JP2004290969A - Polymer flocculant - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer flocculant which is used for the dehydration of organic sludge such as sewage sludge or inorganic waste water such as plant waste water and has excellent flocculating performance (realizing high floc strength, coarse floc and dehydrated cake of higher water content). <P>SOLUTION: The polymer flocculant is composed of: at least one kind of (co)polymer between at least one kind of compound (a) and a water-soluble unsaturated monomer (b); and/or a (co)polymer obtained by (co)polymerizing the water-soluble unsaturated monomer (b) in the presence of the compound (a), wherein the compound (a) is selected from a group consisting of amidine, urea, guanidine, derivatives of them, and polycondensation substances resulting from reaction between these compounds and formaldehyde. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a polymer flocculant used for dehydrating organic or inorganic sludge or wastewater such as sewage, human waste, and industrial wastewater, a method for producing the same, and a method for treating sludge or wastewater using the polymer flocculant.

Conventionally, for the dehydration of organic sludge such as sewage or night soil (hereinafter abbreviated as sewage sludge) or industrial wastewater (hereinafter abbreviated as wastewater), polymethacryloyloxyethyltrimethylammonium chloride, acrylamide-acryloyloxyethyltrimethyl are used. Cationic polymer flocculants such as ammonium chloride copolymer and polyvinylamidine, and amphoteric polymer flocculants such as acrylamide-acrylic acid-acryloyloxyethyltrimethylammonium chloride copolymer are widely used.
For dehydration of inorganic sludge or wastewater such as wastewater, nonionic polymer flocculants such as polyacrylamide and anionic polymer flocculants such as acrylamide-sodium acrylate copolymer are widely used.
As a method for producing these polymer flocculants, an aqueous solution polymerization method, a thin film polymerization method, a reversed phase suspension polymerization method, a precipitation polymerization method, an emulsion polymerization method and the like are known.
Among these polymer flocculants, in recent years, especially with respect to dehydration of organic sludge, the need for increasing the dewatering treatment speed has increased due to the increase in the amount of generated sludge, and polymer flocculants that form stronger floc strength have been increasing. Agents are desired. In addition, polymer coagulants that can reduce the water content in dewatered cakes due to soaring costs of incineration when dewatering cakes are incinerated and tight landfills when landfilling dewatered cakes as they are Is desired.
Recently, as a polymer coagulant for the purpose of improving the performance, for example, in water-in-oil emulsion polymerization, a substance produced by adding hydrogen peroxide or a substance that generates hydrogen peroxide during polymerization (for example, , Patent Document 1), an amphoteric polymer flocculant that forms a partial cross-link by adding and reacting a cross-linking agent that chemically bonds to a carboxylic acid group in the polymer during or after polymerization (for example, see Patent Document 2). One 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 3), one produced by adding a nitroxy radical during polymerization (for example, , Patent Document 4), an amphoteric polymer having a cationic unit having an amino group and an anionic unit having two carboxyl groups during polymerization. Compounds that produced by adding (e.g., Patent Document 5 references) have been proposed.

JP 2002-114810 A (page 1) Japanese Patent No. 3305688 (1 page) JP-A-2002-97236 (page 1) JP 2001-139606 A (page 1) JP 2001-329004 A (page 1)

However, the currently used polymer flocculants have not yet reached a sufficiently satisfactory level, and the above proposed polymer flocculants are somewhat somewhat degraded in terms of floc strength and dewatered cake moisture content. Has been improved but not yet satisfactory.
An object of the present invention is to solve the above problems. That is, an object of the present invention is to provide a polymer flocculant which can coarsen floc, exhibits strong floc strength, and has a low water content in a dehydrated cake.

The present inventors have conducted intensive studies to solve this problem, and as a result, by adding a compound having a specific structure in the molecule at the time of polymerization and polymerizing, a remarkable aggregation performance (high floc strength, floc And a water content of the dehydrated cake was reduced, the same applies hereinafter), and a cationic or amphoteric polymer flocculant capable of performing efficient dehydration treatment was found.
That is, the present invention
Compounds (a1) and (a1) represented by the following general formulas (1), (2), (3) and (4), and salts represented by the following general formulas (5), (6) and (7) At least one compound (a) selected from the group consisting of a compound (a2), a salt of (a2), and a polycondensate (a3) composed of (a2) and formaldehyde, and at least one of a water-soluble unsaturated monomer (b) A polymer coagulant comprising a (co) polymer obtained by (co) polymerizing at least one of (b) in the presence of one (co) polymer and / or (a) (A)

[Wherein, R ¹ is H or a hydrocarbon group having 1 to 20 carbon atoms; R ² and R ³ are a hydrocarbon group having 1 to 20 carbon atoms which may contain an O, N or S atom, or H; X is O, NR ⁴ or S; R ⁴ is a hydrocarbon group having 1 to 20 carbon atoms which may contain an O, N or S atom, or H. ]
[Wherein, R ⁵ is a direct bond or a hydrocarbon group having 1 to 20 carbon atoms; R ⁶ , R ⁷ , R ⁸ , and R ⁹ have 1 to 20 carbon atoms which may contain an O, N, or S atom. Or H. ]
[In the formula, R ¹⁰ is a hydrocarbon group having 1 to 20 carbon atoms; R ¹¹ is a hydrocarbon group having 1 to 20 carbon atoms, which may contain an O, N, or S atom, or H. ]
[Wherein, R ¹² is a hydrocarbon group having 1 to 20 carbon atoms; R ¹³ is a hydrocarbon group having 1 to 20 carbon atoms, which may contain an O, N, or S atom, or H]. ]
[Wherein, R ¹⁴ , R ¹⁵ , R ¹⁶ , and R ¹⁷ are a hydrocarbon group having 1 to 20 carbon atoms which may contain an O, N, or S atom, or H; X is O, NR ¹⁸ or S ; R ¹⁸ is O, N, or a hydrocarbon group carbon atoms which may contain 1 to 20 S atoms, or H. ]
[Wherein, R ¹⁹ is a hydrocarbon group having 1 to 20 carbon atoms which may contain an O, N or S atom; R ²⁰ and R ²¹ are carbon atoms which may contain an O, N or S atom. T is O, NR ²² , or S; R ²² is a hydrocarbon group having 1 to 20 carbon atoms which may contain an O, N, or S atom, or H It is. ]
[Wherein, R ²³ is a hydrocarbon group having 1 to 20 carbon atoms which may contain an O, N, or S atom; R ²⁴ is a hydrocarbon group having 1 to 2 carbon atoms which may contain an O, N, or S atom. Z is H, a hydrocarbon group having 1 to 20 carbon atoms, OR ²⁵ , NR ²⁶ R ²⁷ or SR ²⁸ ; R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ are O, N, Or a hydrocarbon group having 1 to 20 carbon atoms which may contain an S atom, or H. ]
A method for treating sewage sludge or wastewater, comprising adding the polymer flocculant to sewage sludge or wastewater to form flocs, and then performing solid-liquid separation; and papermaking comprising the polymer flocculant Chemicals or additives for increasing crude oil production.

  The polymer flocculant of the present invention forms a strong and coarse aggregate (floc) when reacting with suspended particles in sewage sludge or wastewater, and once formed floc is hard to break and redisperse. Therefore, there is no re-contamination during the coagulation treatment, and the stability of the coagulation treatment and the speed of the dehydration treatment can be remarkably increased. Further, since the dense flocs are formed, the water content of the cake after the dehydration step is low, so that the amount of generated waste and the cost for incineration can be reduced.

  Compound (a) used in the present invention includes salts of (a1) and (a1) represented by the above general formulas (1), (2), (3) or (4); 6) or at least one selected from the group consisting of compounds (a2) represented by (7), salts of (a2), and polycondensates (a3) composed of (a2) and formaldehyde.

Examples of the compound (a1) include the following compounds.
(A1-1) Carboxamide represented by the above general formula (1) and its derivative formamide, carboxylic acid [carbon number (hereinafter abbreviated as C) 1 to 20] amide (acetamide, propionamide, butyric amide, amide Valic acid amide), aryl (C6-20) amide (benzamide, etc.), N-alkyl (C1-20) carboxylic acid (C1-20) amide (N-methylformamide, N-ethylformamide, N-methylacetamide, N -Methylpropionamide, N-ethylacetamide, N-ethylpropionamide and the like, and acetyl, propionyl and benzyl compounds thereof; N, N-dialkyl (C1-20) carboxylic acid (C1-20) amide (N, N -Dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide N, N-dimethylpropionamide, N, N-diethylacetamide and N, N-diethylpropionamide); N (, N)-(di) methylolcarboxylic acid (C1-20) amide (N-methylolformamide, N -Methylolacetamide, N-methylolpropionamide, etc.); N-alkoxy (C1-20) alkyl (C1-20) carboxylic acid (C1-20) amide (N-methoxymethylformamide, N-ethoxymethylformamide, N-methoxy) Methylacetamide, N-methoxymethylpropionamide, etc.)

(A1-2) Amidine represented by the general formula (1) and derivatives thereof: Formamidine, alkanoyl (C1-20) amidine (acetamidine, propionylamidine, butyrylamidine, etc.), N (, N)-(di) alkyl ( C1-20) formamidine (N-methylformamidine, N-ethylformamidine, N, N-dimethylformamidine, etc.), N (, N)-(di) alkyl (C1-20) alkanoyl (C1-20) Amidine (N-methylacetamidine, N-methylpropionamidine, N, N-dimethylacetamidine, etc.), N, N′-dialkyl (C1-20) alkanoyl (C1-20) amidine (N, N′-dimethylacetamide) Amidine, N, N'-dimethylpropionamidine, etc.), N, N, N'-trialkyl (C1-20) alkyl Noyl (C1-20) amidine (N, N, N'-trimethylacetamidine, N, N, N'-trimethylpropionamidine, etc.) and salts thereof [inorganic acids (hydrochloric acid, chloric acid, perchloric acid, odor Hydrofluoric acid, hydroiodic acid, sulfuric acid, sulfurous acid, phosphoric acid, nitric acid, carbonic acid, sulfamic acid, etc.) salts and organic acids (C1-20, for example, formic acid, acetic acid, propionic acid, benzenesulfonic acid, toluenesulfonic acid, methane) Sulfonic acid, etc.) salts] and the like.

