JP2007117956A - Polymer flocculant - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer flocculant excellent in the function of imparting a high strength to a floc, the function of increasing the particle size of the floc, the function of decreasing the water content of dewatered cake and the like. <P>SOLUTION: The polymer flocculant comprises a (co)polymer (A) including as an essential constituent unit a monomer (a) represented by general formula (1) (CH<SB>2</SB>=CR<SP>1</SP>-CH<SB>2</SB>)<SB>2</SB>N<SP>+</SP>HR<SP>2</SP>Z<SP>-</SP>in the presence of (A), a water-soluble (co)polymer (B) other than the (co)polymer (A) made by polymerizing a monomer comprising a monomer (b) represented by general formula (2) CH<SB>2</SB>=CR<SP>3</SP>-CO-X-Q-N<SP>+</SP>R<SP>4</SP>R<SP>5</SP>R<SP>6</SP>Z<SP>-</SP>and a water-soluble copolymer (C) including amidine as an essential constituent unit. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a polymer flocculant used for treating organic or inorganic sludge or wastewater such as sewage or human waste (hereinafter abbreviated as sewage) or factory wastewater, and sludge or wastewater using the polymer flocculant. It relates to the processing method.

  Conventionally, as a polymer flocculant used for dehydration of organic sludge generated by treatment of sewage and the like, and inorganic sludge generated by treatment of factory wastewater, etc., a polymer of a tertiary salt or quaternized salt of diallylamine is used. (For example, refer to Patent Document 1), a copolymer of a tertiary salt or quaternized salt of diallylamine and a tertiary salt or quaternized salt of dialkylaminoethyl (meth) acrylate (for example, Patent Documents 2, 3) Are known).

JP 56-18611 (first page) JP 51-37986 A (first page) JP 63-242309 A (first page)

  However, with these polymer flocculants, when sludge or wastewater is treated, the floc particle size produced is small and the drainage is poor, the water content of the solid-liquid separated cake is high, and the belt press dehydrator or filter press dehydrator It was difficult to obtain a sufficient dehydration effect, for example, the filter cloth and sludge were not easily peelable when using.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have reached the present invention. That is, the present invention is represented by the general formula (2) in the presence of the (co) polymer (A) having the monomer (a) represented by the general formula (1) as an essential structural unit and (A). And a water-soluble (co) polymer (B) other than (A), and a water-soluble copolymer (C) having amidine as an essential constituent unit. Characteristic polymer flocculant

^{_{(CH 2 = CR 1 -CH 2}} ) 2 N + HR 2 · Z - (1)

^{_{CH 2 = CR 3 -CO-X}} -Q-N + R 4 R 5 R 6 · Z - (2)

Wherein R ¹ and R ³ are each independently H or a methyl group, R ² is H, a (meth) allyl group, an alkyl group having 1 to 16 carbon atoms or a hydroxyalkyl group having 2 to 4 carbon atoms, R ⁴ R ⁵ and R ⁶ are each independently H, an alkyl group having 1 to 16 carbon atoms or an aralkyl group; X is O or NH; Q is an alkylene group having 1 to 4 carbon atoms or a hydroxyalkylene group having 2 to 4 carbon atoms; Z ⁻ represents a counter anion. And the polymer flocculant or (A), (B) and (C) in combination and added to sludge or wastewater, mixed to form flocs and solid-liquid separation, or sludge or This is a wastewater treatment method.

The polymer flocculant of the present invention has the following effects.
(1) By adding and mixing to sludge or wastewater, a strong and large particle size floc is formed.
(2) Since the flocs once formed are not easily broken or redispersed, there is no recontamination during agglomeration or dehydration, and the stability and processing speed of the agglomeration or dehydration can be significantly improved.
(3) Since the formed flocs are dense and the moisture content of the cake after dehydration is low, the amount of waste generated and the incineration costs can be greatly reduced.
(4) The COD of the filtrate generated during the dehydration step can be reduced and the colored components can be removed.

[(Co) polymer (A)]
(A) in the present invention is a (co) polymer having the monomer (a) represented by the general formula (1) as an essential constituent unit.
In the general formula (1), R ¹ represents H or a methyl group, and H is preferable from the viewpoint of aggregation performance described later. R ² represents H, a (meth) allyl group, an alkyl group having 1 to 16 carbon atoms (hereinafter abbreviated as C), or a C2 to 4 hydroxyalkyl group [where (meth) allyl group is an allyl group and / or Or a methallyl group, and the same description is used hereafter.
In the case where R ² is an alkyl group, when C exceeds 16, the solubility in water becomes poor. When R ² is a hydroxyalkyl group, it is difficult to obtain C less than 2 or C greater than 4, and this is not preferable from an industrial viewpoint.

Examples of the C1-16 alkyl group in R ² include methyl group, ethyl group, n- and i-propyl group, n-, i-, sec- and t-butyl group, n-, i- and sec-. And t-amyl group and lauryl group. Examples of the C2-4 hydroxyalkyl group in R ² include CH ₂ CH ₂ OH, CH ₂ CH ₂ CH ₂ OH, and CH ₂ CH (CH ₂ OH) CH ₃ .
Among R ² , H and C2-4 hydroxyalkyl groups are preferred from the viewpoint of aggregation performance, more preferred are H, CH ₂ CH ₂ OH, CH ₂ CH ₂ CH ₂ OH, and particularly preferred are H and CH _2. CH ₂ OH, most preferably H.

Examples of Z ⁻ in the general formula (1) include the following anions.
Inorganic acids such as hydrohalic acids (eg HF, HCl, HBr and HI), sulfuric acid, nitric acid and phosphoric acid sulfates such as C1-30 sulfates [eg alkyl or alkenyl sulfates (eg methyl sulfate, ethyl sulfate) Lauryl sulfate, myristyl sulfate, palmityl sulfate, stearyl sulfate, oleyl sulfate, linole sulfate and cetyl sulfate) and higher alcohols (C10-20) ethylene oxide (hereinafter abbreviated as EO) 1-60 mol adduct sulfate]

Sulfonic acids such as C1-30 sulfonic acids [eg alkyl (C1-10) sulfonic acids (eg methyl sulfonic acid and ethyl sulfonic acid), alkylaryl (C7-30) sulfonic acids [alkylbenzene sulfonic acid, alkylphenol sulfonic acid and Alkyl naphthalene sulfonic acid], higher alkyl (C10-30) sulfonic acid, higher fatty acid ester (C10-30) sulfonic acid, higher alcohol ether (C10-30) sulfonic acid, sulfosuccinic acid ester, higher fatty acid amide (C10-30) Alkyl sulfonic acid, alkyl diphenyl ether sulfonic acid and alkylbenzimidazole sulfonic acid]

Phosphate esters, such as mono- and dialkyl (C1-30) phosphate esters, mono- and dialkenyl (C1-30) phosphate esters, (poly) oxyalkylenes [EO 1-60 mol addition and / or propylene oxide (hereinafter , Abbreviated as PO) 1-60 mol addition] alkyl (C1-30) ether phosphate ester, sugar phosphate ester (eg glucose-phosphate ester, glucoseamine phosphate ester, maltose-1-phosphate and sucrose phosphate) Esters) and glycerin phosphate (eg phosphatidic acid)

Phosphonic acids, eg C1-30 phosphonic acids [eg alkyl (C1-10) phosphonic acids (eg methylphosphonic acid and ethylphosphonic acid), alkylaryl (C7-30) phosphonic acids (eg alkylbenzene phosphonic acid and alkylphenol phosphonic acid) , Higher alkyl (C10-30) phosphonic acid]
Organic acids such as C1-30 carboxylic acids [eg formic acid, oxalic acid, acetic acid, propionic acid, maleic acid, fumaric acid and adipic acid]

Among these Z ⁻ , anion of sulfonic acid is preferable from the viewpoint of dehydration performance, and an anion of sulfuric acid, halogen (for example, Cl ⁻ and Br ⁻ ), sulfate ester (for example, alkyl and alkenyl sulfate) is more preferable, particularly preferred are sulfuric, Cl ^-, anions of methyl sulphate and ethyl sulphate, and most preferred is Cl ^- it is.

Examples of (a) include the following.
(A1) A salt of a secondary or tertiary amine containing two (meth) allyl groups (the counter anion is as exemplified above)
For example, a salt of a di (meth) allylamine and a di (meth) allylamine derivative [for example, N-methyldi (meth) allylamine, Nn-propyldi (meth) allylamine and N-β-hydroxyethyldi (meth) allylamine] (a2) A salt of a tertiary amine containing three (meth) allyl groups (the counter anion is as exemplified above)
For example, a salt of tri (meth) allylamine

  Of these, di (meth) allylamine, N-methyldi (meth) allylamine, and agglomeration performance (improvement of floc strength, increase of floc particle size and reduction of moisture content of dehydrated cake, the same shall apply hereinafter) are preferable. Tri (meth) allylamine salts, more preferred are the hydrochlorides and sulfates thereof, particularly preferred are di (meth) allylamine hydrochlorides, and most preferred are diallylamine hydrochlorides.

(A) has (a) as an essential constituent unit, but sulfur dioxide can be added as a monomer constituting (A) if necessary. Moreover, you may add other monomers other than (a) and sulfur dioxide as a monomer which comprises (A) if necessary.
The other monomer includes a monomer (b) represented by the following general formula (2), another water-soluble unsaturated monomer (c), and a water-insoluble monomer (d). The (b), (c) and (d) will be described later.

The lower limit of (a) based on the total number of moles of all monomers constituting (A) is preferably 50 mol% from the viewpoint of aggregation performance, more preferably 60 mol%, and the upper limit preferable from the viewpoint of aggregation performance is 99. 9 mol%, more preferably 99 mol%.
The proportion of sulfur dioxide is usually 50 mol% or less, the lower limit preferable from the viewpoint of aggregation performance is 0.05 mol%, more preferably 0.1 mol%, and the upper limit preferable from the viewpoint of increasing the molecular weight is 45 mol%, more preferably. 40 mol%; the proportion of monomer (b) is usually 50 mol% or less, preferably from 0 to 45 mol%, more preferably from 0 to 40 mol% from the viewpoint of aggregation performance; the proportion of monomer (c) is usually 50 mol% or less, preferably from 0 to 45 mol%, more preferably from 0 to 40 mol%, from the viewpoint of agglomeration performance; and the proportion of monomer (d) is usually 40 mol% or less to produce (co) polymer From the viewpoint of water solubility, it is preferably 0 to 30 mol%, more preferably 0 to 20 mol%.

Since (a) contains two or three (meth) allyl groups, it is generally known that it is easy to cyclize to a 5-membered or 6-membered ring structure at the time of polymerization. In the case where the polymerization is carried out without using the polymer, a crosslinked structure tends to be formed, which adversely affects the solubility in water. For this reason, from the viewpoint of solubility in water, (A) preferably contains, as a structural unit, a cyclic structure in which (a) is cyclized, and the polymer chain is more rigid due to the formation of the cyclic structure. This is also preferable from the viewpoint that it becomes easy to effectively act with sludge because it does not easily form a string in an aqueous solution. From such a viewpoint, the proportion of the structural unit (a) having a 5-membered or 6-membered ring structure is preferably 90 mol% or more, more preferably 95 to 100 mol%. The ratio of the ring structure can be calculated from the integrated value of the absorption peak corresponding to each repeating unit of the ¹³ C-NMR spectrum.

