JP2008183541A - Polymer flocculant - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a polymer flocculant in which particles are restrained from being agglomerated with one another or stuck to the inner wall surface of a polymerization tank when polymerization is performed in a reversed phase suspension polymerization method and the polymer flocculant is dried so that the productivity of the polymer flocculant can be improved remarkably and to provide the polymer flocculant obtained by this production method. <P>SOLUTION: The polymer flocculant consists of a water-soluble (co)polymer (A) obtained by reversed phase suspension polymerization of a water-soluble unsaturated monomer (a) in a hydrophobic dispersion medium (b) by using a dispersant (c). The dispersant (c) consists of a polymer obtained by (co)polymerizing a specific monomer. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

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

Conventionally, a cationic water-soluble polymer has been used as a cationic polymer flocculant for the purpose of dehydrating organic sludge produced by activated sludge treatment. The product form of the cationic polymer flocculant is various in addition to powder, such as low concentration aqueous solution, emulsion and suspension. Among these, powdered products are characterized by high active ingredient concentration, low production and transportation costs, and excellent stability over time of the product. However, the current powder product has an indefinite particle shape, so when using a powder feeder, etc., powder flowability is poor, often causing problems such as clogging in the hopper, and the powder is stable and quantitative. There was a problem that it could not be supplied.
Polymerization methods for obtaining powdery polymer flocculants include aqueous solution polymerization method, thin film polymerization method, reverse phase suspension polymerization method, etc. Among these, the reverse phase suspension polymerization method has a spherical polymer particle shape. Therefore, it is known that the powder feeder can be stably and quantitatively supplied without any trouble such as clogging. Further, since the heat of polymerization can be easily removed by the hydrophobic dispersion medium, it is excellent in that it can be polymerized at a constant temperature and a polymer flocculant having a high molecular weight and a relatively sharp molecular weight distribution can be obtained. As a method for obtaining a polymer flocculant by the reverse phase suspension polymerization method, conventionally, a method using a cellulose compound as a dispersant (see, for example, Patent Documents 1 to 3), an α-olefin and an α, β-unsaturated polysiloxane. A method using a copolymer with a carboxylic acid (anhydride) or a derivative thereof (see, for example, Patent Documents 4 and 5) is known.

JP 54-56690 A Japanese Patent Laid-Open No. 54-56691 JP 54-69196 A JP-A-57-74309 JP 2004-181449 A

  However, the methods described in Patent Documents 1 to 3 have a problem that the particles are coalesced and coarsened during polymerization due to the stickiness of a small amount of dispersant remaining on the surface of the powder particles, Patent Document 4, Although the method described in 5 can solve the above problem, when the concentration is increased in order to increase production efficiency, a large amount of a dispersing agent is required to maintain dispersion stability. Production of polymer flocculant particles agglomerates and agglomerates because the amount of molecular flocculant used increases and the cake of polymer flocculant particles from which the solvent has been separated in the drying step after polymerization is excessively applied. There was a problem that the performance dropped significantly. An object of the present invention is to provide a polymer flocculant which is free from the above-mentioned problems and has excellent aggregation performance.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve these problems.
That is, the present invention relates to a water-soluble (co) polymer (A) obtained by reverse-phase suspension polymerization using a water-soluble unsaturated monomer (a), a hydrophobic dispersion medium (b) and a dispersant (c). And (c) comprises a polymer obtained by (co) polymerizing a monomer represented by the following general formula (1); and comprises a water-soluble (co) polymer (A). In the method for producing a polymer flocculant, a dispersion phase comprising a water-soluble unsaturated monomer (a) and a radical polymerization initiator (d), a hydrophobic dispersion medium (b) and the following general formula (1) A method for producing a polymer flocculant, comprising reverse-phase suspension polymerization using a continuous phase containing a dispersing agent (c) comprising a polymer obtained by (co) polymerizing a monomer to be polymerized; and Add the polymer flocculant to sewage sludge or wastewater to form floc And then, a processing method of the sewage sludge or waste water and performing solid-liquid separation.
[Wherein, R ¹ represents H or a methyl group, A represents an alkylene group having 2 to 4 carbon atoms, n represents 0 or an integer of 1 to 20, and R ² represents a branched alkyl group having 16 to 44 carbon atoms. ]

The polymer flocculant and the method for producing the same of the present invention have the following effects.
(1) The polymer flocculant has a narrow molecular weight distribution and excellent aggregation performance.
(2) The production method enables high monomer concentration polymerization with a small amount of dispersant.
(3) The production method does not coalesce between the polymer particles during polymerization and does not become coarse.
(4) This manufacturing method is excellent in productivity.

(A) in the present invention is a water-soluble (co) polymer having a water-soluble unsaturated monomer (a) as a structural unit, and (a) includes the following nonionic monomer (a1), cationic monomer ( a2), anionic monomers (a3) and mixtures of two or more of these.
As the monomer constituting (A), in addition to (a), a water-insoluble unsaturated monomer (x) and a crosslinkable monomer (y) may be used in combination as necessary, as long as the effects of the present invention are not impaired. Here, the water-soluble unsaturated monomer or water-soluble (co) polymer means an unsaturated monomer or (co) polymer having a solubility in water (20 ° C.) of 1 g / 100 g or more of water, and is water-insoluble unsaturated. Monomer means an unsaturated monomer having a solubility in water (20 ° C.) of less than 1 g / 100 g of water.

(A1) Nonionic monomer The following are mentioned, and these mixtures.
(A11) (Meth) acrylate Carbon number (hereinafter abbreviated as C) 4 to weight average molecular weight [hereinafter abbreviated as Mw. The measurement is based on a gel permeation chromatography (GPC) method. ] 5,000, 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, polyglycerol (degree of polymerization 1 to 10) mono (meth) acrylate] and alkyl acrylate (C1-2) ester (C4-5, such as methyl acrylate, ethyl acrylate, etc.);
(A12) (Meth) acrylamide and derivatives thereof C3-30, such as (meth) acrylamide, N-alkyl (C1-3) (meth) acrylamide [N-methyl and -isopropyl (meth) acrylamide etc.], N-alkylol (Meth) acrylamide [N-methylol (meth) acrylamide etc.];
(A13) Nitrogen-containing ethylenically unsaturated compounds other than the above C3-30, such as acrylonitrile, N-vinylformamide, N-vinyl-2-pyrrolidone, N-vinylimidazole, N-vinylsuccinimide, N-vinylcarbazole and 2 -Cyanoethyl (meth) acrylate and the like.

(A2) Cationic monomer The following, these salts [for example, inorganic acid (hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, etc.) salts, methyl chloride salts, dimethyl sulfate salts, benzyl chloride salts, etc.], and mixtures thereof are mentioned. It is done.
(A21) Nitrogen atom-containing (meth) acrylate C5-30, such as aminoalkyl (C2-3) (meth) acrylate, N, N-dialkyl (C1-2) aminoalkyl (C2-3) (meth) acrylate [N N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, etc.], heterocycle-containing (Meth) acrylate [N-morpholinoethyl (meth) acrylate etc.] etc .;
(A22) Nitrogen atom-containing (meth) acrylamide derivative C5-30, such as N, N-dialkyl (C1-2) aminoalkyl (C2-3) (meth) acrylamide [N, N-dimethylaminoethyl (meth) acrylamide, etc. ]etc;
(A23) Ethylenically unsaturated compound having amino group C5-30, such as vinylamine, vinylaniline, (meth) allylamine, p-aminostyrene, etc.];
(A24) Compound having amine imide group C5-30, such as 1,1,1-trimethylamine (meth) acrylimide, 1,1-dimethyl-1-ethylamine (meth) acrylimide, 1,1-dimethyl-1- ( 2′-phenyl-2′-hydroxyethyl) amine (meth) acrylimide and the like;
(A25) Nitrogen atom-containing vinyl monomers other than the above C5-30, such as 2-vinylpyridine, 3-vinylpiperidine, vinylpyrazine, vinylmorpholine and the like.