(A1-3) Diamide represented by the general formula (2) and derivatives thereof: diacetamide, malonic acid diamide, N-methylmalonic acid diamide, N, N′-dimethylmalonic acid diamide, succinic diamide, N-methylsuccinic acid Diamides such as diamide, N, N'-dimethylsuccinic diamide, glutaric diamide, N-methylglutaric diamide, N, N'-dimethylglutaric diamide and acetyl, propionyl and benzyl compounds thereof.

(A1-4) Lactam represented by general formula (3) and derivatives thereof β-propiolactam, ε-caprolactam, N-methyl-β-propiolactam, N-methyl-ε-caprolactam, 2-pyrrolidone, 2-piperidone, N-methyl-2-pyrrolidone, N-methyl-2-piperidone and the like.

(A1-5) Cyclic imide represented by the general formula (4) and derivatives thereof: succinimide, N-methylsuccinimide, glutarimide, N-methylglutarimide, phthalimide, N-methylphthalimide and the like.

Examples of the compound (a2) include the following compounds.
(A2-1) Urea represented by the general formula (5) and derivatives thereof Urea, thiourea, N-alkyl (C1-20) (thio) urea [N-methyl (thio) urea, N-ethyl (thio) Urea, etc.], N, N (, N ′)-(poly) (2-3) alkyl (C1-20) (thio) urea [N, N-dimethyl (thio) urea, N, N′-dimethyl (thio) ) Urea, N, N'-dipropyl (thio) urea, trimethyl (thio) urea, N, N'-ethylene (thio) urea and the like], N, N, N ', N'-tetraalkyl (C1-20) (Thio) urea [N, N, N ', N'-tetramethyl (thio) urea, etc.], N, N, N'-[poly (2-3)] aryl (C6-20) (thio) urea [ N, N'-diphenyl (thio) urea and the like, and acetyl, propionyl and benzyl compounds thereof; N, N, N ', N'-te Traaryl (C6-20) (thio) urea [N, N, N ', N'-tetraphenyl (thio) urea and the like]; N (, N')-(di) -methylol (thio) urea, N (, (N ')-(di) -alkoxy (C1-20) methyl (thio) urea [N-methoxymethyl (thio) urea, N, N'-dimethoxymethyl (thio) urea, etc.]; (thio) allophanic acid and the like Derivatives [(thio) allophanic acid and their alkali metal (lithium, sodium, potassium, etc., the same applies hereinafter) salt, alkaline earth metal (magnesium, calcium, etc., the same applies hereinafter) salt, methyl (thio) allophanate, ( Ethyl thio) allophanate], (thio) hydantoic acid and its derivatives [(thio) hydantoin, (thio) hydantoic acid and their alkali metal salts, alkaline earth metal salts, ) Hindatoin methyl, (thio) Hindatoin ethyl, etc.], biuret and its derivatives (biuret, N- methyl biuret, N, N'-dimethyl biuret, N- benzoyl biuret, etc.) and the like.

(A2-2) Guanidine represented by the general formula (5) and derivatives thereof Guanidine, alkyl (C1-20) guanidine (for example, 1-N-methylguanidine, 2-N-methylguanidine, 1-N-ethylguanidine, 2- (N-ethylguanidine, etc.), poly (2-5) alkyl (C1-20) guanidine (for example, 1,2-N-dimethylguanidine, 1,3-N-dimethylguanidine, 1,1,3,3, -N-tetramethylguanidine, etc.), biguanides, biguanide derivatives (eg, N-methyl biguanide, N-benzoyl biguanide, cyanobiguanide, etc.), and acetyl, propionyl and benzylated products thereof; guanylalkyl (C1-20) urethane ( For example, guanyl methyl urethane, guanyl ethyl urethane, etc.); guanyl-O-al Kill (C1-20) isourea (eg, guanyl-O-methylisourea, guanyl-O-ethylisourea, etc.); carbamoylguanyl-O-alkyl (C1-20) isourea (eg, carbamoylguanyl-O-methylisourea) Carbamoylguanyl-O-ethylisourea, etc .; other guanidine derivatives [eg, dicyandiamide, dicyanguanidine, guanyl (thio) urea, cyanoguanyl (thio) urea, guanoline, aminoguanidine, etc.]; The above) and organic acid (above) salts; glycosiamine, alanosiamine, and acetyl, propionyl and benzylated compounds thereof, and alkali metal salts and alkaline earth metal salts thereof.

(A2-3) Compound represented by general formula (6) and derivatives thereof Glycoluril and derivatives thereof [glycoluril, N1 (, N2) (, N3) (, N4)-(poly) methylglycoluril and the like]; Cyanuric acid and its derivatives [methyl cyanurate, ethyl cyanurate and the like]; cyclic amidine derivatives [glycocyanidin, N (, N ')-(di) methylglycocyanidin and the like]; guanazine and its derivatives (guanadine, Guanazole and the like); guanine and the like.

(A2-4) Compound represented by general formula (7) and derivatives thereof Melamine, guanamine, ammeline, ammelide, benzoguanamine, acetyl, propionyl, benzylated products thereof, etc., and inorganic acids (above) and organic acids thereof (Above) salts and the like.

(A3) Polycondensate comprising (a2) and formaldehyde A urea-formaldehyde resin, guanidine-formaldehyde resin, dicyandiamide-formaldehyde resin, melamine-formaldehyde resin and guanamine having a number average molecular weight (hereinafter abbreviated as Mn) of 500 to 100,000. -Formaldehyde resins and the like.

  Of these, from the viewpoint of affinity with the water-soluble unsaturated monomer (b) described below, (a1-1) is preferable, and (a1-2), (a2-1), (A2-2), particularly preferably (a2-1) and (a2-2), most preferably urea, thiourea and biuret in (a2-1), and guanidine in (a2-2) , Biguanides, dicyandiamides, guanyl (thio) ureas and their inorganic and organic acid (above) salts.

The method of use of (a) includes a method of adding (1) a monomer {(b) and, if necessary, a monomer aqueous solution before or during polymerization of a water-insoluble unsaturated monomer (x)} [(a) A method in which a monomer is polymerized in the presence thereof], and (2) a method of adding the monomer to an aqueous solution after the polymerization. Among them, a method preferable from the viewpoint of aggregating performance is a method of adding to a monomer aqueous solution before or during polymerization of a monomer.
Although the mechanism of action between the monomer and / or polymer and (a) is unknown, it is probably that (a) interacts with the monomer and / or polymer through hydrogen bonding, hydrophobic bonding, electrostatic attraction, etc. It is presumed that the higher order structure of the polymer flocculant of the present invention is different from the conventional polymer flocculant.

The amount (% by weight) of (a) used in the method (1) is preferably 0.01 or more, more preferably 0.1 or more, and particularly preferably 0.1 or more, from the viewpoint of aggregation performance. It is preferably 1 or more, most preferably 4 or more, preferably 50 or less, more preferably 40 or less, particularly preferably 30 or less, and most preferably 20 or less.
The amount (% by weight) of (a) used in the method (2) is preferably 0.01 or more, more preferably 0.1 or more, and particularly preferably, based on the weight of the polymer, from the viewpoint of aggregation performance. Is 1 or more, most preferably 4 or more, preferably 50 or less, more preferably 40 or less, particularly preferably 30 or less, and most preferably 20 or less.

Examples of the water-soluble unsaturated monomer (b) in the present invention include the following.
(B1) Nonionic monomers The following, and mixtures thereof (b1-1) (meth) acrylate [C5 to 250, for example, hydroxyethyl (meth) acrylate, diethylene glycol mono (meth) acrylate, polyethylene glycol (polymerization degree 3 to 50) Mono (meth) acrylate, polyglycerol (polymerization degree 1 to 10) mono (meth) acrylate, 2-cyanoethyl (meth) acrylate, etc.]
(B1-2) (Meth) acrylamide and derivatives thereof [C3-30, for example, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-methylol (meth) acrylamide, etc.]
(B1-3) Nitrogen atom-containing vinyl monomers other than (b1-1) and (b1-2) [C3-12, for example, (meth) acrylonitrile, N-vinylformamide, N-vinyl-2-pyrrolidone, vinylimidazole, N-vinyl succinimide, N-vinyl carbazole, etc.].

(B2) Cationic monomers The following, salts thereof (hydrochloride, sulfate, phosphate, nitrate, methyl chloride salt, dimethyl sulfate, benzyl chloride salt, etc.), and mixtures thereof (b2-1) Nitrogen Atom-containing (meth) acrylate derivatives [C6-30, for example, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N N-diethylaminopropyl (meth) acrylate, N-morpholinoethyl (meth) acrylate, etc.]
(B2-2) (Meth) acrylamide derivative [C6-20, for example, N, N-dimethylaminoethyl (meth) acrylamide and the like]
(B2-3) Vinyl compound having an amino group [C2-12, for example, vinylamine, vinylaniline, (meth) allylamine, p-aminostyrene, etc.] (b2-4) Compound having an amine imide group [C7-20, for example 1,1,1-trimethylamine (meth) acrylimide, 1,1-dimethyl-1-ethylamine (meth) acrylimide, 1,1-dimethyl-1- (2′-phenyl-2′-hydroxyethyl) amine ( Meth) acrylimide, 1,1,1-trimethylamine (meth) acrylimide and the like].
(B2-5) Other than the above, nitrogen atom-containing vinyl monomers [C7-20, for example, 2-vinylpyridine, 3-vinylpiperidine, vinylpyrazine, vinylmorpholine, etc.] and the like.