  The production method (A) is not particularly limited, and various radical polymerization methods such as aqueous solution polymerization, solution polymerization, reverse phase suspension polymerization, photopolymerization, precipitation polymerization, and reverse phase emulsion polymerization can be employed. Among these, aqueous solution polymerization and photopolymerization are preferable from an industrial viewpoint.

As aqueous solution polymerization, for example, the monomer other than (a) and, if necessary, (a) is dissolved in water (monomer concentration is usually 5 to 80% by weight, preferably 10 to 70% by weight), and a polymerization initiator is added thereto. Can be used by adding 0.01 to 30%, preferably 0.1 to 10% based on the total weight of the monomers and polymerizing at 0 to 100 ° C. (for example, Japanese Examined Patent Publication No. 62-5163).
Examples of the polymerization initiator include water-soluble azo compounds [for example, azobisamidinopropane (salt) [for example, 2,2′-azobis (2-methylpropionamidine) dihydrochloride], azobiscyanovaleric acid (salt), and 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] (salt)] and water-soluble peroxides (eg hydrogen peroxide, peracetic acid, t-butyl peroxide) Can be mentioned.

  As the photopolymerization, for example, (a) and, if necessary, the above-mentioned monomers other than (a) are dissolved in water and polymerized by irradiation with light having a wavelength of 300 to 500 nm (for example, Japanese Patent Publication No. 45-37033). Can be used.

As for the molecular weight of (A), the intrinsic viscosity (dl / g) measured at 30 ° C. in a 1N—NaNO ₃ aqueous solution is usually 0.01 or more, preferably 0.05 or more, more preferably 0.1 from the viewpoint of aggregation performance. These are usually 5 or less, preferably 3 or less, more preferably 2 or less from the same viewpoint.

[Water-soluble (co) polymer (B)]
(B) in the present invention is a water-soluble (co) heavy other than (A) obtained by polymerizing a monomer comprising the monomer (b) represented by the following general formula (2) in the presence of (A). It is a coalescence.
(B) includes one or more monomers selected from monomers (b) represented by general formula (2).

^{_{CH 2 = CR 3 -CO-X}} -Q-N + R 4 R 5 R 6 · Z - (2)

In the formula, R ³ is H or a methyl group, R ⁴ , R ⁵ and R ⁶ are each independently H, a C1-16 alkyl group or an aralkyl group, Q is a C1-4 alkylene group or a C2-4 hydroxyalkylene. The group, X and Z ⁻ are the same as those in the general formula (1).

C1-4 alkylene groups of Q include methylene, ethylene, n- and i-propylene, 1,2-, 1,3- and 2,3-butylene groups and tetramethylene groups; C2-4 The hydroxyalkylene groups include hydroxyethylene, 1- and 2-hydroxypropylene, 1-hydroxy-i-propylene, 1- and 2-hydroxytetramethylene, 2-hydroxymethylpropylene and 2-methyl-2-hydroxypropylene groups Is included.
Examples of the alkyl group for R ⁴ , R ^5, and R ⁶ include those exemplified above for R ² , and examples of the aralkyl group include benzyl and phenylethyl groups.

Examples of (b) include the following, and mixtures thereof.
Salt of (meth) acrylate [when X in general formula (2) is O] primary amino group-containing (meth) acrylate [C5-20, such as aminoethyl (meth) acrylate and aminopropyl (meth) acrylate], Secondary amino group-containing (meth) acrylate [C6-20, such as methylaminoethyl (meth) acrylate, methylaminopropyl (meth) acrylate and aminoethyl (meth) acrylate] and tertiary amino group-containing (meth) acrylate [C7 -20, for example, dimethylaminoethyl (meth) acrylate and dimethylaminopropyl (meth) acrylate], inorganic acid (same as above) salts, organic acid (same as above) salts and amine salts thereof as quaternizing agents ( For example, quaternization with methyl chloride, dimethyl sulfate and benzyl chloride) Quaternary ammonium salt

Salt of (meth) acrylamide compound [when X in general formula (2) is N] Primary amino group-containing (meth) acrylamide [C5-30, such as aminoethyl (meth) acrylamide and aminopropyl (meth) acrylamide] Secondary amino group-containing (meth) acrylamide [eg methylaminoethyl (meth) acrylamide and methylaminopropyl (meth) acrylamide] and tertiary amino group-containing (meth) acrylamide [eg dimethylaminoethyl (meth) acrylamide and dimethylamino Propyl (meth) acrylamide] inorganic acid (above) salt, organic acid (above) salt and quaternary ammonium salt obtained by quaternizing the above amine with a quaternizing agent (above)

Among these, a salt of (meth) acrylate in which X is O is preferable from the viewpoint of easy industrial production, and more preferable is that R ⁴ and R ⁵ are both CH ₃ and Z is Cl or 1 Dimethylaminoethyl (meth) acrylate hydrochloride or sulfate which is / 2SO ₄ , and quaternary ammonium salts obtained by quaternizing these amines (salts) with a quaternizing agent.

In addition, (B) may be copolymerized with other water-soluble unsaturated monomer (c) if necessary.
(C) includes the following (c1) to (c3) and mixtures thereof. Here, water-soluble means that the solubility in water at 20 ° C. (g / 100 g of water) is 1 or more.
(C1) Nonionic monomer The following, and mixtures thereof (c11) (Meth) acrylate Molecular weight of 100 or more and number average molecular weight [hereinafter abbreviated as Mn. The measurement is based on a gel permeation chromatography (GPC) method. ] 3,000 or less, for example, hydroxyl group-containing (meth) acrylate [for example, hydroxyethyl (meth) acrylate, diethylene glycol mono (meth) acrylate, polyethylene glycol (degree of polymerization 3 to 50) mono (meth) acrylate and (poly) glycerol (polymerization] Degree 1-10) mono (meth) acrylate] and 2-cyanoethyl (meth) acrylate (c12) (meth) acrylamide compound C3-30, such as (meth) acrylamide, N-methyl (meth) acrylamide, N-isopropyl (meth) ) Acrylamide and N-methylol (meth) acrylamide (c13) Nitrogen atom-containing vinyl monomers other than the above C3-30, for example, acrylonitrile, N-vinyl-2-pyrrolidone, N-vinylformamide, vinylimida Lumpur

(C2) Cationic monomer The following, salts thereof (for example, the inorganic acid, organic acid salt and quaternary ammonium salt), and mixtures thereof (c21) vinyl compound having an amino group C2-30, for example, vinylamine, Compounds having vinylaniline, (meth) allylamine, di (meth) allylamine, p-aminostyrene, 2-vinylpyridine, 3-vinylpiperidine, vinylpyrazine and vinylmorpholine (c22) amine imide groups C4-30, 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) acryl Imido and 1,1,1-trimethylamine (meth) acrylic De

(C3) Anionic monomer The following acids, salts thereof [for example, alkali metal (for example, lithium, sodium and potassium) salts, alkaline earth metal (for example, magnesium and calcium) salts, ammonium salts and amines (C1-20, for example, methyl) Amines, ethylamines and ethanolamines), and mixtures thereof

(C31) Unsaturated carboxylic acids Monocarboxylic acids [C3-30, such as (meth) acrylic acid, vinylbenzoic acid and allyl acetic acid] and poly (2-4) carboxylic acids [C4-30, such as (anhydrous) maleic acid, Fumaric acid and itaconic acid]

(C32) Unsaturated sulfonic acid Alkene sulfonic acid [C2-20, such as vinyl sulfonic acid and (meth) allyl sulfonic acid]; Unsaturated aromatic sulfonic acid [C6-20, such as styrene sulfonic acid and α-methylstyrene sulfonic acid Alkenyl and alkyl (C1-18) alkenyl esters of sulfocarboxylic acids (eg α-sulfoalkanoic acids and sulfosuccinic acids) [C3-20, eg methyl vinyl, propyl (meth) allyl and stearyl (meth) allyl sulfosuccinate And (meth) allylsulfolaurate]; sulfonic acid group-containing (meth) acrylate [C4-30, such as sulfoalkyl (C2-20) (meth) acrylate [for example, 2- (meth) acryloyloxyethanesulfonic acid, 2 -(Meth) acryloyl Xipropanesulfonic acid, 3- (meth) acryloyloxypropanesulfonic acid, 2- (meth) acryloyloxybutanesulfonic acid, 4- (meth) acryloyloxybutanesulfonic acid, 2- (meth) acryloyloxy-2,2- Dimethylethanesulfonic acid and p- (meth) acryloyloxymethylbenzenesulfonic acid]]; sulfonic acid group-containing (meth) acrylamide [C4-30, such as 2- (meth) acryloylaminoethanesulfonic acid, 2- (meth) acryloyl Aminopropanesulfonic acid, 3- (meth) acryloylaminopropanesulfonic acid, 2- (meth) acryloylaminobutanesulfonic acid, 4- (meth) acryloylaminobutanesulfonic acid, 2- (meth) acryloylamino-2,2- Dimethylethanesulfonic acid And p- (meth) acryloylaminomethylbenzenesulfonic acid]; and alkyl (C1-20) (meth) allylsulfosuccinic acid ester [eg methyl (meth) allylsulfosuccinic acid ester]
(C33) (meth) acryloyl polyoxyalkylene (C1-6) sulfate ester (meth) acryloyl polyoxyethylene (degree of polymerization 2-50) sulfate ester

  Among (c), (c11) and (c22) are preferable from the viewpoint of increasing the molecular weight of (B), and (c12), (c13), (c31), and (c32) are particularly preferable. Are (meth) acrylamide, acrylonitrile, N-vinylformamide, (meth) acrylic acid, (anhydrous) maleic acid, itaconic acid and alkali metal salts thereof, 2- (meth) acryloyloxyethanesulfonic acid, 2- (meth) ) Acryloyloxypropane sulfonic acid, 3- (meth) acryloyloxypropane sulfonic acid, 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid and alkali metal salts thereof.