(A3) Anionic monomer The following acids, salts thereof [alkali metal (lithium, sodium, potassium, etc., the same shall apply hereinafter) salts, alkaline earth metals (magnesium, calcium, etc., the same shall apply hereinafter) salts, ammonium salts and amines (C1-20) salts and the like], and mixtures thereof.
(A31) unsaturated carboxylic acid C3-30, such as (meth) acrylic acid, (anhydrous) maleic acid, fumaric acid, (anhydrous) itaconic acid, vinyl benzoic acid, allyl acetic acid and the like;
(A32) Unsaturated sulfonic acid C2-20 aliphatic unsaturated sulfonic acid (such as vinyl sulfonic acid), C6-20 aromatic unsaturated sulfonic acid (such as styrene sulfonic acid), sulfonic acid group-containing (meth) acrylate [ Sulfoalkyl (C2-20) (meth) acrylate [2- (meth) acryloyloxyethanesulfonic acid, 2- (meth) acryloyloxypropanesulfonic acid, 3- (meth) acryloyloxypropanesulfonic acid, 2- (meth) Acryloyloxybutanesulfonic acid, 4- (meth) acryloyloxybutanesulfonic acid, 2- (meth) acryloyloxy-2,2-dimethylethanesulfonic acid, p- (meth) acryloyloxymethylbenzenesulfonic acid, etc.], sulfonic acid Group-containing (meth) acrylamide [2- (meth) acryloyl Aminoethanesulfonic acid, 2- and 3- (meth) acryloylaminopropanesulfonic acid, 2- and 4- (meth) acryloylaminobutanesulfonic acid, 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid, p- (meth) acryloylaminomethylbenzenesulfonic acid and the like], alkyl (C1-20) (meth) allylsulfosuccinate [methyl (meth) allylsulfosuccinate and the like] and the like;
(A33) (Meth) acryloyl polyoxyalkylene (C1-6) sulfate ester (meth) acryloyl polyoxyethylene (degree of polymerization 2 to 50) sulfate ester and the like.

Of these, (a), (a1), (a21), (a22), (a31), (a32) are preferable, and (a12), (a13), (a21) are more preferable. , (A22), (a31), and (a32), sulfonic acid group-containing (meth) acrylate, sulfonic acid group-containing (meth) acrylamide, particularly preferably (a12), (a13), (a21), Of (a31) and (a32), sulfonic acid group-containing (meth) acrylate, sulfonic acid group-containing (meth) acrylamide, most preferably (meth) acrylamide of (a12), of (a13) Acrylonitrile, N-vinylformamide, N, N-dimethylaminoethyl (meth) acrylate of (a21) and salts thereof (above), (meth) acrylic acid, (anhydrous) maleic acid, (anhydrous) itaconic acid and alkali metal salts thereof in (a31), 2- (meth) acryloyloxyethanesulfonic acid in (a32), 2- and 3 -(Meth) acryloyloxypropanesulfonic acid, 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid and alkali metal salts thereof. Moreover, these (a) can be arbitrarily mixed and copolymerized.

  The use amount (mol%) of (a) is preferably 50 to 50 from the viewpoint of agglomeration performance (floc strength, low water content, etc., the same shall apply hereinafter) based on the total number of moles of monomers constituting (A). 100%, more preferably 80 to 100%.

Examples of the water-insoluble unsaturated monomer (x) that may be used in combination with (a) if necessary include the following (x1) to (x5), and mixtures thereof.
(X1) (Meth) acrylate of C6-23 (meth) acrylate of aliphatic or alicyclic alcohol (C3-20) [propyl-, butyl-, lauryl-, octadecyl- and cyclohexyl (meth) acrylate etc.] and epoxy Group (C4-20) -containing (meth) acrylate [glycidyl (meth) acrylate and the like];

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

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

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

(Y3) Vinyl group (2 to 20 or more) -containing monomers C4 to Mn6,000, such as divinylamine, polyvalent (2 to 5 or more) amine [C2 to Mn3,000, such as ethylenediamine, polyethyleneimine ( C4-Mn3,000)] poly (2-20) vinylamine, divinyl ether, polyhydric alcohol [C2-Mn3,000, for example, alkylene (C2-6 or higher) glycol [ethylene glycol (hereinafter abbreviated as EG)] , Propylene glycol (hereinafter abbreviated as PG), 1,6-hexanediol (hereinafter abbreviated as HG), etc.], polyoxyalkylene [Mn 2 to 3000, for example, polyethylene glycol (hereinafter abbreviated as PEG) (molecular weight 106 to Mn 3 , 000), PPG (molecular weight 134-Mn 3,000), Reoxyethylene (molecular weight: 106 to Mn3,000) / polyoxypropylene (molecular weight: 134 to Mn3,000) block copolymer, etc.], trimethylolethane (hereinafter abbreviated as TME), trimethylolpropane (hereinafter abbreviated as TMP), Poly (2-20) vinyl ether of (poly) (2-50) glycerin (hereinafter abbreviated as GR), pentaerythritol (hereinafter abbreviated as PE), sorbitol (hereinafter abbreviated as SO), starch, etc.];

(Y4) Allyl group (2 to 20 or more) -containing monomers C6 to Mn3000, such as di (meth) allylamine, N-alkyl (C1-20) di (meth) allylamine, polyvalent amines (above) Poly (2-20) (meth) allylamine, di (meth) allyl ether, poly (2-20) (meth) allyl ether of polyhydric alcohol (above), poly (2-20) (meth) allyloxy Alkanes (C1-20) (tetraallyloxyethane and the like) and the like;
(Y5) Epoxy group-containing monomer C8 to Mn6,000, for example, EG diglycidyl ether, PEG diglycidyl ether, GR triglycidyl ether and the like.

The use amount (mol%) of (x) is usually 40 or less, based on the total number of moles of the monomers constituting (A), and the lower limit preferable from the viewpoint of expressing the aggregation performance is 0.1, more preferably 0.5 From the viewpoint of solubility of the resulting polymer flocculant in water, the upper limit is preferably 20, and more preferably 10.
The amount (mol%) of (y) used is usually 5 based on the total number of moles of the monomer constituting (A), although it depends on the polymerizability or reactivity of the crosslinkable monomer (y) used. Hereinafter, the preferable lower limit from the viewpoint of the aggregation performance expression is 0.001, more preferably 0.01, and the preferable upper limit is 1, more preferably 0.5 from the viewpoint of solubility of the resulting polymer flocculant in water. .

The hydrophobic dispersion medium (b) in the present invention means a dispersion medium having a solubility in water (20 ° C.) of less than 1 g / 100 g of water.
As (b), hydrocarbon [aliphatic (C5-12, such as n-hexane, n-heptane, n-octane, n-nonane, n-decane), alicyclic (C5-12, such as cyclopentane, Cyclohexane, cycloheptane, methylcyclohexane, cyclooctane, decalin) and aromatic hydrocarbons (C6-12, such as benzene, toluene, xylene, ethylbenzene), etc.], ketones [aliphatic (C3-10, such as methyl-n-propyl). Ketone, diethyl ketone, methyl isobutyl ketone), alicyclic (C5-10, such as cyclopentanone, cyclohexanone) and aromatic ring-containing ketone (C8-13, such as acetophenone, benzophenone), etc.], ether [aliphatic (C4- 8, for example di-n-propyl ether, di-n-butyl ether, di- Ethylene glycol dimethyl ether), cyclic ethers (C4-18, such as tetrahydropyrine) and aromatic ring-containing ethers (C7-12, such as anisole)], esters [aliphatic esters (C3-10, such as n-butyl acetate), fats Ring-containing ester (C7-12, such as cyclohexyl acetate, cyclohexanecarboxylate), aromatic ring-containing ester (C8-13, such as methyl benzoate, ethyl benzoate, n-butyl benzoate, benzyl acetate, dimethyl phthalate, diethyl phthalate , Di-n-butyl phthalate) and the like, and mixtures thereof.
Among these, from the viewpoint of handling during production and high molecular weight, preferred are aliphatic and alicyclic hydrocarbons, and more preferred are n-hexane, n-heptane, n-octane, n-nonane, n -Decane, cyclohexane and methylcyclohexane.