(B3) Anionic monomer The following acids, salts thereof [alkali metal salts, alkaline earth metal salts, ammonium salts and amines [C1-20 primary, secondary and tertiary amines (methylamine, ethylamine, dipropyl Amines, triethylamines, etc.) and C2-12 alkanolamines (ethanolamine, N, N-dimethylethanolamine, etc.)] and mixtures thereof (b3-1) unsaturated carboxylic acids [C3-12, for example (meth) acrylic) Acid, (anhydride) maleic acid, fumaric acid, itaconic acid, vinylbenzoic acid, allylacetic acid, etc.]
(B3-2) unsaturated sulfonic acid [C2-20 aliphatic unsaturated sulfonic acid (vinyl sulfonic acid, etc.), C6-20 aromatic unsaturated sulfonic acid (styrene sulfonic acid, etc.), sulfonic acid group-containing (meth ) Acrylates [C5-24, for example 2- (meth) acryloyloxyethanesulfonic acid, 2- (meth) acryloyloxypropanesulfonic acid, 3- (meth) acryloyloxypropanesulfonic acid, 2- (meth) acryloyloxybutanesulfone Acid, 4- (meth) acryloyloxybutanesulfonic acid, 2- (meth) acryloyloxy-2,2-dimethylethanesulfonic acid, p- (meth) acryloyloxymethylbenzenesulfonic acid, etc.), ) Acrylamide [C4-20, for example 2- (meth) acryloylaminoeta Sulfonic acid, 2- (meth) acryloylaminopropanesulfonic acid, 3- (meth) acryloylaminopropanesulfonic acid, 2- (meth) acryloylaminobutanesulfonic acid, 4- (meth) acryloylaminobutanesulfonic acid, 2- ( (Meth) acryloylamino-2,2-dimethylethanesulfonic acid, p- (meth) acryloylaminomethylbenzenesulfonic acid, etc.), alkyl (C1-20) (meth) allyl sulfosuccinate [C5-20, for example, methyl (meth) ) Allylsulfosuccinate, etc.]
(B3-3) (Meth) acryloylpolyoxyalkylene (C1-6) sulfate [C5-60, for example, (meth) acryloylpolyoxyethylene (polymerization degree 2-50) sulfate, etc.] and the like.

  Among the above (b), (b1-1) and (b2-2), and more preferably (b1-), have a high affinity with the above (a) and can be made to have a higher molecular weight. 2) Among (b1-3), (b2-1), (b3-1), and (b3-2), a sulfonic acid group-containing (meth) acrylate and a sulfonic acid group-containing (meth) acrylamide are particularly preferable. Are (meth) acrylamide of (b1-2), N-vinylformamide of (b1-3), N, N-dimethylaminoethyl (meth) acrylate of (b2-1) and these. Salts, (meth) acrylic acid (b3-1), maleic acid (anhydride), itaconic acid and salts thereof, (b3-2) 2- (meth) acryloyloxyethanesulfone among unsaturated sulfonic acids Acid, 2- ( TA) acryloyloxypropanesulfonic acid, 3- (meth) acryloyloxypropanesulfonic acid, 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid and salts thereof, and mixtures of these with (meth) acrylonitrile Most preferably, (b1-2) is (meth) acrylamide, (b1-3) is N-vinylformamide, (b2-1) is N, N-dimethylaminoethyl (meth) acrylate And their salts, (meth) acrylic acid of (b3-1) and their salts (especially alkali metal salts), and (b3-2) of unsaturated sulfonic acid, 2- (meth) acryloyloxyethanesulfonic acid. Acid, 2- (meth) acryloyloxypropanesulfonic acid, 2- (meth) acryloylamino-2,2-di Chill ethanesulfonic acid and salts thereof (especially alkali metal salts), and mixtures of these and (meth) acrylonitrile.

  The above (b) may be polymerized singly or may be arbitrarily mixed and copolymerized. In (b), the proportion (mol%) of acrylamide in (b) is preferably 49 or less, more preferably 45 or less, and still more preferably from the viewpoint of the required amount of the obtained polymer flocculant and the flocculation performance. It is 40 or less, particularly preferably 20 or less, and most preferably 0.

  In the above (b), if necessary, one or more water-insoluble unsaturated monomers (x) may be used in combination. In this case, the molar ratio of (b) to (x) is preferably 99.5 / 0. The ratio is 5/60/40, more preferably 99/1 to 80/20.

Examples of the water-insoluble unsaturated monomer (x) include the following.
(X1) to (x5) below, and mixtures thereof (x1): C4-23 (meth) acrylates [C1-20 aliphatic and alicyclic alcohol (meth) acrylates [methyl, ethyl, butyl, lauryl] Octadecyl and cyclohexyl (meth) acrylate, etc.], C4-20 epoxy group-containing (meth) acrylate [glycidyl (meth) acrylate, etc.]

(X2) Polypropylene glycol (degree of polymerization 2 to 50) [monoalkyl (C1 to 20), monocycloalkyl (C3 to 12) or monophenyl ether] unsaturated carboxylic acid monoester [propylene oxide of monool or diol (hereinafter (Abbreviated as PO) adduct [monool (C1-20) PO adduct] (meth) acrylate [ω-methoxy, ω-ethoxy, ω-propoxy, ω-butoxy, ω-cyclohexoxy and ω-phenoxy] Polypropylene glycol mono (meth) acrylate, etc.], (meth) acrylic acid ester of diol (C2-20) PO adduct [ω-hydroxyethyl (poly) oxypropylene mono (meth) acrylate, etc.] etc.]

(X3) unsaturated hydrocarbon [C2-30, for example, ethylene, nonene, styrene, 1-methylstyrene, etc.]
(X4) Carboxylic acid (C2-20, for example, acetic acid, propionic acid) ester of unsaturated alcohol [C2-20, for example, vinyl alcohol, (meth) allyl alcohol] (for example, vinyl acetate)
(X5) Halogen-containing compounds (for example, vinyl chloride).

  In the presence of (a), the pH of the monomer solution (monomer concentration 20 to 80) when polymerizing or copolymerizing (b) and if necessary (x) is usually 0.5 or more and 5.5 or less. From the viewpoint of preventing hydrolysis of (a) and (b) and the aggregating performance of the obtained polymer flocculant, a preferred lower limit is 1, more preferably 2, particularly preferably 2.5, most preferably 3, and a preferred upper limit. It is 5.4, more preferably 5.3, particularly preferably 5.2, and most preferably 5.0.

The pH adjuster used for adjusting the pH is not particularly limited, but when the aqueous monomer solution is alkaline, sulfuric acid, hydrochloric acid, or a mineral acid such as phosphoric acid; acidic sodium phosphate, acidic sodium nitrate, ammonium chloride, Inorganic solid acidic substances such as ammonium sulfate, ammonium bisulfate, and sulfamic acid; and organic acids such as oxalic acid, succinic acid, and malic acid. When the aqueous monomer solution is acidic, examples thereof include inorganic alkaline substances such as sodium hydroxide, potassium hydroxide, and ammonia; and organic alkaline substances such as guanidine.
The pH may be measured by directly measuring the stock solution of the monomer solution to be polymerized at 20 ° C.

The method for producing the polymer flocculant (A) of the present invention means (co) polymerization or polymerization of at least one of (b) in the presence of (1) (a). same as below. [2] a method of adding (a) to at least one (co) polymer of (b), and [3] a method of forming a mixture of those obtained by these methods. Among these, the method of [1] is preferable from the viewpoint of aggregation performance, and more preferably a method of (co) polymerizing while maintaining the pH of the monomer solution at the time of polymerization at 0.5 or more and 5.5 or less. .
As the polymerization method, known radical polymerization methods such as aqueous solution polymerization, reversed phase suspension polymerization, photopolymerization, precipitation polymerization, and reversed phase emulsion polymerization can be employed. Among these, aqueous solution polymerization, reverse phase suspension polymerization, and reverse phase emulsion polymerization are more preferable from an industrial viewpoint.

For the aqueous solution polymerization, a known method can be used. For example, a method in which an aqueous solution of the monomer is placed in a container in which heat does not enter and exit from outside and subjected to adiabatic polymerization (Japanese Patent Publication No. 59-40843, etc.). A method of performing constant temperature polymerization in a container whose temperature can be controlled from the outside (JP-A-3-189000).
Known methods can also be used for reverse phase suspension polymerization. For example, a method in which an aqueous solution of a water-soluble vinyl monomer is dispersed in a water-in-oil type using an oil-soluble polymer as a dispersion stabilizer and polymerized (Japanese Patent Laid-Open No. -53111) and the like.
Oil-soluble polymer substances include cellulose ethers (ethyl cellulose, ethyl hydroxyethyl cellulose, etc.), sucrose fatty acid esters (sucrose distearate, sucrose tristearate, etc.), sorbitan fatty acid esters (sorbitan monostearate, sorbitan monooleate, etc.) , Polyglycerin fatty acid ester (glyceryl monostearate, etc.), copolymer of alkene and α, β-unsaturated polycarboxylic acid (anhydride) or a derivative thereof [1-olefin having C20 or more and 40 or less and (anhydrous) Copolymer of maleic acid, etc.]. The amount (% by weight) of these is usually 0.1 or more, preferably 0.2 or more, more preferably 0.5 or more, and usually 10 or less, preferably 5 or more, based on the weight of the organic solvent used. Or less, more preferably 3 or less.
Examples of the organic solvent to be used include aliphatic hydrocarbons (C6-12, for example, heptane and cyclohexane), aromatic hydrocarbons (C6-20, for example, benzene, toluene and xylene).

Known methods can also be used for the inverse emulsion polymerization. For example, a method of forming a water-in-oil emulsion by using an aqueous solution of a water-soluble vinyl monomer with a surfactant (Japanese Patent No. 2676483, No. 9-208802).
Examples of the dispersion medium used include hydrocarbons [paraffins (n- and i-paraffins), mineral oils (kerosene, light oil, medium oil, etc.), hydrocarbon-based synthetic oils and the like, and mixtures thereof.