In addition to the above (b) and (c), the monomer constituting the water-soluble (co) polymer (B) may further contain a water-insoluble monomer (d) as long as the effect of the present invention is not inhibited, if necessary. May be. Here, water-insoluble means that the solubility in water at 20 ° C. (g / 100 g of water) is less than 1.
(D) includes the following (d1) to (d6) and mixtures thereof.
(D1) C4-23 (cyclo) alkyl (meth) acrylate [C1-20 aliphatic and alicyclic alcohol (meth) acrylates [eg methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth)] Acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate and cyclohexyl (meth) acrylate]
(D2) C4-20 epoxy group-containing (meth) acrylate [eg glycidyl (meth) acrylate]]

(D3) Poly (degree of polymerization 2-50) propylene glycol [monoalkyl (C1-20)-, monocycloalkyl (C3-12)-or monophenyl ether] unsaturated carboxylic acid monoester [eg C1-20 mono (Meth) acrylic acid esters of all PO adducts [eg ω-methoxy-, ω-ethoxy-, ω-propoxy-, ω-butoxy-, ω-cyclohexoxy- and ω-phenoxypolypropylene glycol mono (meth) acrylates And (meth) acrylic acid monoesters of PO adducts of diols [e.g. ω-hydroxyethyl (poly) oxypropylene mono (meth) acrylate]]

(D4) C2-30 unsaturated hydrocarbon monomers [eg, ethylene, nonene, styrene and 1-methylstyrene]
(D5) Carboxylic acid (C2-20, eg acetic acid, octylic acid and lauric acid) esters of unsaturated alcohols [C2-8, eg vinyl alcohol and (meth) allyl alcohol] (eg vinyl acetate, vinyl octylate and lauric acid) vinyl)
(D6) Halogen-containing monomer (C2-8, such as vinyl chloride)
(D7) Nitrogen atom-containing vinyl monomer (C3-10, such as N-vinylsuccinimide and N-vinylcarbazole)

  Based on the total number of moles of all monomers constituting (B), the proportion of (b) is preferably 10 mol% or more, more preferably 20 mol% or more, particularly preferably 30 to 70 mol, from the viewpoint of aggregation performance. %; The proportion of (c) is usually 90 mol% or less, preferably from the viewpoint of agglomeration performance, preferably 80 mol% or less, more preferably 30 to 70 mol%; and the proportion of (d) is usually 40 mol% or less. From the viewpoint of solubility of (B) in water, it is preferably 0 to 20 mol%, more preferably 0 to 10 mol%.

The production method of (B) is not particularly limited, and for example, radical polymerization methods such as aqueous solution polymerization, reverse phase suspension polymerization, photopolymerization, precipitation polymerization, and reverse phase emulsion polymerization can be used. Of these, preferred from the industrial viewpoint are reversed-phase emulsion polymerization, and more preferred are aqueous solution polymerization and reversed-phase suspension polymerization.
As the aqueous solution polymerization, for example, a monomer aqueous solution is put in a container in which heat does not enter and exit from the outside, and adiabatic polymerization is performed (for example, Japanese Examined Patent Publication No. Sho 59-40843) and a monomer aqueous solution can be controlled from the outside. And a method of performing constant temperature polymerization (for example, JP-A No. 3-189000) can be used.

As the reverse phase suspension polymerization, for example, an aqueous solution of a water-soluble vinyl monomer is dispersed in a water-in-oil type polymerization using an oil-soluble polymer substance or a nonionic surfactant as a dispersion stabilizer (for example, JP-A-56-56). -53111).
Examples of the oil-soluble polymer substance include cellulose ether (molecular weight of 100 or more and Mn of 100,000 or less, such as ethyl cellulose and ethyl hydroxyethyl cellulose), a copolymer of alkene and α, β-unsaturated polycarboxylic acid (anhydride). Alternatively, a derivative thereof [a copolymer of 1-olefin and (anhydrous) maleic acid having a molecular weight of 100 or more and Mn of 100,000 or less, for example, C20 to 40] may be mentioned.
Nonionic surfactants include, for example, sucrose fatty acid esters (C13-100, such as sucrose distearate and sucrose tristearate), sorbitan fatty acid esters (C7-100, such as sorbitan monostearate and sorbitan monooleate) and poly Glycerin fatty acid ester (C6-100, for example, glyceryl monostearate) is mentioned.
The amount of oil-soluble polymer substance used is usually 0.1%, preferably 0.2%, more preferably 0.5%, and the upper limit is usually 10%, preferably based on the weight of the organic solvent used. Is 5%, more preferably 3%.
Examples of the dispersion medium (organic solvent) used include aliphatic hydrocarbons (C6-30, such as hexane, heptane and n-decane), alicyclic hydrocarbons (C6-30, such as cyclohexane and decalin), aromatics, and the like. Group hydrocarbons (C6-12, such as benzene, toluene and xylene) and the like.

Further, as the inverse emulsion polymerization, for example, a method of polymerizing an aqueous solution of a water-soluble vinyl monomer by using a surfactant to form a water-in-oil emulsion (for example, Japanese Patent No. 2676483 and Japanese Patent Laid-Open No. 9-208802). Publication) can be used.
Examples of the dispersion medium to be used include hydrocarbons [C6-30, such as paraffin (for example, n-paraffin and isoparaffin), mineral oil (for example, kerosene, light oil and medium oil), and synthetic oil) and mixtures thereof.
As the surfactant used for emulsification, known ones described in, for example, Japanese Patent No. 2676483 and Japanese Patent Application Laid-Open No. 9-208802 can be used, and among these, preferred from the viewpoint of emulsion stability. Are nonionic surfactants and combinations of nonionic surfactants with other ionic surfactants.

Nonionic surfactants include, for example, higher fatty acid esters (for example, sorbitan monostearate, sorbitan distearate, sorbitan monooleate and oleic acid sorbitan ester EO adduct), polyoxyethylene long chain alkyl ether (for example, lauryl alcohol polyester). Oxyethylene ethers and polyoxyethylene nonylphenyl ethers) and long chain alkyl alkanolamides such as N, N-dihydroxyethyllaurylamide.
The amount of these surfactants used is usually 0.05%, preferably 0.1%, more preferably 0.12%, and the upper limit is usually 1%, preferably 0, based on the weight of the dispersion medium. 0.5%, more preferably 0.25%.
In addition, when the water-in-oil emulsion is diluted with water and used, a phase inversion agent may be added to the water-in-oil emulsion in advance so that the water-in-oil emulsion is poured into water and phase inversion is performed quickly. As the phase inversion agent, a highly hydrophilic surfactant [for example, HLB (Hydrophile-Lipophile Balance, an index indicating a balance between hydrophilicity and lipophilicity, based on the Griffin's HLB theory) of 9 to 20] For example, cationic surfactants and / or nonionic surfactants described in Japanese Patent No. 2676483 and JP-A-9-208802 can be used.

Various radical polymerization initiators in the radical polymerization method, such as water-soluble azo compounds [for example, azobisamidinopropane (salt) [for example, 2,2′-azobis (2-methylpropionamidine) dihydrochloride] Azobiscyanovaleric acid (salt) and 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] (salt)], oil-soluble azo compounds (for example, azobiscyanovaleronitrile) Azobisisobutyronitrile and azobiscyclohexanecarbonitrile), water-soluble peroxides (eg hydrogen peroxide, peracetic acid and t-butyl peroxide), oil-soluble peroxides (eg benzoyl peroxide and cumene hydroxyperoxide) Oxides) and inorganic peroxides (eg ammonium persulfate and persulfate) Thorium), and the like.
The above peroxides may be used as a redox initiator in combination with a reducing agent, such as bisulfite (eg, sodium bisulfite, potassium bisulfite and ammonium bisulfite), reducing metal salts [eg, iron sulfate] (II)], tertiary amines [eg dimethylaminobenzoic acid (salt) and dimethylaminoethanol], amine complexes of transition metal salts [eg pentamethylenehexamine complex of cobalt (III) chloride and diethylenetriamine complex of copper (II) chloride And an organic reducing agent (for example, ascorbic acid). In addition, the azo compound, peroxide and redox initiator may be used alone or in combination of two or more initiators.

  From the viewpoint of obtaining an optimal molecular weight as (B), the amount of the radical polymerization initiator used is preferably 0.001 based on the total weight of (b) and (c) and (d) used as necessary. %, More preferably 0.005%, particularly preferably 0.01%, most preferably 0.02%, the preferred upper limit is 1%, more preferably 0.5%, particularly preferably 0.1%, most preferably Is 0.05%.

Moreover, you may use the chain transfer agent for radical polymerization as needed. The chain transfer agent for radical polymerization is not particularly limited. For example, a compound having one or more hydroxyl groups in the molecule [molecular weight of 32 or more and Mn of 50,000 or less, such as methanol, ethanol, isopropyl alcohol, ethylene glycol, propylene glycol. , Polyethylene glycol (molecular weight of 100 or more and Mn 50,000 or less) and polyethylene polypropylene glycol (molecular weight of 100 or more and Mn 50,000 or less)], compounds having one or more amino groups in the molecule [for example, ammonia and amine ( C1-30, such as methylamine, dimethylamine, triethylamine and propanolamine)] and compounds having one or more thiol groups in the molecule (described later).
Among these, a compound having one or more thiol groups in the molecule is preferable from the viewpoint of molecular weight control.

Compounds having a thiol group in the molecule include the following, mixtures thereof and salts thereof [alkali metal (for example, lithium, sodium and potassium) salts, alkaline earth metal (for example, magnesium and calcium) salts, ammonium salts, Amine (C1-20) salts and inorganic acids (eg hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid) salts].
-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), 1-thioglycerol, thioglycolic acid monoethanolamine, thiomaleic acid, cysteine and 2-mercaptoethylamine], cycloaliphatic thiols (C5-20, eg Cyclopentanethiol and cyclohexanethiol) and aromatic (aliphatic) thiols (C6-12, such as benzenethiol and benzyl mercaptan and thiosalicylic acid).

Polyvalent thiol dithiol [aliphatic (C2-40) dithiol (eg ethanedithiol, diethylenedithiol, triethylenedithiol, propanedithiol, 1,3- and 1,4-butanedithiol, 1,6-hexanedithiol, neopentane Dithiols, etc.), alicyclic (C5-20) dithiols (eg cyclopentanedithiol and cyclohexanedithiol) and aromatic (C6-16) dithiols (eg benzenedithiol, biphenyldithiol), trithiols (C3-20, eg thioglycerin) Is mentioned.

  From the viewpoint of obtaining an optimum molecular weight as (B), the amount used when using a chain transfer agent for radical polymerization is preferably 0.0001%, more preferably 0.0005%, based on the total weight of monomers. The upper limit is preferably 0.001%, most preferably 0.005%, and the upper limit is preferably 10%, more preferably 5%, particularly preferably 3%, and most preferably 1%.

The monomer concentration in the aqueous monomer solution in radical polymerization is usually 20% based on the total weight of the aqueous monomer solution in aqueous polymerization, preferably 25%, more preferably 30%, and particularly preferably 40% from the viewpoint of increasing the molecular weight. %, Most preferably 50%, the upper limit is usually 80%, preferably 75%, more preferably 70%, particularly preferably 65%, most preferably 60% from the viewpoint of controlling the polymerization temperature.
In the reverse phase suspension polymerization, the lower limit is usually 30%, preferably 40%, more preferably 45%, particularly preferably 50%, most preferably 55%, and the upper limit is usually 90%. From the viewpoint of control, it is preferably 85%, more preferably 80%, particularly preferably 78%, and most preferably 75%.
In the reverse phase emulsion polymerization, the lower limit is usually 10%, preferably 20% from the viewpoint of increasing the molecular weight, more preferably 30%, particularly preferably 40%, most preferably 55% or more, the upper limit is usually 90%, the polymerization temperature. From the viewpoint of control, it is preferably 80%, more preferably 75%, particularly preferably 70%, and most preferably 65%.