  The amount of (b) used is preferably 25%, more preferably 40%, particularly preferably 65% from the viewpoint of dispersion stability, based on the weight of the aqueous monomer solution, and preferably 1% from the viewpoint of production efficiency. 1,000%, more preferably 400%, particularly preferably 200%.

The dispersant (c) in the present invention comprises a polymer obtained by (co) polymerizing the monomer (c01) represented by the following general formula (1).

In the formula, R ¹ represents H or a methyl group. A represents a C2-4 alkylene group. When C of the alkylene group exceeds 4, the dispersion stability of the water-soluble (co) polymer (A) becomes poor.
n represents 0 or an integer of 1 to 20, and when n exceeds 20, the dispersion stability of (A) is deteriorated.
R ² represents a branched alkyl group of C16 to 44, and if C of the branched alkyl group is less than 16, the solubility of (c) in the hydrophobic dispersion medium deteriorates, and if it exceeds 44, the dispersion stability of (A) is reduced. Deteriorate. Among R ² , a branched alkyl group represented by the following general formula (2) is preferable from the viewpoint of preventing particle coalescence.

In the formula, R ³ and R ⁴ are C1-41, preferably 6-24, alkyl groups in which the sum of their C is from 14 to 42, preferably from 16 to 38, more preferably from 18 to 34. R ³ and R ⁴ may be a linear alkyl group or a branched alkyl group, and one of them may be linear and one of them may be branched. Preferred is when both R ³ and R ⁴ are straight chain alkyl groups.

Specific examples of R ² include the following groups.
C16: 2-methylpentadecyl group, 2-hexyldecyl group, etc. C17: 2-methylhexadecyl group, etc. C18: 2-octyldecyl group, 2-hexyldecyl group, 2-methylheptadecyl group, etc. C19: 2-methyloctadecyl C20: 2-octyldodecyl group, etc. C24: 2-decyltetradecyl group, etc. C28: 2-dodecylhexadecyl group, etc. C32: 2-tetradecyloctadecyl group, etc. C34: 2-hexadecyloctadecyl, 2-tetradecyleico Syl group,
C36: 2-hexadecyleicosyl group etc. C40: 2-octadecyl docosyl group etc. C44: 2-docosyl tetracosyl group etc.

In the general formula (1), A is a C2-4 alkylene group, for example, ethylene group, 1,2- and 1,3-propylene group, 1,2-, 1,3- and 1,4-butylene group. Is mentioned. Of these, ethylene group and 1,2-propylene group are preferable from the viewpoint of dispersion stability of (A).
In general formula (1), n is an integer of 0 or 1-20 (preferably 0 or 1-10, more preferably 0 or 1-5).

Specific examples of (c01) include 2-octyldodecyl (meth) acrylate, 2-decyltetradecyl acrylate, 2-decyltetradecyl methacrylate (hereinafter abbreviated as MA-i24), 2-dodecylhexadecyl (meth) acrylate. 2-tetradecyl octadecyl acrylate, 2-tetradecyl octadecyl methacrylate (hereinafter abbreviated as MA-i32), 2-octyldecyloxyethyl (meth) acrylate, 2-decyltetradecyloxyethyloxyethyl (meth) acrylate, 2 -Decyltetradecyloxyethyl methacrylate (hereinafter abbreviated as MA-EO-i24), 2-decylhexadecyloxypropyloxypropyl (meth) acrylate, and 2-dodecylhexadecyloxybutyl (meth) acrylate It is below.
Among these, from the viewpoint of dispersion stability of (A), 2-octyldodecyl (meth) acrylate, 2-decyltetradecyl (meth) acrylate, 2-dodecylhexadecyl (meth) acrylate, and 2-tetradecyloctadecyl are preferable. (Meth) acrylate and MA-EO-i24.

  (C) includes a homopolymer of (c01), two or more copolymers of (c01), and a copolymer of one or more of (c01) and another vinyl monomer (z). . From the viewpoint of preventing particle coalescence, two or more types of (c01) copolymers and a copolymer of one or more types of (c01) and another vinyl monomer (z) are preferred. ) Include, for example, the following (z1) to (z13) and combinations of two or more thereof.

(Z1): (Meth) acrylic acid hydrocarbyl ester other than (c01) (the hydrocarbyl group represents a monovalent hydrocarbon group)
The following are mentioned.

(Z1-1) (Meth) acrylic acid alkyl ester having C1-7 alkyl group:
For example, methyl (meth) acrylate, ethyl (meth) acrylate, n- and i-propyl (meth) acrylate, n-, i- and sec-butyl (meth) acrylate, n-pentyl (meth) acrylate N-hexyl (meth) acrylate;

(Z1-2) (meth) acrylic acid alkyl ester having a C8-15 linear and / or branched alkyl group or a C16-24 linear alkyl group:
For example, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-decyl (meth) acrylate, n-isodecyl (meth) acrylate, n-undecyl (meth) acrylate, n-acrylate Dodecyl, n-dodecyl methacrylate (abbreviated as MA-12), 2-methylundecyl (meth) acrylate, n-tridecyl (meth) acrylate, 2-methyldodecyl (meth) acrylate, (meth) acrylic N-tetradecyl acid, 2-methyltridecyl (meth) acrylate, n-pentadecyl (meth) acrylate, 2-methyltetradecyl (meth) acrylate, n-hexadecyl acrylate, n-hexadecyl methacrylate (MA- 16), n-octadecyl acrylate, n-octadecyl methacrylate (MA-18 and Serial to), (meth) acrylic acid n- eicosyl (meth) acrylate n- docosyl;

(Z1-3) (Meth) acrylic acid alkenyl ester having C2-30 linear or branched alkenyl group:
For example, (meth) acrylic acid butenyl ester, (meth) acrylic acid octenyl ester, (meth) acrylic acid decenyl ester, (meth) acrylic acid dodecenyl ester, (meth) acrylic acid oleyl ester;

(Z1-4) (Meth) acrylic acid aralkyl ester having C7-30 aralkyl group:
For example, (meth) acrylic acid benzyl ester, (meth) acrylic acid phenylethyl ester and (meth) acrylic acid phenyloctyl ester;

(Z1-5) (Meth) acrylic acid (alkyl-substituted) cycloalkyl ester:
For example, cyclohexyl (meth) acrylate, cyclohexylethyl (meth) acrylate, cyclohexylmethyl (meth) acrylate and cycloheptylethyl (meth) acrylate;

(Z2): (Poly) alkylene glycol monoalkyl [alkyl group is an alkyl group other than R ² in the above general formula (1)] ether mono (meth) acrylate ester (z2) (poly) alkylene glycol monoalkyl ether As the oxyalkylene group constituting the oxyalkylene group, C is an oxyalkylene group having 2 to 20 (preferably C2 to 4), such as an oxyethylene group, an oxypropylene group, an oxybutylene group, an oxy-2-butylene group and an oxyisobutylene group. It is done. Further, examples of the alkyl group constituting the monoalkyl ether include a linear and / or branched alkyl group having 1 to 15 carbon atoms, or a linear alkyl group having 16 to 24 carbon atoms.
The number of oxyalkylene units in the (poly) alkylene glycol (hereinafter abbreviated as p) is preferably 1 to 50, more preferably 1 to 20.
Specific examples of (z2) include polyethylene glycol (p = 6) monomethyl ether mono (meth) acrylate [abbreviated as (M) A-EO9-Me], ethylene glycol mono-2-ethylhexyl ether mono (Meth) acrylic acid ester [abbreviated as (M) A-EO-2eH], polypropylene glycol (p = 3) monobutyl ether mono (meth) acrylate [abbreviated as (M) A-PO3-Bu] Is mentioned.