As the surfactant used at the time of emulsification, known surfactants described in Japanese Patent No. 2676483, Japanese Patent Application Laid-Open No. 9-208802 and the like can be used. A combination of a surfactant or a nonionic surfactant with another ionic surfactant is preferred. Examples of nonionic surfactants include, for example, higher fatty acid (C8-24) esters [eg, sorbitan monostearate, sorbitan distearate, sorbitan monooleate, sorbitan oleate ethylene oxide (hereinafter abbreviated as EO) addition] Products), polyoxyethylene long chain alkyl (C8-24) ether (lauryl alcohol polyoxyethylene ether, polyoxyethylene nonylphenyl ether, etc.), long chain alkyl (C8-24) alkanolamide (N, N-dihydroxyethyl) Lauryl amide, etc.).
The addition amount (% by weight) of these surfactants is usually 0.05 or more, preferably 0.1 or more, more preferably 0.12 or more, and usually 1 or less, preferably 1 to the total amount of the dispersion medium. Is 0.5 or less, more preferably 0.25 or less.
When the water-in-oil type emulsion is diluted with water and used, a phase change agent may be added to the water-in-oil type emulsion in advance so that the emulsion is put into water and the phase is rapidly changed. As the phase inverting agent, a surfactant having high hydrophilicity [eg, HLB (HLB of glycine, abbreviated to Hydrophile-Lipophile Balance, which represents a balance between hydrophilicity and lipophilicity) 9 to 20] is used. Examples thereof include cationic surfactants and / or nonionic surfactants described in Japanese Patent No. 2676483 and JP-A-9-208802.

As the radical polymerization initiator used in the above production, known ones, for example, a water-soluble azo initiator [azobisamidinopropane (salt), azobiscyanovaleric acid (salt), 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] (salt), etc., oil-soluble azo initiators (azobiscyanovaleronitrile, azobisisobutyronitrile, azobiscyclohexanecarbonitrile, etc.), water-soluble Examples include peroxides (hydrogen peroxide, ammonium persulfate, sodium persulfate, peracetic acid, t-butyl peroxide, etc.), oil-soluble peroxides (benzoyl peroxide, cumene hydroxy peroxide, etc.).
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 [sulfate Iron (II), etc.], tertiary amines [dimethylaminobenzoic acid (salt), dimethylaminoethanol, etc.], amine complexes of transition metal salts [pentamethylenehexamine complex of cobalt (III) chloride, diethylenetriamine of copper (II) chloride] Complex) and organic reducing agents (such as ascorbic acid). The azo initiator, the peroxide initiator and the redox initiator may be used alone or in combination of two or more.

  The amount (% by weight) of the radical polymerization initiator used is preferably 0.1% based on the total weight of (b) and (x) used as necessary from the viewpoint of obtaining the optimum molecular weight as the polymer flocculant of the present invention. 001 or more, more preferably 0.005 or more, particularly preferably 0.01 or more, most preferably 0.02 or more, preferably 1 or less, more preferably 0.5 or less, particularly preferably 0.1 or less, Most preferably, it is 0.05 or less.

If necessary, a chain transfer agent for radical polymerization may be used. As the chain transfer agent for radical polymerization, a known agent can be used without any particular limitation. For example, compounds having one or two or more hydroxyl groups in a molecule [C1 to 200, for example, monool (methanol, ethanol, isopropyl alcohol, etc.), diol (ethylene glycol, propylene glycol, poly (degree of polymerization 2 to 50)) Ethylene glycol, poly (degree of polymerization 2-50) ethylene poly (degree of polymerization 2-50) propylene glycol, etc.], a compound having one or more amino groups in the molecule {ammonia, amine [C1-200, for example, Monoamine (methylamine, dimethylamine, triethylamine, propanolamine, etc.), diamine [ethylenediamine, poly (polymerization degree: 2 to 50) ethyleneimine, etc.]] etc., compounds having one or more thiol groups in the molecule (Described later) and the like.
Among these, compounds having one or more thiol groups in the molecule are preferable from the viewpoint of controlling the molecular weight.

Examples of the compound having a thiol group in the molecule include the following compounds, a mixture thereof and, if necessary, a salt thereof [alkali metal (the above) salt, alkaline earth metal (the above) salt, ammonium salt, amine (C1-20, For example, methylamine, ethylamine) salts, inorganic acid (hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, etc.) salts and the like].
(1) monovalent thiol aliphatic thiol [C1-20, for example, methanethiol, ethanethiol, propanethiol, n-octanethiol, n-dodecanethiol, hexadecanethiol, n-octadecanethiol, 2-mercaptoethanol, mercaptoacetic acid, 3-mercaptopropionic acid, 1-thioglycerol, monoethanolamine thioglycolate), 1-thioglycerol, monoethanolamine thioglycolate, thiomaleic acid, cysteine and 2-mercaptoethylamine], alicyclic thiols (C5-20 For example, cyclopentanethiol and cyclohexanethiol) and aromatic (fatty) thiols (C6-12, such as benzenethiol and benzylmercaptan and thiosalicylic acid).

(2) polyvalent thiol dithiol [aliphatic (C2-40) dithiol (for example, ethanedithiol, diethylenedithiol, triethylenedithiol, propanedithiol, 1,3- and 1,4-butanedithiol, 1,6-hexanedithiol, Neopentanedithiol, etc.), alicyclic (C5-20) dithiols (eg, cyclopentanedithiol and cyclohexanedithiol) and aromatic (C6-16) dithiols (eg, benzenedithiol, biphenyldithiol).

  The amount (% by weight) when the chain transfer agent for radical polymerization is used is preferably based on the total weight of (b) and (x) from the viewpoint of obtaining the optimum molecular weight as the polymer flocculant of the present invention. Is 0.0001 or more, more preferably 0.0005 or more, particularly preferably 0.001 or more, most preferably 0.005 or more, preferably 10 or less, more preferably 5 or less, particularly preferably 3 or less, most preferably Preferably it is 1 or less.

The monomer concentration (% by weight) in the aqueous monomer solution at the time of production is usually 20 or more, preferably 25 or more, more preferably 30 or more, particularly preferably 40 or more, most preferably 40 or more, based on the weight of the monomer aqueous solution. It is preferably at least 50, usually at most 80, preferably at most 75, more preferably at most 70, particularly preferably at most 65, most preferably at most 60; usually 30 or more, preferably at least 40, in reverse phase suspension polymerization. It is preferably 45 or more, particularly preferably 50 or more, most preferably 55 or more, usually 90 or less, preferably 85 or less, more preferably 80 or less, particularly preferably 78 or less, and most preferably 75 or less; Is usually 10 or more, preferably 20 or more, more preferably 30 or more, particularly preferably 40 or more, and most preferably. Is 55 or more, usually 90 or less, preferably 80 or less, more preferably 75 or less, particularly preferably 70 or less, most preferably 65 or less.
Here, the weight of the aqueous monomer solution refers to the total weight of the monomer {(b) and, if necessary, (x)}, (a), water, an initiator, a chain transfer agent if necessary, and other additives (described later).

The amount (% by weight) of the dispersion medium used in the reverse phase suspension polymerization is preferably 25 or more, more preferably 40 or more, and particularly preferably, based on the total weight of the aqueous monomer solution from the viewpoint of stabilizing the dispersion system. It is 65 or more, preferably 1,000 or less, more preferably 400 or less, and particularly preferably 200 or less.
The amount (% by weight) of the dispersion medium used in the inverse emulsion polymerization is preferably 20 or more, more preferably 30 or more, and particularly preferably 40 or more, based on the total weight of the aqueous monomer solution from the viewpoint of the stability of the emulsion. , Preferably 80 or less, more preferably 70 or less, particularly preferably 60 or less.

  The polymerization temperature (° C.) is usually −10 or more, preferably 0 or more, more preferably 5 or more, particularly preferably 10 or more, and most preferably 15 or more in aqueous solution polymerization, and usually 50 or less, preferably 40 or less, It is more preferably 30 or less, particularly preferably 25 or less, and most preferably 20 or less. During the polymerization, the temperature may be appropriately adjusted by heating and cooling so as to keep the predetermined temperature constant (for example, the predetermined polymerization temperature ± 5 ° C.), or the adiabatic polymerization may be performed in a glass heat insulating container or the like. . At the time of adiabatic polymerization, it is preferable to adjust the starting temperature or the total amount of monomers in the system so that the boiling point of water (100 ° C.) is not increased by the heat of polymerization.

  In the reverse phase suspension polymerization, the polymerization temperature (° C.) is usually 10 or more, preferably 20 or more, more preferably 30 or more, particularly preferably 40 or more, and most preferably 50 or more, and usually 95 or less, preferably 90 or more. Or less, more preferably 80 or less, particularly preferably 70 or less, and most preferably 60 or less. During the polymerization, it is preferable to adjust the temperature by heating and cooling appropriately so as to keep the predetermined polymerization temperature constant (for example, the predetermined polymerization temperature ± 5 ° C). In order to keep the polymerization temperature constant, the monomer may be dropped as needed into the dispersion medium whose temperature has been adjusted to a predetermined polymerization temperature under stirring. 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.

  In the reverse phase emulsion polymerization, the polymerization temperature (° C.) is usually 0 or more, preferably 5 or more, more preferably 10 or more, particularly preferably 15 or more, and most preferably 20 or more, and usually 95 or less, preferably 90 or more. Or less, more preferably 80 or less, particularly preferably 70 or less, and most preferably 55 or less. During the polymerization, the temperature may be adjusted by heating and cooling as appropriate so as to keep the predetermined polymerization temperature constant (for example, the predetermined polymerization temperature ± 5 ° C), or the polymerization may be carried out at a relatively low temperature (for example, 15 to 35 ° C). After the polymerization is started, the temperature may be raised (for example, 55 to 80 ° C.) after polymerization for a certain time (for example, 1 to 3 hours).