The amount of the dispersion medium used in the reverse phase suspension polymerization is preferably 25%, more preferably 40%, particularly preferably 65%, and the raw material cost based on the total weight of the aqueous monomer solution from the viewpoint of dispersion stability. From the viewpoint of yield, the upper limit is preferably 1,000%, more preferably 400%, and particularly preferably 200%.
The amount of the dispersion medium used in the inverse emulsion polymerization is preferably 20%, more preferably 30%, particularly preferably 40%, and the active ingredient content based on the total weight of the aqueous monomer solution from the viewpoint of the viscosity of the emulsion. Therefore, the preferable upper limit is 80%, more preferably 70%, and particularly preferably 60%.

  In aqueous solution polymerization, the lower limit is usually −10 ° C., and preferably 0 ° C., more preferably 5 ° C., particularly preferably 10 ° C., most preferably 15 ° C., and the upper limit is usually 50 ° C. From the viewpoint of preventing thermal degradation, the temperature is preferably 40 ° C, more preferably 30 ° C, particularly preferably 25 ° C, and most preferably 20 ° C. Further, during polymerization, the temperature may be adjusted by appropriately heating and cooling so as to keep a predetermined temperature constant (for example, a predetermined polymerization temperature ± 5 ° C.), or adiabatic polymerization may be performed in a glass heat insulating container or the like. . In the adiabatic polymerization, it is preferable to adjust the starting temperature so that the boiling point of water (100 ° C.) or higher is not exceeded due to the heat of polymerization.

The polymerization temperature in the reverse phase suspension polymerization is usually 10 ° C. at the lower limit, preferably 20 ° C. from the viewpoint of the polymerization rate, more preferably 30 ° C., particularly preferably 40 ° C., most preferably 50 ° C., and the upper limit is usually 95 ° C. From the viewpoint of preventing thermal degradation of the polymer, it is preferably 90 ° C., more preferably 80 ° C., particularly preferably 70 ° C., and most preferably 60 ° C.
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 added dropwise to the dispersion medium that has been previously 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, and preferably 1 to 10 hours from the viewpoint of productivity and temperature control.
In the reverse emulsion polymerization, the lower limit of the polymerization temperature is usually 0 ° C., preferably 5 ° C. from the viewpoint of polymerization rate, more preferably 10 ° C., particularly preferably 15 ° C., most preferably 20 ° C., and the upper limit is usually 95 ° C. From the viewpoint of preventing thermal deterioration, the temperature is preferably 90 ° C, more preferably 80 ° C, particularly preferably 70 ° C, and most preferably 55 ° C.
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 polymerization time can be confirmed to end when the exotherm is eliminated by polymerization, but from the viewpoint of completing the polymerization from 1 to 24 hours from the point of confirming the start of polymerization by normal exotherm, and reducing the residual monomer. , Preferably 2 to 12 hours. As in the case of reverse phase suspension polymerization, when the monomer is dropped at any time, it is preferable to carry out the polymerization for the above time after completion of the dropping.
The monomer concentration, polymerization temperature, and polymerization time can be appropriately adjusted depending on the monomer composition, polymerization method, initiator type, and the like.

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

The pH of the aqueous monomer solution during polymerization is not particularly limited, but is preferably 1 to 8, more preferably 2 to 7, particularly preferably 3 to 6. from the viewpoint of the polymerization rate and the solubility of the resulting water-soluble polymer. 5.
The pH adjuster used for adjusting the pH is not particularly limited. When the monomer aqueous solution is alkaline, an inorganic acid (for example, hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid), an inorganic solid acidic substance (for example, Acid sodium phosphate, acid sodium nitrate, ammonium chloride, ammonium sulfate, ammonium bisulfate and sulfamic acid) and organic acids (eg oxalic acid, succinic acid and malic acid), and inorganic alkaline substances (if the aqueous monomer solution is acidic) Examples include sodium hydroxide, potassium hydroxide and ammonia) and organic alkaline substances (eg guanidine). The pH is a value measured at room temperature (20 ° C.) for a stock solution of the monomer aqueous solution used in the polymerization.

  Further, (B) may be polymerized in advance by the above method and then polymer-modified. As the polymer modification reaction, for example, when a water-soluble unsaturated monomer (c) having a hydrolyzable functional group in its molecule such as acrylamide is used, a caustic alkali (for example, sodium hydroxide and potassium hydroxide) is used during or after polymerization. ) Or alkali carbonate (for example, sodium carbonate and potassium carbonate) to partially hydrolyze the amide group of monomer (c) (the hydrolysis rate is about 1 to 60 mol% based on the total moles of all monomers) ) To introduce a carboxyl group (for example, JP-A-56-16505), formaldehyde, dialkyl (C1-12) amine and halogenated (for example, chloride, bromide and iodide) alkyl (C1-12) (Eg methyl chloride and ethyl chloride) and partially cationized by the Mannich reaction And a method for forming an amidine ring in a molecule by a ring-closing reaction between a nitrile group such as acrylonitrile and an amino group obtained by hydrolysis of vinylformamide (for example, JP-A-5-192513) Is mentioned.

  Moreover, when using 2 or more types of water-soluble (co) polymer as (B), you may mix after superposing | polymerizing each beforehand, superposing | polymerizing one beforehand and adding and polymerizing at the time of the other superposition | polymerization May be.

  In the present invention (B), in the presence of (A), (b) and other monomers used as necessary [hereinafter referred to as a monomer comprising (b). ], Which is obtained by polymerizing a part or the whole amount of the monomer (b) in (A). That is, (B) includes, in addition to the graft polymer in which the monomer (b) is grafted to (A), the (co) polymer of the monomer (b) [the polymer of (b) and / or Or a copolymer of (b) and other monomers]. Hereinafter, a mixture of (A) and (B) obtained by polymerizing the monomer comprising (b) in the presence of (A) is abbreviated as (AB).

  In the method of polymerizing the monomer comprising (b) in the presence of (A), for example, (1) the aqueous solution of (A) or (A) and the aqueous solution of the monomer comprising (b) are preliminarily mixed and polymerized. (2) A method in which an aqueous solution of the monomer comprising (b) is dropped into the aqueous solution of (A) or (A) to polymerize, and (3) an aqueous solution of the monomer comprising (b) (A) or ( A method in which the aqueous solution of A) is dropped and polymerized is included. Among these, the method (1) is preferable from the viewpoint of introducing a uniform graft structure into (A) and exhibiting excellent coagulation performance, and more preferable is the aqueous solution (A) and (b). In this method, an aqueous solution of the monomer is mixed in advance and polymerized.

When the molecular weight of (AB) is expressed in terms of intrinsic viscosity (dl / g) measured at 30 ° C. in a 1N-NaNO ₃ aqueous solution from the viewpoint of aggregation performance, the lower limit is usually 1, and the aggregation performance (particularly increases in floc particle size) ) Is preferably 1.5, more preferably 2, particularly preferably 4, most preferably 6, the upper limit is usually 40, and from the viewpoint of agglomeration performance (especially improvement of floc strength), preferably 30, more preferably 20, particularly preferably 15, and most preferably 12.

［式中、Ｒ⁷、Ｒ⁸はそれぞれ独立にＨまたはメチル基、Ｚ^-は式（１）と同じである。］ [Water-soluble copolymer (C)]
(C) in the present invention is a water-soluble copolymer essentially comprising an amidine structural unit represented by the following general formula (3). Examples of the monomer capable of forming an amidine structural unit include a primary amino group-containing monomer and a cyano group-containing monomer, which will be described later. (C) is usually a copolymer of a primary amino group-containing monomer and a cyano group-containing monomer. Further, it can be obtained by reacting a primary amino group and a cyano group in the copolymer to form an amidine.
Moreover, you may copolymerize another monomer in the case of manufacture of (C). Examples of other monomers include the monomers exemplified in the above (A) and (B).

[Wherein, R ⁷ and R ⁸ are each independently H or a methyl group, and Z ⁻ is the same as in formula (1). ]

  The production method of (C) is not particularly limited, but generally has a primary amino group or an ethylenically unsaturated monomer having an amide group capable of forming a primary amino group by a conversion reaction and a cyano group. A copolymer with an ethylenically unsaturated monomer [C3 to 10, for example, (meth) acrylonitrile] is produced, and further, a primary amino group represented by the following formula (5) in the copolymer and the following It can be obtained by reacting with a cyano group represented by the formula (6) to form an amidine.

式中、Ｒ⁷、Ｒ⁸はそれぞれ独立にＨまたはメチル基、Ｒ⁹ はＨまたはＣ１〜４のアルキル基、Ｚ^-は式（１）と同じである。
該アミド基を有するエチレン性不飽和モノマーとしては、Ｎ−ビニルホルムアミド（Ｒ⁸ ＝Ｈ、Ｒ⁹ ＝Ｈ）、Ｎ−ビニルアセトアミド（Ｒ⁸ ＝Ｈ、Ｒ⁹ ＝ＣＨ₃）等が挙げられる。 The ethylenically unsaturated monomer having an amide group includes a general formula CH ₂ ═CR ⁸ —NHCOR ⁹ (wherein R ⁸ represents H or a methyl group, and R ⁹ represents a C1-4 alkyl group or H). The vinylamide compound represented by these is included. In the copolymer, the amide group in the formula (4) is easily converted into a primary amino group by hydrolysis or alcoholysis [formula (6)], and the primary amino group is further converted to an adjacent formula. (5) It reacts with the cyano group in it to be amidined.

In the formula, R ⁷ and R ⁸ are each independently H or a methyl group, R ⁹ is H or a C1-4 alkyl group, and Z ⁻ is the same as in formula (1).
Examples of the ethylenically unsaturated monomer having an amide group include N-vinylformamide (R ⁸ = H, R ⁹ = H), N-vinylacetamide (R ⁸ = H, R ⁹ = CH ₃ ) and the like.

  The copolymerization molar ratio of the ethylenically unsaturated monomer having an amide group and the ethylenically unsaturated monomer having a cyano group is usually 20:80 to 80:20, preferably 40:60 to 60: from the viewpoint of aggregation performance. 40.

As the copolymerization method, an ordinary radical polymerization method is used, and any of bulk polymerization, aqueous solution precipitation polymerization, suspension polymerization, emulsion polymerization and the like can be used. The monomer concentration in the case of polymerization in a solvent is usually 5 to 80% by weight, preferably 20 to 60% by weight.
As the polymerization initiator, the above-mentioned general radical polymerization initiator can be used. From the viewpoint of adjusting the molecular weight, an azo compound is preferred, and 2,2'-azobis-2-amidinopropane hydrochloride is more preferred. is there.
Moreover, a polymerization reaction is normally implemented at the temperature of 30-100 degreeC under inert gas stream. The obtained copolymer can be used as it is or diluted (that is, in the form of a solution or suspension) for the amidation reaction. In addition, the solvent can be removed and dried by a known method. After separating the coalescence as a solid, it can be subjected to an amidation reaction in a solid state.