(Z3): ester of unsaturated carboxylic acid other than (meth) acrylic acid C1-30 alkyl, cycloalkyl or aralkyl ester of unsaturated monocarboxylic acid [crotonic acid etc.] other than (meth) acrylic acid, and unsaturated C1-C24 alkyl diesters [dimethyl maleate, dimethyl fumarate, diethyl maleate, dioctyl maleate, etc.] of dicarboxylic acids [maleic acid, fumaric acid, itaconic acid, etc.].

(Z4): Aliphatic hydrocarbon vinyl monomer For example, C2-30 alkene [ethylene, propylene, 1-butene, isobutylene, 1-pentene, 1-heptene, 4-methylpentene-1,1-hexene, diisobutylene 1-octene, 1-dodecene, 1-octadecene and other α-olefins, etc.], C4-18 (preferably C4-5) alkadienes [butadiene, isoprene, 1,4-pentadiene, 1,6-hexadiene and 1,7-octadiene etc.].

(Z5): alkyl alkenyl ether C1-30, preferably alkyl vinyl ether having a linear or branched alkyl group of C1-24 [methyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether, etc.], alkyl (meth) allyl ether [methyl allyl] Ether, ethyl allyl ether, n-butyl allyl ether, etc.], alkyl propenyl ether, alkyl isopropenyl ether and the like. Of these, methyl vinyl ether, ethyl vinyl ether, methyl allyl ether and ethyl allyl ether are preferred from the viewpoint of the dispersion stability of (A).

(Z6): Monocarboxylic acid vinyl ester Examples of the monocarboxylic acid include C2-30, preferably C1-18 aliphatic, alicyclic and aromatic saturated and unsaturated monocarboxylic acids. Aliphatic monocarboxylic acids include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl hexanoate, vinyl heptanoate, vinyl 2-ethylhexanoate, vinyl n-octanoate, vinyl oleate, vinyl linoleate, vinyl linolenate, etc. As the alicyclic monocarboxylic acid, vinyl cyclohexane acid,
Examples of aromatic monocarboxylic acids such as vinyl cyclooctanoate include vinyl benzoate.

(Z7): Vinyl ketone C1-8 alkyl or aryl vinyl ketone [methyl vinyl ketone, ethyl vinyl ketone, phenyl vinyl ketone, etc.] can be mentioned.

(Z8): Alicyclic hydrocarbon vinyl monomer Cyclohexene, (di) cyclopentadiene, vinylcyclohexene, ethylidenebicycloheptene, pinene, limonene, indene and the like having a C5-24 alicyclic group are exemplified.

(Z9): aromatic hydrocarbon vinyl monomer styrene, substituted styrene (substituent C1-18) [alkyl-substituted styrene (α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene) ), Cycloalkyl-substituted styrene (cyclohexyl styrene, etc.), aryl-substituted styrene (phenyl styrene, etc.), aralkyl-substituted styrene (benzyl styrene, etc.)], divinyl-substituted aromatic hydrocarbons [divinylbenzene, divinyltoluene, divinylxylene, etc.], And vinyl naphthalene.

(Z10): nitrogen atom-containing monomer (z10-1): primary to tertiary amino group-containing vinyl monomer aminoalkyl (C1-8) (meth) acrylate or (meth) acrylamide [aminoethyl (meth) acrylate, aminopropyl ( Meth) acrylate, N-aminoethyl (meth) acrylamide, etc.] and their mono- and dialkyl (C1-6) substitutes [dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, t-butylaminoethyl methacrylate, etc. ], A heterocyclic amino group-containing vinyl monomer [morpholinoethyl (meth) acrylate, 4-vinylpyridine, 2-vinylpyridine, vinylimidazole, N-vinylpyrrole, etc.] and mono and di (meth) allylamine.
(Z10-2): Quaternary nitrogen atom-containing vinyl monomer Dialkyl (C1-4) aminoalkyl (C2-8) (meth) acrylate or quaternized product of (meth) acrylamide [dimethylaminoethyl (meth) acrylate, diethylaminoethyl Quaternized products such as (meth) acrylate, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide], and quaternized products of diallylamine. Examples of the quaternizing agent include compounds having a C1-12 alkyl or aralkyl group such as methyl chloride, dimethyl sulfate, benzyl chloride and dimethyl carbonate, or those quaternized with an alkylene oxide (C2-4). .

(Z10-3): Amide group-containing vinyl monomer Unsubstituted or monoalkyl (C1-4) substituted (meth) acrylamide, [(meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N -I-propyl (meth) acrylamide, Nn- and i-butyl (meth) acrylamide, etc.], dialkyl (C1-4) substituted (meth) acrylamide [N, N-dimethyl (meth) acrylamide, N, N- Diethyl (meth) acrylamide, N, N-di-n-butyl (meth) acrylamide], N-vinylcarboxylic acid amide [N-vinylformamide, N-vinylacetamide, N-vinyl-n- and i-propionylamide, N -Vinylhydroxyacetamide] and heterocyclic (thio) amide group-containing vinyl And monomers [N-vinylpyrrolidone, N-vinylthiopyrrolidone] and the like.

(Z10-4): Nitrile group-containing monomer (meth) acrylonitrile, cyanostyrene and the like.

(Z10-5): a nitro group-containing monomer such as 4-nitrostyrene.

(Z11): Hydroxyl group-containing vinyl monomer (z11-1): Hydroxyl group-containing aromatic vinyl monomer p-hydroxystyrene and the like.
(Z11-2): hydroxyl-containing aliphatic monomer vinyl alcohol (formed by hydrolysis of vinyl acetate unit), C3-12 alkenol [(meth) allyl alcohol, crotyl alcohol, isocrotyl alcohol, 1-octenol 1-undecenol, etc.], C4-12 alkenediol [1-buten-3-ol, 2-buten-1-ol, 2-butene-1,4-diol, etc.], hydroxyalkyl (C1-6) alkenyl (C3-10) ether [2-hydroxyethylpropenyl ether and the like] and mono (meth) acrylic acid ester of (poly) alkylene glycol [oxypolyalkylene group constituting (poly) alkylene glycol includes those described above, The preferable range of p is also the same. For example, (meth) acrylic acid hydroxyethyl ester, polyethylene glycol (p = 9) mono (meth) acrylic acid ester, polypropylene glycol (p = 3) mono (meth) acrylic acid ester] and the like.

(Z12): Halogen atom-containing vinyl monomer Vinyl chloride, vinyl bromide, vinylidene chloride, (meth) allyl chloride, halogenated styrene (mono and dichlorostyrene and tetrafluorostyrene) and the like.

(Z13): Anionic monomer (z13-1): Carboxyl group-containing vinyl monomer Unsaturated monocarboxylic acid [(meth) acrylic acid, α-methyl (meth) acrylic acid, crotonic acid, cinnamic acid, etc.], unsaturated dicarboxylic acid Monoalkyl (C1-24) ester of acid [maleic acid monoalkyl ester, fumaric acid monoalkyl ester, itaconic acid monoalkyl ester, etc.], unsaturated dicarboxylic acid [maleic acid, fumaric acid, itaconic acid, citraconic acid, aconitic acid Etc.] and unsaturated dicarboxylic anhydrides [maleic anhydride, itaconic anhydride, etc.].
(Z13-2): Sulfo group-containing vinyl monomer C2-6 alkene sulfonic acid [such as vinyl sulfonic acid and (meth) allyl sulfonic acid], C8-12 aromatic vinyl group-containing sulfonic acid [styrene sulfonic acid, α- Methyl styrene sulfonic acid etc.], sulfoalkyl (C2-6) (meth) acrylate [sulfoethyl (meth) acrylate, sulfopropyl (meth) acrylate etc.], (meth) acrylamide alkane (C2-8) sulfonic acid [2- ( Meth) acrylamide-2-methylpropane sulfonic acid, etc.], vinyl monomers containing a sulfo group and a hydroxyl group [3- (meth) acrylamide-2-hydroxypropane sulfonic acid, 3-allyloxy-2-hydroxypropane sulfonic acid and 3- (Meth) acryloyloxy-2-hydroxyp Bread acid, etc.] and alkyl (C3～18) (meth) allyl sulfosuccinate [dodecyl (meth) allyl sulfosuccinate] and the like.
(Z13-3): sulfate group-containing vinyl monomer poly (p = 2-30) oxyalkylene (C2-4: ethylene, propylene, butylene, etc .: any of single addition, random and / or block addition) of glycol Examples thereof include sulfuric ester of mono (meth) acrylic acid ester, and poly (p = 2 to 30) oxyalkylene (alkylene is the same as described above) and sulfuric acid ester of mono (meth) acrylic acid ester of bisphenol A.