The termination of the polymerization can be confirmed when the heat generated by the polymerization has been eliminated. From the viewpoint of completing the polymerization and reducing the residual monomer, it is desirable to carry out the polymerization for a longer time than when the heat generation is stopped. The polymerization time is usually 1 or more from the time when the initiation of polymerization is confirmed by heat generation, preferably 2 or more, more preferably 3 or more, particularly preferably 4 or more, most preferably 5 or more from the above viewpoint, and usually 48 or less, and industrially 48 or less. From the viewpoint of, it is preferably 36 or less, more preferably 24 or less, particularly preferably 20 or less, and most preferably 16 or less. When the monomer is dropped at any time as in the case of reverse phase suspension polymerization, it is preferable to carry out the polymerization for the above-mentioned time after the completion of the dropping.
The above-mentioned monomer concentration, polymerization temperature, and polymerization time can be appropriately adjusted depending on the monomer composition, polymerization method, type of initiator, and the like.

  The pressure at the time of polymerization (kPa, hereinafter referred to as absolute pressure) is not particularly limited, but is usually carried out under atmospheric pressure. In the case of reverse phase suspension polymerization, from the viewpoint of easy temperature control during polymerization, preferably at the polymerization temperature, a pressure at which the dispersion medium boils or a pressure at which the hydrophobic dispersion medium and water azeotrope is preferable. . Specifically, it is preferably 5 or more, more preferably 12 or more, particularly preferably 25 or more, preferably 95 or less, more preferably 80 or less, and particularly preferably 65 or less.

  After the polymerization, the polymer flocculant of the present invention may be further subjected to a denaturing reaction of the obtained polymer. As the polymer modification reaction, for example, when (b) having a hydrolyzable functional group such as acrylamide in the molecule is used, a caustic alkali (such as sodium hydroxide and potassium hydroxide) or an alkali carbonate ( Sodium carbonate, potassium carbonate, etc.) to partially hydrolyze the hydrolyzable functional groups such as amide groups [the hydrolysis rate is about 1 to 60 mol% based on the total (co) polymerization moles]. (For example, JP-A-56-16505), formaldehyde, dialkyl (C1-12) amine and halogenated (chlorinated, brominated, iodided, etc.) alkyl (C1-12) (for example, methyl Chloride, ethyl chloride, etc.) and partially introducing a cationic group by Mannich reaction, or acrylonitrile, etc. A method in which an amidine ring is formed in a molecule by a ring-closing reaction between a nitrile group, an amino group obtained by hydrolysis of vinyl formamide or the like, and an amino group obtained by hydrolysis or the like (JP-A-5-192513). Can be

  The water-containing gel after the polymerization can be further dehydrated to obtain a powdery polymer flocculant. The dehydration method at this time is not particularly limited, and may be a dehydration method by drying such as hot air drying, infrared drying, indirect heating drying (vacuum drying, agitating type dryer, drum dryer), or an organic solvent such as acetone or methanol. After dehydration by adding a hydrogel, a method of removing the solvent by the above-mentioned drying method or the like can be used. In the case of the reversed-phase emulsion polymerization method, an emulsion dispersion obtained after the polymerization may be used as it is as a polymer flocculant.

The molecular weight of the polymer flocculant (A) of the present invention is usually 1 or more and 40 or less in terms of intrinsic viscosity (dl / g) measured at 30 ° C. in a 1N aqueous solution of NaNO _3. More preferably, it is 6 or more, particularly preferably 8 or more, most preferably 9.5 or more, preferably 30 or less, more preferably 25 or less, particularly preferably 20 or less, and most preferably 18 or less.

  As a method for measuring the content of (a) in (A), an extraction method utilizing the difference in solubility between (A) and (a) can be used. For example, in a solvent in which the (A) swells and does not dissolve, the mixture is stirred at 20 ° C. for about 24 hours, (a) is extracted from the (A), and the content of the (a) in the extract is determined by high performance liquid chromatography. It can be measured by using a graph or the like. As the solvent used for the extraction, it is necessary to select an appropriate solvent depending on the composition of the polymer flocculant, and examples thereof include a water-soluble polar solvent such as methanol, ethanol, and isopropyl alcohol, and a mixed solvent thereof with water. .

(A) is preferably used as a polymer flocculant for flocculation treatment of sewage sludge or the like or a polymer flocculant for flocculation treatment of wastewater or the like, because it shows a unique flocculation performance which has never been seen before. Is a polymer flocculant for flocculation treatment of sewage sludge and the like.
As the polymer flocculant for flocculation treatment of the above-mentioned sewage sludge, the size of suspended particles in the sewage sludge is relatively large, and the surface of the suspended particles in water is negatively charged. An amphoteric polymer flocculant or an amphoteric polymer flocculant, and a mixture thereof are preferred.
Here, the cationic polymer flocculant is a polymer flocculant having a cationic group in the molecule, that is, a polymer flocculant that exhibits cationicity when dissolved in water. And a polymer flocculant having a cationic group and an anionic group in the molecule, that is, a polymer flocculant that exhibits cationic and anionic properties when dissolved in water. The method for evaluating the cationic or anionic properties of these polymer flocculants in water can be determined as a colloid equivalent value (meq / g). That is, the cationic group equivalent value in the cationic flocculant can be obtained as a cationic 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 value, respectively. It can be obtained as an equivalent value.

The equivalent value of the cationic colloid in the cationic polymer flocculant of the present invention is preferably 0.1 or more, more preferably 0.5 or more, further preferably 1.0 or more, and particularly preferably 1 or more, from the viewpoint of the aggregation performance. 0.5 or more, most preferably 2.0 or more, preferably 7.0 or less, more preferably 6.0 or less, still more preferably 5.5 or less, particularly preferably 5.2 or less, and most preferably 5.5 or less. 0 or less.
Further, the equivalent value of the cationic colloid in the amphoteric polymer flocculant of the present invention is preferably 0.1 or more, more preferably 0.5 or more, still more preferably 1.0 or more, particularly preferably from the same viewpoint as described above. Is 1.5 or more, most preferably 2.0 or more, preferably 7.0 or less, more preferably 6.0 or less, still more preferably 5.5 or less, particularly preferably 5.2 or less, and most preferably. 5.0 or less.
The anionic colloid equivalent value is preferably -13.0 or more, more preferably -10.0 or more, further preferably -8.0 or more, particularly preferably -5.0 or more, and most preferably -3.0 or more. Yes, it is preferably -0.05 or less, more preferably -0.1 or less, still more preferably -0.3 or less, particularly preferably -0.5 or less, and most preferably -1.0 or less.

The colloid equivalent value can be determined by the colloid titration method described below. The subsequent measurement is performed at room temperature (about 20 ° C.).
(1) Preparation of measurement sample (50 ppm aqueous solution) 0.2 g of sample (converted to solid content) was precisely weighed, placed in a 200 ml glass Erlenmeyer flask, and the total weight (total weight of sample and ion-exchanged water) was determined. After adding ion-exchanged water to 100 g, the mixture is completely dissolved by stirring with a magnetic stirrer (1,000 rpm) for 3 hours to prepare a 0.2% by weight polymer flocculant solution. Further, 10 ml of the solution prepared above was placed in a 500 ml glass beaker using a 10 ml hole pipette, and ion-exchanged water was added so that the total weight (total weight of the solution and the ion-exchanged water) was 400 g. In addition, the mixture is again stirred with a magnetic stirrer (1,000 to 1,200 rpm) for 30 minutes to obtain a uniform measurement sample.
The solids content of the polymer coagulant was determined by weighing about 1.0 g of a sample in a Petri dish (W1) and drying it in a circulating drier at 105 ± 5 ° C. for 90 minutes to obtain the remaining weight (W2). ) Is a value calculated from the following equation.
Solid content (% by weight) = (W2) × 100 / (W1)

(2) Measurement of Cationic Colloid Equivalent Value 100 g of a measurement sample is placed in a 200 ml glass conical beaker, and a 0.5% by weight aqueous sulfuric acid solution is gradually added thereto with stirring to adjust the pH to 3. Next, 2-3 drops of a toluidine blue indicator (TB indicator) are added, and titration is performed with an N / 400 polyvinyl potassium sulfate (N / 400 PVSK) reagent. The titration speed is 2 ml / min, and the point at which the measurement sample changes color from blue to magenta and is held for 30 seconds is the end point.
(3) Measurement of anionic colloid equivalent value 100 g of a measurement sample was placed in a 200 ml glass conical beaker, and 0.5 ml of an N / 10 aqueous sodium hydroxide solution was added thereto while stirring with a magnetic stirrer (500 rpm). After adding 5 ml of glycol chitosan aqueous solution using a 5 ml whole pipette, the mixture is stirred for 5 minutes (at that time, the pH is about 10.5). Add 2-3 drops of TB indicator and titrate as in (2).
(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

Cationic or anionic colloid equivalent value (meq / g)
= (１ ／) × (titer of sample−titer of blank test) × (titer of N / 400 PVSK)

  (A) may be an inorganic salt [a metal salt or an ammonium salt of an inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, sulfamic acid, or carbonic acid, for example, sodium carbonate, potassium carbonate, ammonium carbonate, sodium sulfate, ammonium sulfate] , Sodium hydrogen sulfate, etc.], organic acids (salts) [organic acids such as carboxylic acids, sulfonic acids, phenols, and their metal salts or ammonium salts such as sodium acetate, sodium lactate, etc.], surfactants [US Pat. No. 4331447, surfactants such as polyoxyethylene nonylphenyl ether, dioctyl sulfosuccinate, etc., blocking inhibitors [higher fatty acid (C8-24) salts (calcium stearate, calcium oleate, etc.), higher alkyl ( C8-24) Benzenesulfonic acid salt (dodecylbenzenesulfonic acid salt) ), Polyether-modified silicone oils, such as polyethylene oxide-modified silicone, polyethylene oxide / polypropylene oxide-modified silicone, etc., antioxidants [phenol compounds (hydroquinone, methoxyhydroquinone, catechol, etc.), hindered amines [cuperone, 2- (5 -Methyl-2-hydroxyphenyl) benzotriazole, dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine succinate polycondensate, bis (1-octyloxy-2) , 2,6,6-tetramethyl-4-piperidyl) sebacate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl, etc.], sulfur-containing compounds [2-mercaptobenzothiazole and the like. Salt (gold Salts or ammonium salts), tetramethylthiuram disulfide, dimethyldithiocarbamic acid and its salts (metal salts or ammonium salts, etc.), sodium sulfite, sodium thiosulfate, etc.], phosphorus-containing compounds (triphenyl phosphite, triethyl phosphite, Sodium phosphite, sodium hypophosphite, etc.). These additives may be added in advance to the aqueous monomer solution, or may be added to the polymer after polymerization, kneaded and blended.