  When the N-vinylamide compound represented by the above general formula is used as the ethylenically unsaturated monomer having a substituted amino group, the amidine reaction converts the substituted amino group of the copolymer to a primary amino group, The water-soluble copolymer (C) in the present invention can be produced by a two-step reaction in which the produced primary amino group and the adjacent cyano group are reacted to form an amidine structure. (C) can also be produced by a method in which the copolymer is heated in water or an alcohol solution in the presence of a strong acid to produce an amidine structure in one step. Even in this case, it is considered that the primary amino group is first formed as an intermediate structure.

  As specific conditions of the amidation reaction, for example, 0.9 to 5 times equivalent, preferably 1 to 3 times equivalent of strong acid (preferably hydrochloric acid) is usually added to the substituted amino group in the copolymer, Usually, it can be set as (C) by heating at 80-150 degreeC (preferably 90-120 degreeC) normally for 0.5 to 20 hours. In general, the larger the equivalent ratio of strong acid to substituted amino group and the higher the reaction temperature, the easier the amidination proceeds. Further, in the case of amidine formation, water of usually 10% or more, preferably 20% or more is present in the reaction system based on the weight of the copolymer used for the reaction.

Among the water-soluble copolymers (C) in the present invention, from the viewpoint of aggregation performance, the repeating unit represented by (3) is preferably 20 to 90 mol%, and the repeating unit represented by (4) is 0 to 0. 2 mol%, 0 to 70 mol% of the repeating unit represented by the above (5) and 0 to 70 mol% of the repeating unit represented by the above (6).
In addition, the molecular weight of (C) is usually 0.01 or more in terms of intrinsic viscosity (dl / g) measured at 30 ° C. in a 1N—NaNO ₃ aqueous solution, preferably 0.05 or more, more preferably 0 from the viewpoint of aggregation performance. .1 or more, usually 15 or less, preferably 12 or less, more preferably 10 or less from the same viewpoint.

The total of repeating units (3), (4), (5) and (6) in (C) is usually 50 equivalent% or more, and preferably 70 to 100 equivalent% from the viewpoint of aggregation performance. The equivalent ratio [(3) / (5)] of the amidine unit to the repeating unit (5) is usually 0.5 to 10, preferably 2 to 5 from the viewpoint of the aggregation performance, and is generally as many as possible. The unit (4) is preferably converted to the repeating unit (3) or (6).
The total of repeating units (3) and (6) in (C) is usually 40 equivalent% or more, and preferably 60 to 95 equivalent% from the same viewpoint as described above. The equivalent ratio [(3) / (6)] of the amidine unit and the repeating unit (6) is usually 0.5 to 10, and preferably 2 to 5 from the same viewpoint.
As described above, the amidine structure is formed by the reaction between the adjacent repeating unit (5) and the repeating unit (4) [or the repeating unit (6) generated therefrom). Therefore, the unreacted repeating unit (5) is usually used. Partially remains. Therefore, among (C), the total of repeating units (3) and (6) is preferably 60 to 95 equivalent%, and the total of repeating units (3), (4) and (6) is 90 equivalents. % Or more, preferably 97 equivalent% or more. Each composition ratio can be calculated from the integrated value of the absorption peak corresponding to each repeating unit of the ¹³ C-NMR spectrum.

（式中Ｒ⁷ 、Ｒ⁸ はＨまたはメチル基、Ｍ⁺ は陽イオンを表わす。） (C) may contain other repeating units in addition to the above repeating units. Examples of other repeating units include those represented by the following formulas (7) to (10).

(Wherein R ⁷ and R ⁸ represent H or a methyl group, and M ⁺ represents a cation.)

  Repeating units (7) and (8) are produced by hydrolysis of repeating unit (5). That is, when a copolymer of an ethylenically unsaturated monomer having a cyano group and an N-vinylamide compound is heated in the presence of a strong acid and water to form an amidine structure, a part of the cyano group in the copolymer is In the same manner, it is hydrolyzed to produce an amide group of the repeating unit (7) and a carboxyl group of the repeating unit (8).

It is estimated that the repeating unit (9) (lactam unit) is generated from the repeating units (6) and (7).
The content of the repeating unit represented by the formulas (7) to (9) in (C) is usually 10 equivalent% or less, and preferably 5 equivalent% or less from the viewpoint of aggregation performance.

[Polymer flocculant]
The polymer flocculant of the present invention is characterized by comprising the above (A), (B) and (C).
The ratio of (A) based on the total weight of (A), (B) and (C) is preferable from the viewpoints of aggregation performance and the effect of improving the clarification of the filtrate (for example, COD reduction and decolorization, the same shall apply hereinafter). The lower limit is 0.5%, more preferably 1%, particularly preferably 2%, most preferably 5%. From the viewpoint of aggregation performance, the preferable upper limit is 80%, more preferably 70%, particularly preferably 50%, most preferably The ratio of (B) is preferably 30%; from the viewpoint of flocculation performance, the preferred lower limit is 5%, more preferably 10%, particularly preferably 20%, most preferably 50%, flocculation performance and clarification of the filtrate. From the viewpoint of the effect of improving the property, the preferable upper limit is 99%, more preferably 95%, particularly preferably 90%, most preferably 85%; and the ratio (C) is an improvement in the coagulation performance and the clarification of the filtrate. Effect In this respect, the preferable lower limit is 1%, more preferably 3%, particularly preferably 5%, most preferably 10%. From the viewpoint of aggregation performance, the preferable upper limit is 80%, more preferably 60%, and particularly preferably 50%. And most preferably 30%.

  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 it does not inhibit the effects of the present invention. An additive selected from the group consisting of preservatives can be included.

Antifoaming agents include silicone-based (for example, dimethylpolysiloxane), mineral oil (for example, spindle oil and kerosene), C12-22 metal soap (for example, calcium stearate) and the like;
Chelating agents include C6-12 aminocarboxylic acids (eg ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylethylenediaminetriacetic acid, nitrilotriacetic acid and triethylenetetraminehexaacetic acid), polyvalent carboxylic acids (eg maleic acid, polyacrylic acid). Acid (Mn 1,000-10,000) and isoamylene-maleic acid copolymer (Mn 1,000-10,000)], C3-10 hydroxycarboxylic acids (eg citric acid, gluconic acid, lactic acid and malic acid), Condensed phosphoric acid (eg tripolyphosphoric acid and trimetaphosphoric acid) and their salts [eg alkali metal (eg sodium and potassium) salts, alkaline earth metal (eg calcium and magnesium) salts, ammonium salts, C1-2 Alkylamine (e.g. methylamine, ethylamine and octylamine) salts and alkanolamine C2-12 (e.g. mono -, di- - and triethanolamine) salts] and the like;

pH adjusters include caustic (eg caustic soda), amines (eg mono, di and triethanolamine), inorganic acids (salts) [eg inorganic acids (eg hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, sulfamic acid and carbonic acid) , And salts of these metals (eg, alkali metals and alkaline earth metals) (eg, sodium carbonate, potassium carbonate, sodium sulfate, sodium hydrogen sulfate and monosodium phosphate) and ammonium salts (eg, ammonium carbonate and ammonium sulfate)], organic Acids (salts) [eg organic acids (eg carboxylic acids, sulfonic acids and phenols) and their metal (same as above) salts (eg sodium acetate and sodium lactate) and ammonium salts (eg ammonium acetate and ammonium lactate)] etc. ;

As the surfactant, surfactants described in US Pat. No. 4,331,447, such as polyoxyethylene nonylphenyl ether, dioctyl sulfosuccinate soda and the like;
Examples of the anti-blocking agent include polyether-modified silicone oils such as polyethylene oxide-modified silicone and polyethylene oxide / polypropylene oxide-modified silicone;

Antioxidants include phenols [eg hydroquinone, methoxyhydroquinone, catechol, 2,6-di-t-butyl-p-cresol (BHT) and 2,2′-methylenebis (4-methyl-6-t-butylphenol). )], Sulfur-containing compounds [eg thiourea, tetramethylthiuram disulfide, dimethyldithiocarbamic acid and its salts [eg metal (same as above) and ammonium salts], sodium sulfite, sodium thiosulfate, 2-mercaptobenzothiazole and Salts thereof (same as above), dilauryl 3,3′-thiodipropionate (DLTDP) and distearyl 3,3′-thiodipropionate (DSTDP)], phosphorus-containing compounds [eg triphenyl phosphite, triethyl phosphite Fight, sodium phosphite , Sodium hypophosphite, triphenyl phosphite (TPP) and triisodecyl phosphite (TDP)] and nitrogenous compounds [amine systems such as octylated diphenylamine, Nn-butyl-p-aminophenol and N , N-diisopropyl-p-phenylenediamine), urea and guanidine (and the inorganic acid salt)] and the like;

Examples of ultraviolet absorbers include benzophenone (for example, 2-hydroxybenzophenone and 2,4-dihydroxybenzophenone), salicylate (for example, phenyl salicylate and 2,4-di-t-butylphenyl-3,5-di-t). -Butyl-4-hydroxybenzoate), benzotriazoles [eg (2'-hydroxyphenyl) benzotriazole and (2'-hydroxy-5'-methylphenyl) benzotriazole] and acrylics [eg ethyl-2-cyano- 3,3-diphenyl acrylate and methyl-2-carbomethoxy-3- (paramethoxybenzyl) acrylate] and the like;
Examples of the preservative include benzoic acid, p-hydroxybenzoic acid ester and sorbic acid.

These additives may be contained in any of (A), (B) and / or (C), or after (AB) and (C) are mixed to obtain a polymer flocculant (D). It may be added and contained. In addition, additives other than the anti-blocking agent may be preliminarily contained in the monomer aqueous solution before production of (A), (B) and / or (C) as long as the effects of the present invention are not impaired. .
The amount of the additive used is based on the total weight of (A), (B) and (C) when the additive is contained in (A), (B) and / or (C) or (D). The antifoaming agent is usually 5% or less, preferably 1 to 3%, the chelating agent is usually 30% or less, preferably 2 to 10%, the pH adjuster is usually 10% or less, preferably 1 to 5%, The surfactant and the anti-blocking agent are each usually 5% or less, preferably 1 to 3%, and the antioxidant, ultraviolet absorber and preservative are each usually 5% or less, preferably 0.1 to 2%.

Since the polymer flocculant of the present invention exhibits an unprecedented specific flocculation effect and a clarification improvement effect of filtrate, dehydration of organic sludge or inorganic sludge generated by treatment of sludge such as sewage or factory wastewater It can be used as a polymer flocculant for treatment, and is particularly suitably used for dehydration treatment of organic sludge.
In the case of organic sludge, the polymer flocculant of the present invention is (AB) from the viewpoint that the suspended particles have a relatively large size and the surface of the suspended particles is negatively charged in water. Is preferably a cationic water-soluble (co) polymer and / or an amphoteric water-soluble (co) polymer, and from the viewpoint that the above-mentioned effects that are the characteristics of the present invention can be further exhibited, ( AB) is an amphoteric water-soluble (co) polymer.
Here, the cationic water-soluble (co) polymer is a water-soluble (co) polymer having a cationic group in the molecule, that is, a water-soluble (co) polymer that exhibits cationic properties when dissolved in water. The amphoteric water-soluble (co) polymer is a water-soluble (co) polymer having a cationic group and an anionic group in the molecule, or a water-soluble (co) polymer having a cationic group in the molecule and a molecule. It is a mixture of water-soluble (co) polymers having an anionic group therein, that is, a water-soluble (co) polymer that exhibits cationic and anionic properties when dissolved in water. The cationicity or anionicity of these water-soluble (co) polymers in water can be evaluated using the colloid equivalent value (meq / g) as a guide. That is, the cationic group equivalent value in the cationic water-soluble (co) polymer can be determined as the cationic colloid equivalent value, and the cationic group equivalent value and the anionic group equivalent value in the amphoteric water-soluble (co) polymer. Can be determined as a cation colloid equivalent value and an anion colloid equivalent value, respectively.