(Z13-4): Phosphoric acid group-containing vinyl monomer (meth) acryloyloxyalkyl (C2-6) phosphoric acid monoester [(meth) acryloyloxyethyl phosphate etc.], (meth) acryloyloxyalkane (C2-4) phosphonic acid [ 2-acryloyloxyethanephosphonic acid and the like] and the like.

  Among the above (z), from the viewpoint of the dispersion stability of (A), at least selected from the group consisting of (z1), (z2), (z3), (z4), (z9) and (z10) is preferable. One, more preferably at least one selected from the group consisting of (z1), (z2) and (z4), and particularly preferred is a combination of (z2) and (z4).

  The proportion of the unit composed of (c01) in (c) is preferably 30 to 100% based on the weight of (c) (% represents% by weight unless otherwise specified), more preferably Is 30 to 95%, particularly preferably 40 to 75%. Similarly, the proportion of units composed of (z) is preferably 0 to 70%, more preferably 5 to 70%, and particularly preferably 25 to 60% based on the weight of (c).

  The Mw of (c) is preferably 3,000 to 1,000,000, more preferably 10,000 to 500,000, and particularly preferably 50,000 to 300,000 from the viewpoint of dispersion stability.

  The method for producing (c) may be a conventionally known radical polymerization method, for example, solution polymerization method, emulsion polymerization method, suspension polymerization method, reverse phase suspension polymerization method, thin film polymerization method, spray polymerization method, etc. Is mentioned. Among these, the solution polymerization method is preferred, and is usually a method in which (c01) and, if necessary, (z) are radically polymerized in a solvent in the presence of an initiator.

The solvents include mineral oils [solvent refined oils, hydrogenated reformed oils, isoparaffin-containing and / or hydrocracked high viscosity index oils having a viscosity index of 100 to 160, naphthenic oils] and synthetic lubricating oils [carbonized] High flash point solvents (flash point 130 ° C or higher) such as hydrogen synthetic lubricants (poly α-olefin synthetic lubricants and ester synthetic lubricants); other solvents [aliphatic hydrocarbons (pentane, hexane, etc.) ), Aromatic hydrocarbon (toluene, xylene, etc.), alcohol [isopropyl alcohol (hereinafter abbreviated as IPA), octanol, butanol, etc.], ketone (methyl isobutyl ketone, methyl ethyl ketone, etc.), amide (N, N-dimethylformamide, N-methylpyrrolidone etc.), sulfoxide (dimethyl sulfoxide etc.)] and two or more of these Combination is included.
Of these, alcohols and aromatic hydrocarbons are preferable from the viewpoint of uniform solubility of the monomers. In the case of solution polymerization, the solution after polymerization may be used as it is, but it is preferable to distill off the solvent.

Initiators include azo initiators, peroxide initiators, and redox initiators.
Examples of the azo initiator include 2,2′-azobis (2,4-dimethylvaleronitrile) (hereinafter abbreviated as AVN), 2,2′-azobisisobutyronitrile, 2,2′-azobis (2 -Methylbutyronitrile), azobiscyanovaleric acid and its salts (eg hydrochloride), 2,2'-azobis (2-amidinopropane) hydrochloride, 2,2'-azobis-2-methyl-N- (2-hydroxy) And ethyl) propionamide.

  Peroxide initiators include inorganic peroxides [eg, hydrogen peroxide, ammonium persulfate, potassium persulfate, sodium persulfate] and organic peroxides [eg, benzoyl peroxide, di-t-butyl peroxide, Cumene hydroperoxide, succinic peroxide, di (2-ethoxyethyl) peroxydicarbonate, t-butyl peroxypivalate, t-hexyl peroxypivalate, t-butyl peroxyneoheptanoate, t- Butyl peroxyneodecanoate, t-butyl peroxy 2-ethyl hexanoate, t-butyl peroxy isobutyrate, t-amyl peroxy 2-ethyl hexanoate, 1,1,3,3-tetra Methylbutylperoxy 2-ethylhexanoate, dibutylperoxytrimethyla Pies include lauryl peroxide.

Redox initiators include alkali metal sulfites and bisulfites (eg, ammonium sulfite, ammonium bisulfite), ferrous chloride, ferrous sulfate, ascorbic acid and other reducing agents and alkali metal persulfates. , And those composed of a combination with an oxidizing agent such as ammonium persulfate, hydrogen peroxide, and organic peroxide.
The amount of initiator used is preferably 0.05 to 1% based on the total weight of monomers.

  In the radical polymerization method, a chain transfer agent may be used, and the chain transfer agent is not particularly limited, and a chain transfer agent used when producing (A) by the radical polymerization method as described later is used. can do. The amount of the chain transfer agent used is preferably 0 to 3% based on the total weight of the monomers.

The polymerization temperature is preferably 30 to 140 ° C, more preferably 50 to 130 ° C, particularly preferably 70 to 120 ° C. The polymerization temperature can be controlled by an adiabatic polymerization method or a temperature controlled polymerization method (constant temperature polymerization method).
In addition to the method for initiating polymerization by heat, the polymerization can also be initiated by irradiation with radiation, electron beams, ultraviolet rays or the like. From the viewpoint of controlling the molecular weight of (c), a temperature-controlled solution polymerization method is preferred.
The mode of copolymerization may be random addition polymerization and / or alternating copolymerization, and may be either graft copolymerization and / or block copolymerization.

The amount of (c) used is preferably 0.01%, more preferably 0.1%, based on the weight of the hydrophobic dispersion medium (b), from the viewpoint of dispersion stability and particle size control of the dispersed particles. The upper limit is preferably 0.5%, most preferably 1%, and from the viewpoint of particle size control, the upper limit is preferably 10%, more preferably 8%, particularly preferably 5%, and most preferably 3%.

  The water-soluble (co) polymer (A) constituting the polymer flocculant of the present invention comprises a dispersed phase comprising a water-soluble unsaturated monomer (a) and a radical polymerization initiator (d), a hydrophobic dispersion Manufactured by reverse-phase suspension polymerization using a continuous phase containing a dispersant (c) comprising a polymer (b) and a polymer obtained by (co) polymerizing the monomer represented by the medium (b) and the general formula (1) Is done.

  Examples of the reverse phase suspension polymerization method include the following methods. That is, after the hydrophobic dispersion medium (b) and the dispersant (c) are charged into a polymerization tank and adjusted to a predetermined polymerization temperature (usually 20 to 100 ° C., preferably 30 to 80 ° C.) while heating as necessary. The inside of the tank is sufficiently replaced with an inert gas (for example, nitrogen). On the other hand, an aqueous monomer solution is prepared by adding a water-soluble unsaturated monomer (a), a radical polymerization initiator (b), and, if necessary, a water-insoluble unsaturated monomer (x) and / or a crosslinkable monomer (y). After sufficiently substituting with gas, it is added to the polymerization tank under stirring and polymerized while being suspended. The method for charging the aqueous solution may be either batch charging or dropping. In this case, the monomer aqueous solution may be a uniform aqueous solution of (a), (b) and (x) and / or (y) to be added if necessary. It may be dropped simultaneously or separately.

