-2) to (P-6), (R-1) to (R-3)]
In Example 1, the polymer flocculants (P-2) to (P-6) and (P-6) were used in the same manner as in Example 1 except that the raw material mixture was changed to the raw material mixture mixed based on Table 1. R-1) to (R-3) were obtained. The evaluation results are shown in Table 1.

Examples 7 to 12 and Comparative Examples 4 to 6 [Performance evaluation of polymer flocculant]
The obtained polymer flocculants were each dissolved in ion exchange water to obtain an aqueous solution having a solid content of 0.2%. 200 parts of digested sludge [pH 7.4, TS 2.9%, SS 2.7%, organic content 65%, alkalinity 4,543 mg-CaCO ³ / L] collected from the treated city A treatment plant in a 500 mL beaker Then, 20 parts of each aqueous solution of the polymer flocculant was added (the solid content addition amount at this time was 1.6% / TS), and the performance was evaluated. The results are shown in Table 2.

  From Table 2, in Examples 7-12, compared with Comparative Examples 4-6, a floc having a large particle size was formed, and the flocs once formed under low stirring (300 rpm) were broken even under high stirring (650 rpm). It can be seen that it is difficult (strong flock strength), and the amount of liquid after 10 seconds is large, so that the initial filtration rate is fast, and it has an excellent effect on dewaterability (water content of dehydrated cake).

  Since the polymer flocculant of the present invention exhibits unprecedented specific flocculation performance, the polymer flocculant for dewatering such as sewage sludge, the polymer for improving the drainage yield in the papermaking process or the paper strength enhancing polymer In addition to the flocculant, it is widely and suitably used as a polymer flocculant for flocculation and precipitation treatment of industrial wastewater, tertiary recovery of petroleum, etc. and is extremely useful.

Claims (7)

A water-soluble polymer obtained by polymerizing a monomer containing a water-soluble unsaturated monomer (a) in the presence of at least one living radical polymerization initiator (Iv) selected from the group consisting of the following (Iv1) and (Iv2) A polymer flocculant comprising (A).
(Iv1) Organic tellurium compound represented by the following general formula (1) (Iv2) Complex of transition metal selected from the group consisting of ruthenium, palladium, copper, iron, molybdenum, rhodium and nickel, organic iodide and organic chlorinated compound Organic halides selected from the group consisting of, and mixtures of Lewis bases selected from the group consisting of amines and phosphines

R ⁴ R ³ R ² C-Te-R ¹ (1)

[In the formula, R ¹ having 1 to 20 carbon atoms, an alkyl group, an aryl group, a substituted aryl group or an aromatic heterocyclic group; R ² and R ³ are H or an alkyl group having 1 to 8 carbon atoms; R ⁴ is An aryl group, substituted aryl group, aromatic heterocyclic group, acyl group, amide group, oxycarbonyl group or cyano group having 1 to 20 carbon atoms is represented. ] The polymer flocculant according to claim 1, wherein the content of (Iv) based on the total weight of the monomers constituting (A) is 0.001 to 1%. The polymer flocculant according to claim 1 or 2, wherein the ratio (L / η) of the yarn length L (mm) to the intrinsic viscosity η (dl / g) of (A) is 1 to 8. Furthermore, the polymer flocculent in any one of Claims 1-3 formed by using azo compound (Iz) together as a polymerization initiator. The polymer flocculant according to claim 4, wherein the weight ratio of (Iv) to (Iz) is 5/95 to 99/1. The polymer flocculant according to any one of claims 1 to 5, wherein the polymer flocculant is used for dewatering sewage sludge or for coagulating sedimentation of wastewater. The polymer flocculant according to any one of claims 1 to 6, wherein the polymer flocculant is added to and mixed with sludge or wastewater to form flocs and solid-liquid separation. A method for treating sludge or wastewater, characterized by being used.