Among the (AB) in the present invention, the cation colloid equivalent value (meq / g) when (AB) is a cationic water-soluble (co) polymer has a preferable lower limit of 0.1 from the viewpoint of aggregation performance, The upper limit is preferably 0.5, particularly preferably 1, most preferably 1.5, and from the same viewpoint, the upper limit is preferably 20, more preferably 12, particularly preferably 8, and most preferably 6.
In addition, among (AB) in the present invention, the cation colloid equivalent value (meq / g) when (AB) is an amphoteric water-soluble (co) polymer has a preferable lower limit of 1, from the same viewpoint as above. The upper limit is preferably 1.5, particularly preferably 2, and the upper limit is preferably 6, more preferably 5, and particularly preferably 4.5.
The preferred lower limit of the anion colloid equivalent value (meq / g) is -5, more preferably -4, particularly preferably -3, from the viewpoint of solubility of the polymer flocculant in water, and from the viewpoint of aggregation. The preferred upper limit is -0.1, more preferably -0.3, particularly preferably -0.5.
Further, the cation colloid equivalent value (meq / g) of (C) in the present invention is preferably 1 from the viewpoint of aggregation performance, more preferably 2, particularly preferably 3, most preferably 4, and the same viewpoint. Therefore, the upper limit is preferably 20, more preferably 12, particularly preferably 10, and most preferably 8.

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) A sample 0.2 g (converted to solid content) is precisely weighed and taken in a 200 ml Erlenmeyer flask, and the total weight (total weight of sample and ion-exchanged water) is After adding ion-exchanged water so that it may become 100 g, it stirs for 3 hours with a magnetic stirrer (1,000 rpm), and melt | dissolves completely, and a 0.2 weight% polymer flocculant solution is prepared. Further, 10.00 g of the prepared solution was accurately weighed into a 500 ml glass beaker using a balance capable of measuring to the second decimal place, and the total weight (total weight of 10 ml of solution and ion-exchanged water) was 400. Add ion-exchanged water to 0.000 g, and stir again with a magnetic stirrer (1,000 to 1,200 rpm) for 30 minutes to obtain a uniform measurement sample.
The solid content of the polymer flocculant is the residual weight after weighing about 1.0 g of sample in a petri dish (W1) and drying at 105 ± 5 ° C. for 90 minutes in a circulating drier (W2). Is a value calculated from the following equation.

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

(2) Measurement of cation colloid equivalent value 100.0 g of a measurement sample is placed in a 200 ml glass conical beaker, and a 0.5% by weight sulfuric acid aqueous solution is gradually added to adjust to pH 3 while stirring. 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 from blue to magenta and is held for 30 seconds.
(3) Measurement of anion colloid equivalent value 100.0 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 while stirring with a magnetic stirrer (500 rpm). After adding 5 ml of 200 methyl glycol chitosan aqueous solution using a 5 ml whole pipette, it is stirred for 5 minutes (pH at that time 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 100.0 g of ion-exchanged water is used instead of the measurement sample.
(5) Calculation method Cation or anion colloid equivalent value (meq / g) = 1/2 × (sample titration-blank titration) × (N / 400 PVSK titer)

  The form of the polymer flocculant of the present invention may be any known form such as powder (for example, crushed, true spherical and kitchen), film, aqueous solution, w / o emulsion, and suspension.

The sludge or wastewater treatment method of the present invention is a floc obtained by adding the polymer flocculant of the present invention or (A), (B) [or (AB)] and (C) to the sludge or wastewater and mixing them. There is no particular limitation as long as it is a method in which solid-liquid separation is performed.
Among the above treatment methods, (1) is preferable from the viewpoint of the effects of the present invention (for example, high floc strength, increase in floc particle size, low water content of dehydrated cake, COD reduction and decolorization effect of filtrate). (AB) and (C) are mixed in advance to obtain a polymer flocculant (D), and then (D) is added to and mixed with sludge or wastewater to form a floc and solid-liquid separation, (2 ) (AB) added to and mixed with sludge or wastewater, then (C) is added and mixed to form a floc and solid-liquid separation, and (3) (C) is added to sludge or wastewater. Then, after mixing, (AB) is further added and mixed to form a floc, and solid-liquid separation is performed. More preferred is the method (1) and (3), and particularly preferred is (1). It is a method. In addition, when (AB), (C), or (D) is added to sludge or wastewater, it is preferable that all of these are previously in the form of an aqueous solution from the viewpoint of uniform mixing.

  Further, when (AB), (C) or (D) is used in sludge or wastewater, one or more known inorganic and organic coagulants may be used in combination. When these are used in combination, (i) (A), (B), (AB), (C) and / or (D) in advance, (ii) (A), (B), A method of adding (AB), (C) and / or (D) at the same time, (iii) adding an inorganic coagulant and / or an organic coagulant to (A), (B), (AB), (C) and In addition to (D), any of the methods of adding to sludge or wastewater in any order before and / or after the addition thereof may be employed. Among these, the method of adding an inorganic coagulant and / or an organic coagulant among (iii) to sludge or waste water is preferable from the viewpoint of coagulation performance.

Examples of the inorganic coagulant include sulfate band, polyaluminum chloride, ferric chloride, ferric sulfate, polyiron sulfate and slaked lime.
Examples of organic coagulants include polycondensates of epihalohydrin and amine (or its hydrochloride, hereinafter abbreviated as hydrochloride), polycondensates of epihalohydrin and alkylenediamine (hydrochloride), polyethyleneimine (hydrochloride), alkyl, and the like. Range halide-alkylene polyamine polycondensate (hydrochloride), aniline-formaldehyde polycondensate (hydrochloride), polyvinylbenzyltrimethylammonium chloride, polyvinylpyridine (hydrochloride), (di) methyldi (meth) allylammonium chloride and polyvinylimidazoline (Hydrochloride).
These inorganic coagulants and organic coagulants may be used singly or in combination, or both may be used in combination.

  When the coagulant is added to (A), (B), (AB), (C) and / or (D) in advance, the amount used is (A), (B), (AB), ( Based on the weight of C) and / or (D), the inorganic coagulant is usually 100% or less, preferably from 5 to 50%, more preferably from 10 to 30%, and the organic coagulant is usually 20% from the viewpoint of agglomeration performance. Hereafter, from the same viewpoint, it is preferably 1 to 10%, more preferably 2 to 5%.

  When adding an inorganic coagulant and / or an organic coagulant to sludge or waste water separately from (A), (B), (AB), (C) and / or (D) [method (iii) above] The amount of inorganic coagulant and / or organic coagulant used depends on the type of sludge or wastewater, the size of suspended particles, and the TS in the sludge or wastewater, but based on the TS in the sludge or wastewater. In the case of an inorganic coagulant, the lower limit is preferably 0.5%, more preferably 1%, particularly preferably 2% from the viewpoint of cohesiveness, and the upper limit is preferably 10%, more preferably 8%, particularly preferably from the same viewpoint. In the case of an organic coagulant, the lower limit is preferably 0.01%, more preferably 0.05%, particularly preferably 0.1% from the viewpoint of cohesion, and the upper limit is preferably 5% or less from the same viewpoint. More Preferably 3% or less, particularly preferably 1%.

In the above method (3), as a method for adding (C) to sludge or wastewater, it is preferable to add (C) to an aqueous solution and then add it to sludge or wastewater and sufficiently stir from the viewpoint of uniform mixing. , (C) may be directly added to sludge or wastewater and stirred and mixed. When (C) is used as an aqueous solution, the concentration of (C) is preferably 0.01 to 5% by weight, more preferably 0.1 to 1% by weight, from the viewpoint of mixing with sludge or wastewater.
Although the dissolution method of (C) and the dilution method after dissolution are not particularly limited, for example, a predetermined amount of (C) is added while stirring water using a stirrer such as a jar tester, and several A method of stirring and dissolving for a time (about 1 to 4 hours) can be employed.

  The amount of (C) used in the method (3) varies depending on the type of sludge or waste water, the content of suspended particles, the molecular weight of (C), etc., and is not particularly limited. Based on the weight of evaporation residue (hereinafter abbreviated as TS), the lower limit is preferably 0.01%, more preferably 0.05%, particularly preferably 0.1%, from the viewpoint of the effect of improving the clarity of the filtrate. Most preferably, it is 0.2%, and the upper limit is preferably 10%, more preferably 8%, particularly preferably 5%, and most preferably 2% from the viewpoint of aggregation performance.

In the method (3), (AB) is added to the sludge or wastewater treated in (C) without any particular limitation, and (AB) may be added to the sludge or wastewater as it is. From the viewpoint of uniform mixing, a method in which (AB) is made into an aqueous solution and then added to the sludge or wastewater is preferred. When (AB) is used as an aqueous solution, the concentration of (AB) is preferably 0.05 to 1% by weight, more preferably 0.1 to 0.5% by weight from the viewpoint of mixing with sludge or wastewater. .
The dissolution method and the dilution method after dissolution are not particularly limited and are the same as in the case of (C) above. In particular, when (AB) in powder form is dissolved in water, adding (AB) at a time is not preferable because it causes dents and makes it difficult to dissolve in water.

  In the method (3), the amount of (AB) used when added to sludge or wastewater varies depending on the type of sludge or wastewater, the content of suspended particles, the molecular weight of (AB), etc. and is not particularly limited. However, from the viewpoint of flocculation performance based on TS in sludge or wastewater, the preferable lower limit is 0.01%, more preferably 0.1%, particularly preferably 1%, most preferably 1.5%, the same viewpoint. Therefore, the preferable upper limit is 10%, more preferably 8%, particularly preferably 5%, and most preferably 3%.

  Further, the method for adding the polymer flocculant (D) or (AB) to the sludge or waste water in the method (1) or (2) is not particularly limited, and (D) or (AB) is directly treated as sewage. However, from the viewpoint of uniform mixing, the method of adding (D) or (AB) to an aqueous solution and then adding it to sludge or wastewater is preferable. When (D) or (AB) is used as an aqueous solution, the concentration is preferably 0.05 to 3% by weight, more preferably 0.1 to 1% by weight. The dissolution method and the dilution method after dissolution are not particularly limited, and are the same as in the case of (C) and (AB) in the above method (3).