Examples of the polymerization initiator (d) include various compounds such as azo compounds [water-soluble compounds [azobisamidinopropane (salt), azobiscyanovaleric acid (salt), etc.]) and oil-soluble compounds [azobiscyanovalero]. Nitriles, azobisisobutyronitrile, azobiscyclohexanecarbonitrile, etc.]] and peroxides [water-soluble [peracetic acid, t-butyl peroxide, hydrogen peroxide, ammonium persulfate, sodium persulfate, potassium persulfate] Etc.] and oil-soluble ones [benzoyl peroxide, cumene hydroxy peroxide, etc.].
The above peroxide may be used as a redox initiator in combination with a reducing agent. Examples of the reducing agent include bisulfites (sodium bisulfite, potassium bisulfite, ammonium bisulfite, etc.), reducing metal salts [iron sulfate (II ), Etc.], amine complexes of transition metal salts [pentamethylenehexamine complexes of cobalt (III) chloride, diethylenetriamine complexes of copper (II) chloride, etc.], organic reducing agents [ascorbic acid, tertiary amine [dimethylaminobenzoic acid] (Salt), dimethylaminoethanol, etc.].
Further, the azo compound, peroxide and redox initiator may be used alone or in combination of two or more.
(D) is usually present in the dispersed phase, but may be present in either the dispersed phase and / or the continuous phase.

  The amount of (d) used is preferably 0.001%, more preferably 0.005%, particularly preferably from the viewpoint of obtaining an optimum molecular weight based on the total weight of the monomers constituting (A). 0.01%, most preferably 0.02%, the upper limit is preferably 1%, more preferably 0.5%, particularly preferably 0.1%, most preferably 0.05%.

  The total concentration of the monomers in the dispersed phase in the present invention (hereinafter sometimes referred to as the dispersed phase concentration) is preferably 20% or more, more preferably 25% or more, from the viewpoint of productivity, based on the weight of the dispersed phase. Particularly preferably, it is 30% or more, preferably 90% or less, more preferably 85% or less, and particularly preferably 80% or less.

In the production of (A), various oil-soluble polymer substances (e) can be used together if necessary for controlling the particle size of dispersed particles.
Examples of the oil-soluble polymer substance include a copolymer of an alkene and an α, β-unsaturated polyvalent carboxylic acid (anhydride) or a derivative thereof [for example, 1-olefin (C11-100) / (anhydrous) maleic acid copolymer. Polymers], cellulose ethers (eg, ethyl cellulose, ethyl hydroxyethyl cellulose), sucrose fatty acid esters (C22-120, such as sucrose distearate, sucrose tristearate), sorbitan fatty acid esters (C16-120, such as sorbitan monostearate, Sorbitan monooleate), (poly) glycerin fatty acid ester (C12-120, for example, glycerin monostearate) and the like.
Of these, sucrose fatty acid esters and sorbitan fatty acid esters are preferred from the viewpoint of preventing the adhesion of polymer particles to the apparatus during production.
The amount of (e) used is usually 20% or less based on the weight of the hydrophobic dispersion medium (b), preferably from 0 to 10%, more preferably from 0 to 5% from the viewpoint of controlling the particle diameter of (A). It is.

Moreover, you may use the chain transfer agent for radical polymerization as needed. The chain transfer agent is not particularly limited, and examples thereof include compounds having one or more OH groups in the molecule [monohydric alcohol (C1-60, such as methanol, ethanol, n- and i-). Propanol), polyhydric (2-3 or more) alcohols (C2-60, eg ethylene glycol, propylene glycol), high molecular polyols (Mn200-10,000, eg polyethylene glycol, polyethylene / polypropylene glycol) etc.], molecules Compounds having one or more amino groups in them [C0-60, such as ammonia, methylamine, dimethylamine, triethylamine, n- and i-propanolamine], hypophosphite (sodium hypophosphite Etc.), having one or more thiol groups in the molecule Objects (described later) and the like.
Of these, compounds having one or more thiol groups in the molecule are preferred from the viewpoint of molecular weight control.

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

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

  From the viewpoint of obtaining the optimum molecular weight of the polymer flocculant of the present invention, the preferred lower limit of the amount of use of the chain transfer agent for radical polymerization is based on the total weight of (a), (x) and (y). 0.0001%, more preferably 0.001%, particularly preferably 0.01%, most preferably 0.05%, the preferred upper limit is 10%, more preferably 5%, particularly preferably 3%, most preferably 1%.

The pH of the aqueous monomer solution in the present invention is not particularly limited, but from the viewpoint of increasing the molecular weight, the preferable lower limit is 2, more preferably 2.5, particularly preferably 3, and the preferable upper limit is 8 from the viewpoint of preventing hydrolysis. It is preferably 7, particularly preferably 6.5. The pH adjuster used for pH adjustment is not particularly limited, and when the monomer aqueous solution is alkaline, inorganic acid (sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, etc.), inorganic solid acidic substance (acidic sodium phosphate, acidic bladder) Glass, ammonium chloride, ammonium sulfate, ammonium sulfate, sulfamic acid, etc.) and organic acids (C2-20, such as oxalic acid, succinic acid, malic acid, etc.). When the aqueous monomer solution is acidic, inorganic alkaline substances (hydroxylated) Sodium, potassium hydroxide, ammonia and the like) and organic alkaline substances (guanidine and the like).
In addition, pH here is a value measured at room temperature (20 degreeC) using the stock solution of monomer aqueous solution using a pH meter [For example, LAB pH meter M-12, a brand name, HORIBA, Ltd. make].

From the viewpoint of molecular weight and dispersed particle stability, the lower limit is preferably 10, more preferably 30, particularly preferably 40, most preferably 50, and the upper limit is preferably 95. Further preferred is 80, particularly preferred 70, most preferred 60. Further, during polymerization, it is preferable to adjust by appropriately heating and cooling so that the predetermined polymerization temperature is kept constant (for example, the 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, preferably 1 to 10 hours.

The end of the polymerization reaction can be confirmed by the point that the heat generation due to the polymerization is eliminated, but the polymerization time is 1 to 24 hours from the time when the polymerization start is confirmed by the normal heat generation, and the viewpoint that the polymerization is completed and the residual monomer is reduced. Therefore, the preferable lower limit is 2 hours, more preferably 3 hours, and the preferable upper limit from an industrial viewpoint is 12 hours, more preferably 10 hours. When the monomer is added dropwise 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 (kPa, hereinafter referred to as absolute pressure) is not particularly limited, but is usually carried out under atmospheric pressure. From the viewpoint of easy temperature control during polymerization, preferably the pressure at which the hydrophobic dispersion medium (c) boils at the polymerization temperature or the pressure at which (c) and water azeotrope is preferred, and the preferred lower limit of the pressure is 5, More preferably, it is 12, particularly preferably 25, and a preferable upper limit is 95, more preferably 80, particularly preferably 65.

  Further, (A) may be further subjected to a modification reaction. As the polymer modification method, for example, when acrylamide having a hydrolyzable functional group in the molecule is used as the water-soluble unsaturated monomer (a), a caustic alkali (sodium hydroxide, potassium hydroxide, etc.) during or after polymerization Alternatively, a method of adding an alkali carbonate (sodium carbonate, potassium carbonate, etc.) and partially hydrolyzing the amide group of (a) to introduce a carboxyl group (JP 56-16505 A, etc.); formaldehyde, A method in which dialkylamine (C1-12) and halogenated (chlorine, bromine, iodine, etc.) alkyl (C1-12) (methyl chloride, ethyl chloride, etc.) are added, and a cationic group is partially introduced by Mannich reaction; acrylonitrile Amino acids obtained by hydrolysis of nitrile groups such as vinylformamide A method of forming an amidine ring in a molecule by a ring-closing reaction with (a Japanese Patent Laid-Open No. 5-192513), and a method of adding a crosslinkable monomer (y) after polymerization to cause a cross-linking reaction (Japanese Patent No. 3305688) ) And the like.

In the present invention, (A) intrinsic viscosity [η] (measured value at 30 ° C. in 1N-NaNO ³ aqueous solution, unit is dl / g, the same shall apply hereinafter) is usually 1 to 40, and aggregation performance (high floc strength, floc) The lower limit is preferably 4, more preferably 6, particularly preferably 8, most preferably 9.5, and the upper limit preferable from the viewpoint of the aggregation rate. 30, more preferably 25, particularly preferably 20, and most preferably 18.