  The amount (% by weight) of these additives is based on the solid content (monomer content) in the monomer aqueous solution when the additive is previously added to the monomer aqueous solution, and the additive is added in the polymer. In general, the inorganic salt and the organic acid (salt) are each 10 or less, the surfactant and the antiblocking agent are 5 or less, respectively, the antioxidant is 20 or less, and the additives are based on the solid content in the polymer. From the viewpoint of the effect of (A) and the viscosity of the aqueous solution at the time of dissolution, preferably, the inorganic salt and the organic acid (salt) are each 0.05 to 5, the surfactant and the antiblocking agent are each 0.005 to 3, The inhibitor is 0.001 to 10.

  In the case of (A), the above (a) may be further added, blended and kneaded with the polymer after polymerization, if necessary, as long as the effects of the present invention are not impaired. At this time, the addition amount (% by weight) of (a) is preferably 0.01 or more, more preferably 0.1%, based on the polymer content in (A), from the viewpoint of not impairing the aggregation performance of (A). The number is particularly preferably 1 or more, most preferably 4 or more, preferably 50 or less, more preferably 30 or less, particularly preferably 20 or less, and most preferably 10 or less.

The method of adding (A) to sewage sludge or wastewater is not particularly limited, but is preferably a treatment method of adding floc to sewage sludge or wastewater to form flocs and then performing solid-liquid separation.
The amount (% by weight) of (A) to be added to sewage sludge or wastewater varies depending on the type of the sewage sludge or wastewater, the content of suspended particles, the molecular weight of (A), etc., but is particularly limited. It is usually 0.01 to 10 and preferably 0.1 or more, more preferably 0.1 or more, from the viewpoint of coagulation performance, based on the weight of evaporation residue in sewage sludge or wastewater (hereinafter abbreviated as TS). It is 5 or more, particularly preferably 1 or more, preferably 5 or less, more preferably 3 or less, and particularly preferably 2 or less.

It is preferable that (A) is added to the sewage sludge or the wastewater after being made into an aqueous solution from the viewpoint of coagulation performance, but may be added to the wastewater in a solid state. When (A) is used as an aqueous solution, it is preferable to dissolve it in 0.05 to 1% by weight from the viewpoint of solution handling and mixing with sewage sludge or wastewater.
The dissolution method and the dilution method after dissolution are not particularly limited.For example, a predetermined amount of a polymer coagulant is slowly added to water measured in advance while stirring using a stirrer such as a jar tester, and the solution is added for several hours. A method of stirring and dissolving (about 2 to 4 hours) can be employed. In particular, when dissolving the powdery polymer flocculant in water, if the polymer flocculant is added at once, a clogging occurs, and it is difficult to completely dissolve the polymer flocculant in water, which is not preferable.

When the aqueous solution of (A) is added to sewage sludge or wastewater and used, depending on the sewage sludge or wastewater used, an inorganic coagulant (sulfuric acid band, polyaluminum chloride, ferric chloride, ferric sulfate, polyiron sulfate) , Slaked lime, etc.) and an organic coagulant (aniline-formaldehyde polycondensate hydrochloride, polyvinylbenzyltrimethylammonium chloride, dimethyldi (meth) allylammonium chloride, etc.) may be used in combination. When used in combination, (A) may be added in advance, or (A) may be added after adding an inorganic coagulant and / or an organic coagulant to the sewage sludge or wastewater in advance to cause primary coagulation. Good.
The amount (% by weight) of the inorganic coagulant and / or the organic coagulant used depends on the type of the sewage sludge or wastewater, the size of the suspended particles, the type of the coagulant used, and the like, but is not particularly limited. The amount of the inorganic coagulant for TS in sewage sludge or wastewater is usually 20 or less, preferably 0.5 or more, more preferably 1 or more, particularly preferably 3 or more, from the viewpoint of charge neutralization of the suspension. From the viewpoint of the amount of ash after incineration, it is preferably 10 or less, more preferably 8 or less, particularly preferably 5 or less, usually 1 or less for organic coagulants, and preferably 0.01 or less from the viewpoint of suspension charge neutralization. The above is more preferably 0.025 or more, particularly preferably 0.05 or more, and preferably 0.5 or less, more preferably 0.2 or less, particularly preferably 0.15 or less from the viewpoint of treatment cost.

  As a method of dewatering (solid-liquid separation method) the floc sludge formed by adding (A), known centrifugation, belt press, filter press, capillary dewatering, etc. can be applied. From the viewpoint of high floc strength, which is specific coagulation performance, centrifugation, belt press and filter press dewatering can be more suitably applied.

  The product form of (A) may be any known form such as a powder form (crushed, spherical, grape-like, etc.), film, aqueous solution, w / o emulsion, suspension, etc.

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples. In the examples,% indicates% by weight, and the copolymerization ratio indicates a molar ratio.
The intrinsic viscosity [η] (dl / g) is a value measured at 30 ° C. in a 1N-NaNO ₃ aqueous solution. The colloid equivalent value and solid content of the polymer flocculant were measured by the methods described above.
The TS and organic components (ignition loss) in the sludge were measured according to the analysis method described in the Sewerage Test Method (Japan Sewerage Association, 1984 version).

Example 1
65 parts of a 50% aqueous solution of acrylamide, 74 parts of an 80% aqueous solution of a methyl chloride salt of N, N-dimethylaminoethyl acrylate, and 23 parts of urea were added to a kolben equipped with a stirrer, and then the total% of monomers in the system was further reduced. Ion-exchanged water was added so as to be 30% (in this case, 144 parts of ion-exchanged water), and the mixture was stirred until a uniform solution was obtained in the tank. While continuing stirring, the pH of the aqueous monomer solution (20 ° C.) was adjusted to 5.0 using sulfuric acid. Next, the temperature of the solution was adjusted to 40 ° C. in a constant temperature bath at 40 ° C., and the inside of the system was sufficiently replaced with nitrogen (purity: 99.999% or more) (gas phase oxygen concentration: 10 ppm or less). Next, 0.46 parts of a 10% aqueous solution of 2,2'-azobis (2-methylpropionamidine) dihydrochloride was added as an initiator with stirring. Approximately 1 minute later, polymerization started and heat generation was observed. However, the mixture was cooled from the outside and polymerization was performed at a temperature of 40 to 50 ° C. for 10 hours. Thereafter, the mixture was externally heated and aged at 70 ° C. for 1 hour to complete the polymerization. During the polymerization, the contents became highly viscous and stirring became difficult, so the stirring was stopped halfway. After completion of the polymerization, the content was taken out, 2,000 parts of acetone was added thereto, and the mixture was stirred with a mixer for 30 minutes to obtain a precipitate. The precipitate was removed by filtration under reduced pressure (using two types of filter papers according to JIS standards), and the solvent was distilled off from the precipitate in a reduced-pressure drier (reduced pressure: 10 mmHg, 40 ° C. × 2 hours) to obtain a powder. 119 parts of polymer flocculant (1) was obtained (yield 98%, solid content 95%).

Example 2
A powdery product was prepared in the same manner as in Example 1 except that 42 parts of the 50% aqueous acrylamide solution was used instead of 65 parts and 88 parts of the 80% aqueous solution of methyl chloride salt of N, N-dimethylaminoethyl acrylate was used instead of 74 parts. Of the polymer coagulant (2) was obtained (yield 98%, solid content 95%).

Example 3
34 parts instead of 65 parts of 50% aqueous acrylamide solution, and 74 parts of 80% aqueous solution of methyl chloride salt of N, N-dimethylaminoethyl acrylate instead of 74 parts of 80% aqueous solution of methyl chloride salt of N, N-dimethylaminoethyl methacrylate 94 In the same manner as in Example 1 except that 7 parts of guanidine carbonate were used instead of 23 parts of urea and 23 parts of urea, to obtain 104 parts of a powdery polymer flocculant (3) (yield 98%, solid content). 93%).

Example 4
Instead of 65 parts of acrylamide 50% aqueous solution and 74 parts of 80% aqueous solution of methyl chloride salt of N, N-dimethylaminoethyl acrylate, 115 parts of 80% aqueous solution of methyl chloride salt of N, N-dimethylaminoethyl methacrylate, 23 parts of urea Was used in the same manner as in Example 1 except that 9 parts of dicyandiamide was used instead of, to obtain 104 parts of a powdery polymer flocculant (4) (yield 96%, solid content 93%).

Example 5
33 parts instead of 65 parts of 50% aqueous acrylamide solution, 33 parts instead of 74 parts of 80% aqueous solution of methyl chloride salt of N, N-dimethylaminoethyl acrylate, 80 parts of methyl chloride salt of N, N-dimethylaminoethyl methacrylate % Aqueous solution, 7 parts of acrylic acid and 23 parts of urea were replaced with 14 parts of guanyl urea phosphate, and the pH (20 ° C.) of the aqueous monomer solution was adjusted to 3.0 using sulfuric acid. In the same manner as described above, 112 parts of a powdery polymer flocculant (5) were obtained (yield 97%, solid content 92%).

Comparative Example 1
Except not using urea, it carried out similarly to Example 1, and obtained 95 parts of powdery polymer flocculants (ratio 1) (yield 97%, solid content 94%).

Comparative Example 2
Except not using urea, it carried out similarly to Example 2, and obtained 95 parts of powdery polymer flocculants (ratio 2) (yield 97%, solid content 94%).