The amount of (AB) used when added to sludge or wastewater in the method of (1) or (2) depends on the type of sludge or wastewater, the content of suspended particles, the molecular weight of the polymer flocculant, etc. Although not particularly limited, the lower limit is preferably 0.01%, more preferably 0.1%, particularly preferably 1%, and most preferably 1.% from the viewpoint of coagulation performance based on the TS in sludge or wastewater. From the same viewpoint, the upper limit is preferably 10%, more preferably 8%, particularly preferably 5%, and most preferably 3%.
In the method (2), (AB) is added to and mixed with sludge or wastewater, and then the amount of (C) used when (C) is added and mixed is the same as in the method (3).
In addition, the amount of (C) used as (D) in the method (1) is the same as in the method (2) or (3).

  Moreover, as a dehydration method (solid-liquid separation method) of floc sludge formed by the processing method of (1), (2) or (3) above, for example, gravity sedimentation, membrane filtration, column filtration, pressurized flotation, And a method using a concentrator (eg, thickener) and a dehydrator (eg, centrifugal dehydrator, belt press dehydrator, filter press dehydrator and capillary dehydrator). Among these, preferred from the viewpoint of high floc strength, which is the specific aggregation performance of the polymer flocculant of the present invention, is a method using a dehydrator, particularly a centrifugal dehydrator, a belt press dehydrator and a filter press dehydrator. .

  Other uses of the polymer flocculant of the present invention include, for example, a flocculant for excavation and muddy water treatment, a papermaking agent (for example, a formation aid for paper industry, drainage yield improver, drainage improver and paper strength Enhancing agents), crude oil production additives (crude oil secondary and tertiary recovery additives), dispersants, scale inhibitors, coagulants, decoloring agents, thickeners, antistatic agents and textile treatment agents, Of these, preferred are a flocculant for excavation and muddy water treatment, a papermaking agent, and an additive for increasing crude oil production from the viewpoint of the effect to be obtained.

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,% in an Example shows weight% and a copolymerization ratio represents molar ratio.
The intrinsic viscosity [η] (dl / g) is a value measured at 30 ° C. in a 1N—NaNO ₃ aqueous solution. The colloidal equivalent value and solid content of the polymer flocculant were measured by the methods described above.
In addition, TS (evaporation residue) and organic content (ignition loss) in sludge or wastewater were performed according to the analysis method described in the sewer test method (Japan Sewerage Association, 1984 version).
The floc particle size, filtrate amount, filter cloth peelability, cake moisture content, COD and filtrate clarification in this example were carried out according to the following methods.

<Flock particle size>
Jar tester [Miyamoto Riken Kogyo Co., Ltd., Model JMD-6HS-A] and two plate-like PVC stirring blades (diameter 5 cm, height 2 cm, thickness 0.2 cm) up and down to form a cross It was continuously attached to a stirring bar, and 200 ml of sludge or waste water was taken in a 500 ml beaker and set in a jar tester. While rotating the jar tester at 120 rpm and slowly stirring the sludge or wastewater, a predetermined amount of 0.2% by weight of the polymer flocculant aqueous solution was added all at once, and stirred for 30 seconds. The size was visually observed (the floc particle size at a rotational speed of 120 rpm is shown in the table).
Subsequently, the number of revolutions was set to 300 rpm, and further stirred for 30 seconds. Then, the stirring was stopped and the size of the aggregate was visually observed again (the floc particle size at the number of revolutions of 300 rpm is shown in the table).

<Amount of filtrate>
T-1189 nylon filter cloth [Shikishima Kanbusu Co., Ltd., circular shape, diameter 9 cm], Nutsche funnel, graduated cylinder that can measure 300 ml, set sludge after the above floc particle size test and filter at once Then, using a stopwatch, the amount of filtrate after 60 seconds from immediately after the addition was measured to evaluate the treatment speed.
<Filter cloth peelability>
Part of the filtered sludge is removed with a spatula and 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 according to the following criteria: did.
A: Very easy to peel off (almost no filter cloth deposits)
○: Easy to peel off (Slightly attached filter cloth)
Δ: Slightly difficult to peel off (there is a filter cloth deposit, slightly sticking to the inside of the filter cloth)
×: Hard to peel off (attaches to the inside of the filter cloth)

<Moisture content of cake>
About 3.0 g of the dehydrated cake after the filter cloth peelability test is weighed into a petri dish (W3) and dried in a circulating drier until the water has completely evaporated (for example, at 105 ± 5 ° C. for 8 hours). Thereafter, the weight of the dry cake remaining on the petri dish was defined as (W4), and the moisture content of the cake was calculated from the following formula.

Cake moisture content (% by weight) = {(W3) − (W4)} × 100 / (W3)

<COD>
Using the filtrate after measuring the filtrate amount, COD was measured according to the COD _Mn analysis method described in JIS K-0102 (1998 version).
<Filtrate clarity>
Using the filtrate after the filtrate amount measurement, absorbance at wavelengths of 590 nm and 700 nm was measured with an absorptiometer [manufactured by Shimadzu Corporation, UV-1200]. The numerical value (%) of absorbance indicates a value when the absorbance of ion-exchanged water is 100%.

Production Example 1
In an autoclave equipped with a stirrer, a temperature sensor, and a temperature controller, 230 parts of water and 76 parts of 35% hydrochloric acid were charged, and 72 parts of diallylamine was gradually added dropwise while cooling to obtain a diallyl ammonium chloride aqueous solution. Next, after sufficiently replacing the system with nitrogen (purity 99.999% or more), 18 parts of anhydrous sodium bisulfite and 18 parts of 35% hydrochloric acid were charged to generate sulfur dioxide in the system. -29.2 parts of a 10% aqueous solution of azobis (2-methylpropionamidine) dihydrochloride was added with stirring. The inside of the system was gradually heated from the outside, and polymerization started at 50 ° C., and heat generation was observed. Thereafter, the mixture was heated from the outside and aged at 80 ° C. for 1 hour to complete the polymerization. After completion of the polymerization, the content was taken out, 2,000 parts of acetone was added thereto, and the mixture was stirred for 30 minutes with a commercially available juicer mixer to obtain a precipitate. After the precipitate was taken out by vacuum filtration (using JIS standard 2 types of filter paper), the solvent was distilled off in a vacuum dryer (vacuum degree 1.3 kPa, 40 ° C. × 2 hours) to form a powder. 108 parts of a copolymer [A1] was obtained (yield 93%, solid content 95%). The ratio of the 5-membered or 6-membered ring structure in the polymerized diallylammonium chloride in [A1] was 100 mol% as a result of calculation from the integrated value of the absorption peak of the corresponding ¹³ C-NMR spectrum.

Production Example 2
In a Kolben equipped with a stirrer, a temperature sensor and a temperature control device, 970 parts of methyldiallylammonium chloride crystals are placed, and 163 parts of sulfur dioxide is added thereto while cooling from the outside so that the inside of the system becomes 20 to 80 ° C. I gradually blown in. With the exotherm, sulfur dioxide was absorbed by methyldiallylammonium chloride to obtain a liquid mixture. Next, 100 parts of this mixture was placed in a transparent polyethylene bag having a thickness of 0.1 mm and spread on a flat plate having a thickness of about 3 mm and a length and width of 5 cm each. This was placed at a position 10 cm immediately below the center of a fluorescent lamp (40 W, length 120 cm) having a wavelength distribution of 300 to 450 nm and irradiated for 3 hours. Immediately after irradiation, polymerization started with exotherm and the whole solidified. After the polymerization, the content was taken out and thereafter treated in the same manner as in Production Example 1 to obtain 97 parts of a powdery copolymer [A2] (yield 97%, solid content 99%). The ratio of the 5-membered or 6-membered ring structure in the polymerized methyldiallylammonium chloride in [A2] was 100 mol% as a result of calculation from the integrated value of the absorption peak of the corresponding ¹³ C-NMR spectrum.

Production Example 3
A four-necked flask equipped with a stirrer, temperature sensor, temperature controller, nitrogen inlet tube and condenser tube was charged with 34.4 parts of acrylonitrile, 25.6 parts of N-vinylformamide, and 340.0 parts of ion-exchanged water. It is.
The temperature was raised to 60 ° C. with stirring in a nitrogen gas stream, and 1.2 parts of a 10% 2,2′-azobis-2-amidinopropane dihydrochloride aqueous solution was added. The liquid temperature was lowered to 45 ° C. and stirring was continued for 4 hours, then the temperature was raised to 60 ° C. and stirring was further continued for 3 hours to obtain a suspension in which a polymer was precipitated in water. 200 parts of water was added to the suspension, and then 2 equivalents of concentrated hydrochloric acid was added to the formyl group in the polymer and maintained at 100 ° C. for 4 hours with stirring to amidinate the polymer. . The obtained polymer solution was added to acetone for precipitation, and this was vacuum dried to obtain a solid water-soluble polymer [C1]. [C1] had an intrinsic viscosity of 3.8 dl / g and a colloid equivalent value of 5.6 meq / g. The ratio of the repeating unit or functional group in [C1] was calculated from the integrated value of the absorption peak of the corresponding ¹³ C-NMR spectrum, and the following result was obtained (unit is equivalent%). [Amidine unit] = 54, [Formyl group] = 0, [Cyano group] = 23, [Amino group] = 23, [Amido group], [Carboxyl group] and [Lactam unit] = 0

Comparative production example 1
In a Kolben equipped with a stirrer, 115 parts (100 mol%) of an 80% aqueous solution of methyl chloride quaternary ammonium salt of N, N-dimethylaminoethyl methacrylate was added, and the total amount of monomers in the system was 30%. 192 parts of ion exchange water was added and stirred until the inside of the system became a uniform solution. While further stirring, the pH of the monomer aqueous solution (20 ° C.) was adjusted to 4.0 using sulfuric acid while monitoring with a pH meter. Next, the temperature of the solution was adjusted to 40 ° C. in a constant temperature bath at 40 ° C., and the system was sufficiently substituted with nitrogen (purity 99.999% or more) (gas phase oxygen concentration 10 ppm or less). Next, 0.46 part of a 10% aqueous solution of 2,2′-azobis (2-methylpropionamidine) dihydrochloride as an initiator was added all at once with stirring. After about 1 minute, polymerization started and exotherm was observed, but the mixture was cooled from the outside and polymerized at a content temperature of 40 to 50 ° C. for 10 hours. Thereafter, the mixture was heated from the outside and aged at 70 ° C. for 1 hour to complete the polymerization. During the polymerization, the content became highly viscous and stirring became difficult, so stirring was stopped halfway. After the completion of the polymerization, the contents were taken out, and then treated in the same manner as in Production Example 1 to obtain 95 parts of a powdery water-soluble polymer [X1] (yield 98%, solid content 95%).

Comparative production example 2
In Comparative Production Example 1, instead of 115 parts of 80% aqueous solution of methyl chloride quaternary ammonium salt of N, N-dimethylaminoethyl methacrylate, 80% aqueous solution of methyl chloride quaternary ammonium salt of N, N-dimethylaminoethyl acrylate 97 parts of a powdery water-soluble polymer [X2] was obtained in the same manner as in Comparative Production Example 1 except that 74 parts (40 mol%) and 65 parts (60 mol%) of a 50% aqueous solution of acrylamide were used. (Yield 98%, solid content 93%).