Further, the thread length (mm) of the 0.4% by weight aqueous solution of (A) in the present invention is not particularly limited, but in the nonionic and anionic polymer flocculants described later, it is usually 20 to 200 mm, preferably For a cationic and amphoteric polymer flocculant body, it is usually 5 to 100 mm, preferably 6 to 80 mm.
The thread length has a correlation with the molecular weight and molecular weight distribution, and becomes larger as the molecular weight is higher and the molecular weight distribution is wider. Further, at the same molecular weight (or intrinsic viscosity), the shorter the string length, the sharper the molecular weight distribution.

  Here, the string length (mm) can be measured using a stringiness measuring instrument manufactured by Kyowa Interface Science Co., Ltd. Take 0.80 g of water-soluble (co) polymer particles (in terms of solid content) in a 300 ml glass beaker, and add ion-exchanged water so that the total weight of the (co) polymer and ion-exchanged water is 200.0 g. Add quickly and stir using a glass rod or the like until the polymer swells and disperses uniformly (approximately 1 minute). At this time, care is taken so that the polymer does not remain. Then, after covering with a transparent resin film and allowing to stand at room temperature (about 20 ° C.) for about 20 hours, a plate-shaped PVC stirring blade (diameter 5 cm, height 2 cm, thickness 0.2 cm) is attached. And agitation at 120 rpm for 1 hour to prepare a 0.4 wt% aqueous solution of the measurement sample. After the temperature of the measurement sample was adjusted to 25 ± 2 ° C., a glass spheroid (hereinafter referred to as glass sphere) (short diameter 7 mm, long diameter 11 mm) attached to the lower end of the hanging thread of the spinnability measuring instrument The distance from the liquid surface to the lower end of the glass sphere until the glass sphere is pulled up at a speed of 16 mm / second and the yarn of the polymer aqueous solution is broken after being immersed in the measurement sample to a depth of 11 mm corresponding to the major axis and held for 15 seconds. Measure. The immersion position of the glass sphere is changed, the measurement is repeated 10 times, the average value is calculated, and the value is set as the string length (mm).

The polymer flocculant of the present invention is obtained in the form of hydrogel particles immediately after production, but it can be further dehydrated to obtain a solid particle polymer flocculant.
The dehydration method is not particularly limited, and after polymerization, a method of dehydrating by a drying method such as hot air drying, infrared drying, indirect heat drying (vacuum drying, stirring type dryer, drum dryer), or the like in a hydrophobic dispersion medium. A method of boiling and dehydrating under reduced pressure is conceivable. Moreover, these methods can be used together arbitrarily.

The weight average particle diameter (μm) of the polymer flocculant particles of the present invention is preferably 150, more preferably 200, particularly preferably 250, most preferably 300, to water, from the viewpoint of preventing dust generation during use. From the viewpoint of solubility, the upper limit is preferably 2,000, more preferably 1,700, particularly preferably 1,400, most preferably 1,000.
The weight average particle size (μm) is determined by using a low-tap test sieve shaker and a standard sieve defined in JIS Z8801-2000, Perry's Chemical Engineers Handbook, 6th edition (MacGlow Hill Book Company) Publication, 1984, p. 21).
That is, the above standard sieve having an appropriate opening, for example, opening of 2, 1.7, 1.4, 1.18, 11.0 mm, 850, 710, 500, 425, 355, 300, 250, 180 and 150 μm Take 50.0 g of the polymer flocculant particles on each standard sieve, shake for 1 minute with a low-tap test sieve shaker [eg, Iida Seisakusho Co., Ltd.], and weigh the sample remaining on each sieve To do. The results are plotted on logarithmic probability paper, and the particle diameter (median diameter) when the weight is 50% is defined as the weight average particle diameter.

Since the polymer flocculant of the present invention exhibits unprecedented specific flocculation performance, the polymer flocculant for flocculation treatment of industrial wastewater (hereinafter abbreviated as wastewater), and particularly sewage or human waste (hereinafter referred to as sewage sludge). And abbreviated to be a polymer aggregating agent for aggregating treatment.
In sewage sludge, the size of suspended particles is relatively large, and the surface of suspended particles in water has a negative charge. Agents and mixtures thereof are preferred.
Here, the cationic polymer flocculant is a polymer flocculant having a cationic group in the molecule, that is, a polymer flocculant exhibiting a cationic property when dissolved in water, and an amphoteric polymer flocculant and Is a polymer flocculant having a cationic group and an anionic group in the molecule, that is, a polymer flocculant exhibiting cationic and anionic properties when dissolved in water. About the cationic or anionic evaluation method of these polymer flocculants in water, it can obtain | require as a colloid equivalent value (meq / g). That is, the cationic group equivalent value in the cationic flocculant can be determined as the cation colloid equivalent value, and the cationic group equivalent value and the anionic group equivalent value in the amphoteric flocculant are the cationic colloid equivalent value and the anionic colloid respectively. It can be determined as an equivalent value.

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

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

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

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

Cation or anion colloid equivalent value (meq / g) = (1/2) × (sample titration)
-Titrate of blank test) x (N / 400 PVSK titer)

  The polymer flocculant of the present invention is an antifoaming agent (C1), a chelating agent (C2), a pH adjusting agent (C3), a surfactant (C4), as long as it does not inhibit the effects of the present invention. An additive (C) selected from the group consisting of an antiblocking agent (C5), an antioxidant (C6), an ultraviolet absorber (C7) and a preservative (C8) can be used in combination.

Examples of the antifoaming agent (C1) include silicone compounds [Mn 100 to 100,000, such as dimethylpolysiloxane, except for the above (B)], mineral oil (spindle oil, kerosene, etc.), metal soap (C12 to 22, Such as calcium stearate);
Examples of the chelating agent (C2) include aminocarboxylic acids (C6-24, such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylethylenediaminetriacetic acid, nitrilotriacetic acid, and triethylenetetraminehexaacetic acid), and polyvalent carboxylic acids [C4 to Mn10. 1,000, such as maleic acid, polyacrylic acid (Mn 1,000-10,000) and isoamylene / maleic acid copolymer (Mn 1,000-10,000)], hydroxycarboxylic acid (C3-10, such as citric acid, Gluconic acid, lactic acid and malic acid), condensed phosphoric acid (tripolyphosphoric acid, trimetaphosphoric acid, etc.) and their salts [alkali metal salts, alkaline earth metal salts, ammonium salts, alkylamines (C1-20, such as methylamine, ethylamine) , Kuchiruamin etc.) salts and alkanolamine (C2-12, such as mono-, - di - and triethanolamine) salts], and the like;

Examples of the pH adjuster (C3) include caustic alkalis (caustic soda, caustic potash, etc.), amines (C1-20, such as methylamine, ethylamine, mono-, di- and triethanolamine), inorganic acids (salts) [inorganic acids ( Hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, sulfamic acid, carbonic acid, etc.) and their metals [alkali metals, alkaline earth metals, etc.] salts (sodium carbonate, potassium carbonate, sodium sulfate, sodium hydrogen sulfate, monosodium phosphate, etc.) ) And ammonium salts (such as ammonium carbonate and ammonium sulfate)], organic acids (salts) [organic acids [carboxylic acids (C2-15, such as acetic acid, citric acid), sulfonic acids (C1-15, such as methanesulfonic acid, Ethanesulfonic acid, p-toluenesulfonic acid) and phenol], and their metal (same as above) salts (sodium acetate And lactic acid soda) and ammonium salts (ammonium acetate, ammonium lactate, etc.), etc.] and the like;

  As the surfactant (C4), surfactants described in US Pat. No. 4,331,447, such as polyoxyethylene nonylphenyl ether and sodium dioctylsulfosuccinate; as the antiblocking agent (C5), polyether-modified silicone oil ( Mn 100 to 3,000), for example, polyoxyethylene-modified silicone and polyoxyethylene / polyoxypropylene-modified silicone [provided that (B) is not included. ];