Comparative Example 3
Except not using guanidine carbonate, 95 parts of a powdery polymer flocculant (ratio 3) was obtained in the same manner as in Example 3 (yield 97%, solid content 94%).

Comparative Example 4
Except not using dicyandiamide, it carried out similarly to Example 4, and obtained 95 parts of powdery polymer coagulants (ratio 4) (96% of yield, 93% of solid content).

Comparative Example 5
Except not using guanyl urea phosphate, 96 parts of a powdery polymer flocculant (ratio 5) was obtained in the same manner as in Example 5 (yield 97%, solid content 93%).

Example 6
After adding 65 parts of a 50% aqueous solution of acrylamide, 74 parts of an 80% aqueous solution of methyl chloride salt of N, N-dimethylaminoethyl acrylate, and 6 parts of urea, the ion is further added so that the total% of the monomers in the system becomes 60%. Exchanged water (in this case, 8 parts of ion-exchanged water) was added to prepare a mixture at room temperature (20 to 25 ° C). The pH (20 ° C.) of the aqueous monomer solution was adjusted to 5.0 with sulfuric acid while stirring. After sufficiently replacing the obtained liquid mixture with nitrogen (purity 99.999% or more) (gas phase oxygen concentration 10 ppm or less), a 10% aqueous solution of 2,2′-azobis (2-methylpropionamidine) dihydrochloride is used. 0.46 parts by weight was added to make a homogeneous solution to prepare an aqueous monomer solution.
Separately, 230 parts of cyclohexane was charged into a reaction vessel equipped with a reflux dewatering pipe, a dropping funnel, a nitrogen introduction pipe, and a stirring blade (Max blend blade), and then alkene (C30 or more) and a maleic anhydride copolymer (Mitsubishi Chemical Corporation). After adding 7 parts of “Diacarna 30” (trade name, manufactured by Co., Ltd.), the inside of the reaction vessel was purged with nitrogen (gas phase oxygen concentration: 10 ppm or less) while stirring the stirring blades at a rotation speed of 300 rpm. The temperature was raised to ° C. After the temperature reached 55 ° C., the pressure inside the reaction vessel was reduced (60 kPa), and the entire amount of the monomer aqueous solution previously charged in the dropping funnel was introduced into the reaction vessel over 120 minutes. After the completion of the introduction, the mixture was stirred at 55 ° C. for 60 minutes. The polymerization was continued.
The resin slurry after polymerization is supplied to a vacuum filter to perform solid-liquid separation, and then dried in a vacuum dryer (degree of vacuum: 10 mmHg, 40 ° C. × 2 hours) to obtain a spherical polymer flocculant (6). ) 102 parts were obtained (yield 98%, solid content 94%).

Example 7
A spherical form was prepared in the same manner as in Example 6, except that 42 parts of the 50% aqueous acrylamide solution was used instead of 65 parts and 88 parts of the 80% aqueous solution of methyl chloride salt of N, N-dimethylaminoethyl acrylate was used instead of 74 parts. Of a polymer coagulant (7) was obtained (yield 98%, solid content 94%).

Example 8
34 parts instead of 65 parts of 50% aqueous acrylamide solution, and 74 parts of 80% aqueous solution of methyl chloride salt of N, N-dimethylaminoethyl acrylate instead of 74 parts of 80% aqueous solution of methyl chloride salt of N, N-dimethylaminoethyl methacrylate 94 In the same manner as in Example 6 except that 3 parts of guanyl urea phosphate were used instead of 6 parts of urea and 6 parts of urea, to obtain 98 parts of a spherical polymer flocculant (8) (yield 98%, solid Content 95%).

Example 9
Instead of 65 parts of acrylamide 50% aqueous solution and 74 parts of 80% aqueous solution of methyl chloride salt of N, N-dimethylaminoethyl acrylate, 115 parts of 80% aqueous solution of methyl chloride salt of N, N-dimethylaminoethyl methacrylate and 6 parts of urea Was used in the same manner as in Example 6 except that guanidine sulfamate (2 parts) was used instead of to obtain 97 parts of a spherical polymer flocculant (9) (yield 97%, solid content 94%).

Example 10
33 parts instead of 65 parts of 50% aqueous acrylamide solution, 33 parts instead of 74 parts of 80% aqueous solution of methyl chloride salt of N, N-dimethylaminoethyl acrylate, 80 parts of methyl chloride salt of N, N-dimethylaminoethyl methacrylate % Aqueous solution, 7 parts of acrylic acid, and 11 parts of urea instead of 6 parts, and the pH (20 ° C.) of the aqueous monomer solution was adjusted to 3.0 using sulfuric acid. 107 parts of a true spherical polymer flocculant (10) were obtained (yield 98%, solid content 94%).

Comparative Example 6
Except not using urea, it carried out similarly to Example 6, and obtained 95 parts of true spherical polymer flocculants (ratio 6) (yield 97%, solid content 94%).

Comparative Example 7
Except that urea was not used, the same procedure as in Example 7 was carried out to obtain 95 parts of a spherical polymer flocculant (ratio 7) (yield 97%, solid content 94%).

Comparative Example 8
Except that no guanyl urea phosphate was used, 96 parts of a spherical polymer flocculant (ratio 8) was obtained in the same manner as in Example 8 (yield 98%, solid content 94%).

Comparative Example 9
Except not using guanidine sulfamate, it carried out similarly to Example 9, and obtained 96 parts of spherical polymer flocculants (ratio 9) (yield 97%, solid content 93%).

Comparative Example 10
Except not using urea, it carried out similarly to Example 10, and obtained 96 parts of true spherical polymer flocculants (ratio 10) (yield 97%, solid content 93%).

Example 11
68 parts of isoparaffin (boiling point: 190 ° C. to 230 ° C.) and 6.5 parts of sorbitan monooleate were charged into a reaction vessel equipped with a stirrer, a nitrogen inlet tube, and a thermometer, and dissolved by stirring. Next, 41 parts of ion-exchanged water and 7 parts of acrylic acid were weighed into a beaker, and while cooling in an ice bath, 8 parts of a 48% NaOH aqueous solution was gradually added to neutralize while controlling the temperature at 20 ° C. or lower. After neutralization, 33 parts of 50% aqueous solution of acrylamide, 33 parts of 80% aqueous solution of methyl chloride salt of N, N-dimethylaminoethyl acrylate, 52 parts of 80% aqueous solution of methyl chloride salt of N, N-dimethylaminoethyl methacrylate, urea 9 parts, adjusted to pH 4.0 with sulfuric acid, blended with the above oil phase, and homogenized [Toki Kika Kogyo Co., Ltd .; K homomixer], and emulsified by stirring at 1,000 rpm for 15 minutes. 0.02 parts of a 10% aqueous solution of isopropyl alcohol was added to the obtained emulsion, the temperature in the system was maintained at 26 ° C. in a constant temperature bath, and the atmosphere was replaced with nitrogen (gas phase oxygen concentration 10 ppm or less), followed by 2,2′-azobis [ 2- (5-Methyl-2-imidazolin-2-yl) propane] 0.17 parts of a 10% aqueous solution of hydride dichloride was added to initiate polymerization. After polymerization at a reaction temperature of 26 ° C. for 10 hours, 5 parts of polyoxyethylene tridecyl ether is added as a phase inversion agent to the resulting emulsion, and the mixture is uniformly mixed to obtain a water-in-oil emulsion polymer flocculant (11). 262 parts were obtained (yield 100%, solid content 39%).

Comparative Example 11
Except that urea was not used, 253 parts of a water-in-oil emulsion type polymer coagulant (ratio 11) was obtained in the same manner as in Example 11 (yield 100%, solid content 36%).

  Table 1 shows the results of the polymer flocculants (1) to (11) of the present invention and the comparative polymer flocculants (ratio 1) to (ratio 11).

AAM: Acrylamide
DAAQ: N, N-dimethylaminoethyl acrylate methyl chloride salt
DAMQ: N, N-dimethylaminoethyl methacrylate methyl chloride salt
AAc: Acrylic acid

Examples 12 to 17, Comparative Examples 12 to 17
Each of the polymer flocculants shown in Table 2 was dissolved in ion-exchanged water to obtain a polymer aqueous solution having a solid content of 0.2%. As the sludge to be evaluated, digested sludge (pH 7.5, TS 2.3%, organic content 62%) collected from the sewage treatment plant A was used, and the following floc diameter, filtrate amount, filter cloth releasability and cake moisture content were determined. An evaluation was performed. Table 2 shows the test results.

<Flock diameter>
A jar tester [Miyamoto Riken Kogyo Co., Ltd., Model JMD-6HS-A] is used to continuously connect two plate-like PVC stirring blades (diameter 5 cm, height 2 cm, thickness 0.2 cm) so as to form a cross. Then, 200 ml of the sludge was placed in a 500 ml beaker and set in a jar tester. The rotation number of the jar tester was set to 120 rpm, and 20 ml of a 0.2% aqueous polymer solution (the amount of the polymer flocculant added was 0.87% / TS at this time) was added all at once while slowly stirring the sludge, followed by stirring for 30 seconds. Thereafter, the stirring was stopped, and the size of the aggregate was visually observed (floc diameter: 120 rpm). Subsequently, the rotation number was set to 300 rpm, and after stirring for further 30 seconds, the stirring was stopped, and the size of the aggregate was visually observed again (floc diameter: 300 rpm). The floc diameter was determined according to the floc particle size diagram shown in FIG.