Comparative production example 3
In Comparative Production Example 1, instead of 115 parts of an 80% aqueous solution of methyl chloride quaternary ammonium salt of N, N-dimethylaminoethyl methacrylate, 10 parts (5 mol%) of the aqueous solution, N, N-dimethylaminoethyl acrylate Comparative Example 1 except that 58 parts (30 mol%) of an 80% aqueous solution of methyl chloride, 51 parts (45 mol%) of a 50% aqueous solution of acrylamide and 12 parts (20 mol%) of acrylic acid were used. Thus, 95 parts of a powdery water-soluble polymer [X3] was obtained (yield 96%, solid content 93%).

Table 1 shows the contents of (A1), (A2), (C1), and (X1) to (X3) obtained above.

Example 1
In Comparative Production Example 1, instead of 115 parts of an 80% aqueous solution of methyl chloride quaternary ammonium salt of N, N-dimethylaminoethyl methacrylate, 113 parts (100 mol%) of the aqueous solution and 33 parts of a 30% aqueous solution of [A1] In the same manner as in Comparative Production Example 1 except that was used, 105 parts of a powdery water-soluble polymer [AB1] was obtained (yield 99%, solid content 95%). 80 parts of [AB1] and 20 parts of [C1] were put in a glass bottle capable of being sealed and shaken well until uniform to obtain 100 parts of a polymer flocculant [D1].

Example 2
In Comparative Production Example 1, instead of 115 parts of an 80% aqueous solution of methyl chloride quaternary ammonium salt of N, N-dimethylaminoethyl methacrylate, 113 parts (100 mol%) of the aqueous solution and 33 parts of a 30% aqueous solution of [A2] In the same manner as in Comparative Production Example 1 except that was used, 105 parts of a powdered water-soluble polymer [AB2] was obtained (yield 99%, solid content 95%). 75 parts of [AB2] and 25 parts of [C1] were placed in a glass bottle capable of being sealed and shaken well until uniform to obtain 100 parts of a polymer flocculant [D2].

Example 3
In Comparative Production Example 1, instead of 115 parts of 80% aqueous solution of methyl chloride quaternary ammonium salt of N, N-dimethylaminoethyl methacrylate, 73 parts of 80% aqueous solution of methyl chloride salt of N, N-dimethylaminoethyl acrylate (40 Mol%), 64 parts (60 mol%) of a 50% aqueous solution of acrylamide, and 33 parts of a 30% aqueous solution of [A2], in the same manner as in Comparative Production Example 1, [AB3 ] 106 parts were obtained (yield 98%, solid content 93%). 85 parts of [AB3] and 15 parts of [C1] were put in a glass bottle capable of being sealed and shaken well until uniform to obtain 100 parts of a polymer flocculant [D3].

Example 4
In Comparative Production Example 1, instead of 115 parts of an 80% aqueous solution of methyl chloride quaternary ammonium salt of N, N-dimethylaminoethyl methacrylate, 10 parts (5 mol%) of the aqueous solution was added to the N, N-dimethylaminoethyl acrylate. 57 parts (30 mol%) of an 80% aqueous solution of methyl chloride salt, 50 parts (45 mol%) of a 50% aqueous solution of acrylamide and 11 parts (20 mol%) of acrylic acid and 33 parts of a 30% aqueous solution of [A2] were used. Except for the above, in the same manner as in Comparative Production Example 1, 103 parts of a powdered water-soluble polymer [AB4] was obtained (yield 96%, solid content 93%). 70 parts of [AB4] and 30 parts of [C1] were put in a glass bottle capable of being sealed and shaken well until uniform to obtain 100 parts of a polymer flocculant [D4].

Table 2 shows the contents of (D1) to (D4) obtained above.

Comparative Example 1
[X1] 90 parts and [A1] 10 parts were put into a glass bottle that can be sealed, and shaken well until uniform to obtain 100 parts of a polymer flocculant [D5].

Comparative Example 2
[X1] 80 parts and [C1] 20 parts were put into a glass bottle capable of being sealed and shaken well until uniform to obtain 100 parts of a polymer flocculant [D6].

Comparative Example 3
[X2] 90 parts and [A2] 10 parts were put into a glass bottle that can be sealed and shaken well until uniform to obtain 100 parts of a polymer flocculant [D7].

Comparative Example 4
[X2] 85 parts and [C1] 15 parts were placed in a glass bottle capable of being sealed and shaken well until uniform to obtain 100 parts of a polymer flocculant [D8].

Comparative Example 5
[X3] 90 parts and [A2] 10 parts were placed in a glass bottle that can be sealed and shaken well until uniform to obtain 100 parts of a polymer flocculant [D9].

Comparative Example 6
[X3] 70 parts and [C1] 30 parts were put into a glass bottle that can be sealed, and shaken well until uniform to obtain 100 parts of a polymer flocculant [D10].

Table 3 shows the contents of (D5) to (D10) obtained above.

ＡＡｍ ：アクリルアミド
ＤＡＡＱ：Ｎ，Ｎ−ジメチルアミノエチルアクリレートのメチルクロライド４級アンモ
ニウム塩
ＤＡＭＱ：Ｎ，Ｎ−ジメチルアミノエチルメタアクリレートのメチルクロライド４級ア
ンモニウム塩
ＡＡｃ ：アクリル酸

AAm: Acrylamide DAAQ: N, N-dimethylaminoethyl acrylate methyl chloride quaternary ammo
Nium salt DAMQ: N, N-dimethylaminoethyl methacrylate methyl chloride quaternary acrylate
Numonium salt AAc: Acrylic acid

Examples 5-6, Comparative Examples 7-8
Polymer flocculants [D1], [D2], [D5], and [D6] were each dissolved in ion-exchanged water to obtain an aqueous solution having a solid content of 0.2%. J Surplus sludge collected from the sewage treatment plant [pH 6.0, TS 2.4%, organic content 71%] was taken in four separate beakers of 200 parts each, and the above-mentioned <floc particle size was used using 50 parts of each aqueous solution. > Mixing treatment was performed by the apparatus and addition described in the measurement method, and the mixing method, and the floc particle size, filtrate amount, filter cloth peelability, cake moisture content, COD and filtrate clarity were measured by the above method [at this time [D1], [D2], [D5] and [D6] had a solid content addition of 2.1% / TS]. The results are shown in Table 4.
From the result of Table 4, in Examples 5-6, compared with Comparative Examples 7-8, the floc of a large particle size was formed, and the floc once formed was hard to break even under high agitation (300 rpm) (the floc strength is high). Strong), filter cloth peelability, dewaterability (cake water content), COD reduction, and filtrate clarity.

Examples 7-8, Comparative Examples 9-10
Polymer flocculants [D3], [D7], [D8], [AB3], and [C1] were each dissolved in ion-exchanged water to obtain an aqueous solution having a solid content of 0.2%. Excess sludge [pH 6.8, TS 1.4%, organic content 50%] collected from the M food factory was taken in four separate beakers of 200 parts each, and each aqueous solution [D3], [D7], and [D8]. 30 parts were mixed and treated in the same manner as described above. Similarly, after 4.5 parts of an aqueous solution of [C1] was mixed, 25.5 parts of [AB3] was further added and mixed. These treated products were measured for floc particle size, filtrate amount, filter cloth peelability, cake moisture content, COD and filtrate clarity [D3, [D7], [D8] at this time. In addition, the solid content of [C] + [AB3] is 2.1% / TS]. The results are shown in Table 5.
From the results of Table 5, in Examples 7-8, compared to Comparative Examples 9-10, flocs having a large particle diameter are formed, and the flocs once formed are not easily broken even under high agitation (300 rpm) (the floc strength is low). Strong), filter cloth peelability, dewaterability (cake water content), COD reduction, and filtrate clarity.

Examples 9-10, Comparative Examples 11-12
Polymer flocculants [D4], [D9], [D10], [AB4], and [C1] were each dissolved in ion-exchanged water to obtain an aqueous solution having a solid content of 0.2%. Digested sludge collected from the G sewage treatment plant was placed in four separate beakers of 200 parts each and mixed in the same manner as described above using 45 parts of each of the aqueous solutions [D4], [D9], and [D10]. Similarly, after 31.5 parts of an aqueous solution of [AB4] was mixed, 13.5 parts of [C1] was further added and mixed. These treated products were measured for floc particle size, filtrate amount, filter cloth peelability, cake moisture content, COD and filtrate clarity [D4], [D9], [D10] at this time. In addition, the solid content of [C1] + [AB4] is 2.5% / TS]. The results are shown in Table 6.
From the result of Table 6, Examples 9-10 form the floc of a large particle diameter compared with Comparative Examples 11-12, and the floc once formed is hard to break even under high stirring (300 rpm) (the floc strength is Strong), filter cloth peelability, dewaterability (cake water content), COD reduction, and filtrate clarity.

Since the polymer flocculant of the present invention exhibits an unprecedented low addition amount and a high processing speed and a high dewatering rate (that is, low cake moisture content), organic or inorganic sludge such as sewage or factory wastewater or wastewater. It can be used as a polymer flocculant for dehydration treatment, and is particularly suitably used for dehydration treatment of organic sludge.
Other uses include, for example, flocculants for drilling and muddy water treatment, papermaking chemicals (for example, paper industry formation forming aids, drainage yield improvers, drainage improvers and paper strength enhancers), and crude oil production increases. Additives (additives for secondary and tertiary recovery of crude oil), dispersants, scale inhibitors, coagulants, decolorizers, thickeners, antistatic agents and textile treatment agents, among which drilling and muddy water It is suitably used as a processing flocculant, a papermaking chemical and an additive for increasing crude oil production.

Claims (2)

From the (co) polymer (A) having the monomer (a) represented by the general formula (1) as an essential structural unit, and the monomer (b) represented by the general formula (2) in the presence of (A) A polymer aggregate comprising a water-soluble (co) polymer (B) other than (A) and a water-soluble copolymer (C) having amidine as an essential constituent unit Agent.

^{_{(CH 2 = CR 1 -CH 2}} ) 2 N + HR 2 · Z - (1)

^{_{CH 2 = CR 3 -CO-X}} -Q-N + R 4 R 5 R 6 · Z - (2)

Wherein R ¹ and R ³ are each independently H or a methyl group, R ² is H, a (meth) allyl group, an alkyl group having 1 to 16 carbon atoms or a hydroxyalkyl group having 2 to 4 carbon atoms, R ⁴ R ⁵ and R ⁶ are each independently H, an alkyl group having 1 to 16 carbon atoms or an aralkyl group; X is O or NH; Q is an alkylene group having 1 to 4 carbon atoms or a hydroxyalkylene group having 2 to 4 carbon atoms; Z ⁻ represents a counter anion. ] The flocculant according to claim 1, or sludge or (A), (B) and (C) combined with sludge or waste water, mixed to form flocs and solid-liquid separation. Wastewater treatment method.