<Filtrate volume>
A nylon filter cloth of T-1189 (made by Shikishima Canvas Co., Ltd., circular shape, diameter 9 cm), a Nutse funnel, and a measuring cylinder capable of measuring 300 ml are set, and the sludge after the above floc diameter test is put at once and filtered. Using a stopwatch, the amount of filtrate was measured 60 seconds after the sludge was introduced.
<Filter cloth release property>
A part of the filtered sludge is taken out with a spatula, subjected to a dehydration test (2 kg / cm ² , 60 seconds) using a press filter tester, and the peelability of the dewatered cake from the filter cloth after the test is evaluated by the following score. did.
◎: Very easy to peel off (no adhesion to filter cloth)
○: easy to peel off (slightly attached to filter cloth)
△: Somewhat difficult to peel off (there is some adhering matter on the filter cloth, slightly adhered to the inside of the filter cloth)
×: Difficult to peel off (adhered to the inside of the filter cloth)

<Cake moisture content>
Using the dehydrated cake after the filter cloth peeling test, the water content of the cake was measured according to the analysis method described in the Sewerage Test Method (Japan Sewerage Association, 1984 edition).

  From the results shown in Table 2, in Examples, coarse particles were formed, and flocs once formed were less likely to break (higher floc strength) even under high stirring (300 rpm) than in Comparative Examples. And high dehydration (low cake moisture content).

Examples 18 and 19, Comparative Examples 18 and 19
Polymer flocculant shown in Table 3, surplus sludge (pH 6.0, TS 2.0%, organic content 83%) collected from B sewage treatment plant, 35 ml of 0.2% polymer aqueous solution (polymer flocculant added at this time) (TS 1.75% / TS). Table 3 shows the test results.
From the results in Table 3, similarly to the results in Table 2, even in the case of the excess sludge, the example forms coarser particles than the comparative example, and the floc once formed is less likely to break even under high stirring (300 rpm). (High floc strength), good filter cloth releasability, and high dewaterability (low cake moisture content).

Examples 20 to 22, Comparative Examples 20 to 22
Polymer flocculant shown in Table 4, surplus sludge collected from C food factory (pH 4.5, TS 1.8%, organic content 90%, polyiron sulfate 4% / TS), 18 ml of 0.2% polymer aqueous solution (this (The amount of the polymer flocculant added at the time of 1.0% / TS). Table 4 shows the test results.
From the results in Table 4, similar to the results in Tables 2 and 3, even in the case of high organic excess sludge that is relatively difficult to dewater, the example forms coarser particles than the comparative example, and high agitation. It was found that the floc once formed was hard to break (high floc strength), good filter cloth releasability, and high dewaterability (low cake moisture content) even under the lower (300 rpm).

  The polymer flocculant of the present invention is extremely useful as a polymer flocculant for sewage sludge or wastewater treatment, as well as a dispersant, a scale inhibitor, a coagulant, a decolorizing agent, a thickener, an antistatic agent, and a fiber. Treatment agents, etc., especially excavating, muddy water coagulants, papermaking agents (formation forming aids for the paper industry, drainage retention improvers, drainage improvers, paper strength enhancers, etc.), and additives for increasing crude oil production It is suitably used as (an additive for secondary and tertiary recovery of crude oil).

It is a floc particle size diagram for determining the magnitude | size of a floc.

Claims (10)

Compounds (a1) and (a1) represented by the following general formulas (1), (2), (3) and (4), and salts represented by the following general formulas (5), (6) and (7) At least one compound (a) selected from the group consisting of a compound (a2), a salt of (a2), and a polycondensate (a3) composed of (a2) and formaldehyde, and at least one of a water-soluble unsaturated monomer (b) A polymer coagulant comprising a (co) polymer obtained by (co) polymerizing at least one of (b) in the presence of one (co) polymer and / or (a) (A).
[Wherein, R ¹ is H or a hydrocarbon group having 1 to 20 carbon atoms; R ² and R ³ are a hydrocarbon group having 1 to 20 carbon atoms which may contain an O, N or S atom, or H; X is O, NR ⁴ or S; R ⁴ is a hydrocarbon group having 1 to 20 carbon atoms which may contain an O, N or S atom, or H. ]
[Wherein, R ⁵ is a direct bond or a hydrocarbon group having 1 to 20 carbon atoms; R ⁶ , R ⁷ , R ⁸ , and R ⁹ have 1 to 20 carbon atoms which may contain an O, N, or S atom. Or H. ]
[In the formula, R ¹⁰ is a hydrocarbon group having 1 to 20 carbon atoms; R ¹¹ is a hydrocarbon group having 1 to 20 carbon atoms, which may contain an O, N, or S atom, or H. ]
[Wherein, R ¹² is a hydrocarbon group having 1 to 20 carbon atoms; R ¹³ is a hydrocarbon group having 1 to 20 carbon atoms, which may contain an O, N, or S atom, or H]. ]
[Wherein, R ¹⁴ , R ¹⁵ , R ¹⁶ , and R ¹⁷ are a hydrocarbon group having 1 to 20 carbon atoms which may contain an O, N, or S atom, or H; X is O, NR ¹⁸ or S ; R ¹⁸ is O, N, or a hydrocarbon group carbon atoms which may contain 1 to 20 S atoms, or H. ]
[Wherein, R ¹⁹ is a hydrocarbon group having 1 to 20 carbon atoms which may contain an O, N or S atom; R ²⁰ and R ²¹ are carbon atoms which may contain an O, N or S atom. T is O, NR ²² , or S; R ²² is a hydrocarbon group having 1 to 20 carbon atoms which may contain an O, N, or S atom, or H It is. ]
[Wherein, R ²³ is a hydrocarbon group having 1 to 20 carbon atoms which may contain an O, N, or S atom; R ²⁴ is a hydrocarbon group having 1 to 2 carbon atoms which may contain an O, N, or S atom. Z is H, a hydrocarbon group having 1 to 20 carbon atoms, OR ²⁵ , NR ²⁶ R ²⁷ or SR ²⁸ ; R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ are O, N, Or a hydrocarbon group having 1 to 20 carbon atoms which may contain an S atom, or H. ] The polymer flocculant according to claim 1, wherein (b) is a water-soluble unsaturated monomer containing acrylamide in an amount of 49 mol% or less. 3. The polymer flocculant according to claim 1, wherein (b) is a water-soluble unsaturated monomer containing no acrylamide. The polymer flocculant according to any one of claims 1 to 3, wherein (a) is at least one compound selected from the group consisting of amidine, urea, guanidine and derivatives thereof. The polymer flocculant according to any one of claims 1 to 4, wherein (a) is 0.01% or more and 50% or less based on the weight of (b). (B) is (meth) acrylamide, N-vinylformamide, N, N-dimethylaminoethyl (meth) acrylate and salts thereof, (meth) acrylic acid and salts thereof, 2- (meth) acryloyloxyethanesulfone Acid, 2- (meth) acryloyloxypropanesulfonic acid, 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid and salts thereof, and a mixture thereof with (meth) acrylonitrile. The polymer flocculant according to any one of claims 1 to 5, which is at least one water-soluble unsaturated monomer. The polymer flocculant according to any one of claims 1 to 6, having an intrinsic viscosity (dl / g) of 1 or more and 40 or less measured at 30 ° C in a 1N aqueous solution of NaNO ₃ . A method for treating sewage sludge or wastewater, comprising adding the polymer flocculant according to any one of claims 1 to 7 to sewage sludge or wastewater to form flocs, and then performing solid-liquid separation. A papermaking agent or an additive for increasing crude oil production, comprising the polymer flocculant according to any one of claims 1 to 7. Compound (a1) represented by the following general formula (1), (2), (3) or (4), a salt of (a1), represented by the following general formula (5), (6) or (7) In the presence of at least one compound (a) selected from the group consisting of a compound (a2), a salt of (a2), and a polycondensate (a3) composed of (a2) and formaldehyde, and adjusting the pH of the monomer solution to 0. A method for producing a polymer flocculant (A), characterized in that at least one of the water-soluble unsaturated monomers (b) is (co) polymerized while maintaining at least 5.5 and at most 5.5.
[Wherein, R ¹ is H or a hydrocarbon group having 1 to 20 carbon atoms; R ² and R ³ are a hydrocarbon group having 1 to 20 carbon atoms which may contain an O, N or S atom, or H; X is O, NR ⁴ or S; R ⁴ is a hydrocarbon group having 1 to 20 carbon atoms which may contain an O, N or S atom, or H. ]
[Wherein, R ⁵ is a direct bond or a hydrocarbon group having 1 to 20 carbon atoms; R ⁶ , R ⁷ , R ⁸ , and R ⁹ have 1 to 20 carbon atoms which may contain an O, N, or S atom. Or H. ]
[In the formula, R ¹⁰ is a hydrocarbon group having 1 to 20 carbon atoms; R ¹¹ is a hydrocarbon group having 1 to 20 carbon atoms which may contain an O, N, or S atom, or H. ]
[Wherein, R ¹² is a hydrocarbon group having 1 to 20 carbon atoms; R ¹³ is a hydrocarbon group having 1 to 20 carbon atoms, which may contain an O, N, or S atom, or H]. ]
[Wherein, R ¹⁴ , R ¹⁵ , R ¹⁶ , and R ¹⁷ are a hydrocarbon group having 1 to 20 carbon atoms which may contain an O, N, or S atom, or H; X is O, NR ¹⁸ or S ; R ¹⁸ is O, N, or a hydrocarbon group carbon atoms which may contain 1 to 20 S atoms, or H. ]
[Wherein, R ¹⁹ is a hydrocarbon group having 1 to 20 carbon atoms which may contain an O, N or S atom; R ²⁰ and R ²¹ are carbon atoms which may contain an O, N or S atom. T is O, NR ²² , or S; R ²² is a hydrocarbon group having 1 to 20 carbon atoms which may contain an O, N, or S atom, or H It is. ]
[Wherein, R ²³ is a hydrocarbon group having 1 to 20 carbon atoms which may contain an O, N, or S atom; R ²⁴ is a hydrocarbon group having 1 to 2 carbon atoms which may contain an O, N, or S atom. Z is H, a hydrocarbon group having 1 to 20 carbon atoms, OR ²⁵ , NR ²⁶ R ²⁷ or SR ²⁸ ; R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ are O, N, Or a hydrocarbon group having 1 to 20 carbon atoms which may contain an S atom, or H. ]