  Antioxidants (C6) include phenol compounds [hydroquinone, methoxyhydroquinone, catechol, 2,6-di-t-butyl-p-cresol (BHT) and 2,2′-methylenebis (4-methyl-6-t). -Butylphenol), etc.], sulfur-containing compounds [thiourea, tetramethylthiuram disulfide, dimethyldithiocarbamic acid and its salts [for example, metal (same as above) salts and ammonium salts, etc.], sodium sulfite, sodium thiosulfate, 2-mercapto Benzothiazole and salts thereof (same as above), dilauryl 3,3′-thiodipropionate (DLTDP) and distearyl 3,3′-thiodipropionate (DSTDP), etc.], phosphorus-containing compounds [triphenyl phosphite , Triethyl phosphite, sodium phosphite , Sodium hypophosphite, triphenyl phosphite (TPP) and triisodecyl phosphite (TDP) and the like] and nitrogen-containing compounds [amines (octylated diphenylamine, Nn-butyl-p-aminophenol and N, N-diisopropyl-p-phenylenediamine etc.), urea, guanidine and guanidine inorganic acid (same as above) salts] and the like;

Examples of the ultraviolet absorber (C7) include benzophenone compounds (2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, etc.), salicylate compounds (phenyl salicylate, 2,4-di-t-butylphenyl-3,5-di). -T-butyl-4-hydroxybenzoate, etc.), benzotriazole compounds [(2′-hydroxyphenyl) benzotriazole, (2′-hydroxy-5′-methylphenyl) benzotriazole, etc.] and acrylates [ethyl-2-cyano −3,3-diphenyl acrylate, methyl-2-carbomethoxy-3- (paramethoxybenzyl) acrylate, etc.] and the like;
Examples of the preservative (C8) include benzoic acid, paraoxybenzoic acid ester and sorbic acid.

The above (C) may be added in advance to the monomer aqueous solution before polymerization or may be added to the polymer after production. (C) The total amount used is usually 30% or less based on the monomer or polymer weight, and preferably 0 to 10% from the viewpoint of aggregation performance.
The amount of each additive of (C1) to (C8) used is based on the same weight as above, (C1) is usually 5% or less, preferably 1 to 3%, (C2) is usually 20% or less, Preferably 2 to 10%, (C3) is usually 10% or less, preferably 1 to 5%, (C4) and (C5) are each usually 5% or less, preferably 1 to 3%, (C6), (C7 ) And (C8) are each usually 5% or less, preferably 0.1 to 2%.

The method for adding the polymer flocculant of the present invention to sewage sludge or wastewater is not particularly limited, and examples thereof include the method described in Japanese Patent No. 13111340 or Japanese Patent No. 2038341.
The amount of the polymer flocculant used in the present invention varies depending on the type of sewage sludge or waste water, the content of suspended particles, the molecular weight of the polymer flocculant, etc., but there is no particular limitation, and evaporation residue in the sewage sludge or waste water. Based on the weight of the product (hereinafter abbreviated as TS), usually 0.01 to 10%, and the preferable lower limit from the viewpoint of agglomeration performance is 0.1%, more preferably 0.5%, particularly preferably 1%, and processing cost. From this viewpoint, the upper limit is preferably 5%, more preferably 3%, and particularly preferably 2%.

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

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

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

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

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

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In addition, the part in an Example represents a weight part and% represents weight%.
The intrinsic viscosity [η], the solid content, the weight average particle diameter, and the kite length of the polymer flocculant are measured by the above-described methods, and other evaluation items are as follows.
1. Adhesion rate (wt%)
Ratio based on the theoretical yield of polymer solids attached to the reaction vessel inner wall or stirring blade after polymerization.
2. Bonding rate (wt%)

Cohesion rate = 100 × (weight of agglomerates having an opening of 1,000 μm or more) / total dry matter weight

The weight of agglomerated material having a mesh size of 1,000 μm or more and the total dry matter weight in the above formula can be obtained by the following operation. That is, using a vacuum filtration type solid-liquid separator equipped with a Nutsche with a stainless steel filter medium having an opening of 105 μm, full vacuum is performed with a water circulation aspirator to obtain a cake of particles by separating the solvent. Is dried on a stainless steel bat and further dried at 90 ° C. under reduced pressure to obtain polymer particles (total dry matter weight), which is sieved to obtain an agglomerated product having a mesh size of 1,000 μm or more (agglomerated). Compound weight).

3. Water insoluble content (wt%)
Add 500 g of 0.1% sodium chloride aqueous solution into a 1 L beaker, add 2.5 g sample to the aqueous solution, and dissolve by stirring for 2 hours with a motor equipped with 50 mm long and 20 mm wide stirring blades. Let The lysate is filtered through a 100 μm mesh weighed in advance. The residue is placed on an aluminum dish together with the mesh and dried for 2 hours in a circulating air dryer at 120 ° C. Let the value calculated | required with the following formula be a water-insoluble amount (weight%).

Water-insoluble amount = 100 × [residue weight after drying (g)] / [sample weight at dissolution (g)]

In addition, it carried out according to the analysis method of TS in sludge, organic content (ignition loss), and a "sewage test method" (above) description. The floc particle size, filtrate amount, filter cloth peelability and cake moisture content in this example were evaluated according to the following methods.
<Flock particle size>
Jar tester [Miyamoto Riken Kogyo Co., Ltd., model JMD-6HS-A, and so on. ] Two plate-shaped stirring blades made of polyvinyl chloride (diameter 5 cm, height 2 cm, thickness 0.2 cm) were attached to the stirring bar continuously in a vertical shape so as to form a cross, and 200 ml of sludge was taken in a 300 ml beaker, Set it on the jar tester. The rotation speed of the jar tester was set to 120 rpm, and while gradually stirring the sludge, the aqueous solution of (A) having a predetermined concentration was added by a predetermined method. After stirring for 30 seconds, the stirring was stopped and the size of the floc was visually observed. [The floc particle size (unit: mm) at 120 rpm is shown in Table 2].
Subsequently, the number of revolutions was set to 300 rpm, and after stirring for 30 seconds, the stirring was stopped and the size of the floc was again visually observed. [Table 2 shows the floc particle size (unit: mm) at the number of revolution of 300 rpm] .

<Amount of filtrate>
Set T-1189 nylon filter cloth [Shikishima Kanbusu Co., Ltd., circular shape, diameter 9 cm], Nutsche funnel, 300 ml measuring graduated cylinder. Using a stopwatch, measure the amount of filtrate 60 seconds after the start.
<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: To do.

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 g of dehydrated cake after the filter cloth peelability test was weighed (W3) in a petri dish and dried in a circulating dryer until the water was completely evaporated (for example, at 105 ± 5 ° C. for 8 hours). Using the weight of the dry cake remaining on the petri dish as (W4), the moisture content of the cake is calculated from the following equation.

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

<Measurement method of Mw by GPC>
Apparatus: HLC-802A manufactured by Tosoh Corporation
Column: TSK gel GMH6 2 Measurement temperature: 40 ° C
Sample solution: 0.5 mass% tetrahydrofuran solution solution injection amount: 200 μl
Detector: Refractive index detector Standard: Polystyrene

Production Example 1
A reaction vessel equipped with a stirrer, heating / cooling device, thermometer, dropping funnel and nitrogen blowing tube was charged with 210 parts of IPA as a polymerization solvent, and after replacing the gas phase part of the reaction vessel with nitrogen, the temperature was raised to 80 ° C. under sealing. A monomer-initiator solution consisting of 1,092 parts of MA-i24, 210 parts of MA-EO9-Me, 98 parts of styrene and 2.8 parts of initiator AVN is added dropwise at a constant rate over 3 hours from the dropping funnel. The mixture was further aged at the same temperature for 3 hours. The obtained polymer solution was heated to 120 ° C., and IPA was removed under reduced pressure to obtain 1,290 parts of a dispersant (c-1) composed of a polymer having an Mw of 140,000.

Production Example 2
In Production Example 1, MA-i24 1,092 parts, MA-EO9-Me 210 parts, and styrene 98 parts, instead of MA-i24 910 parts and MA-PO12-Bu 490 parts, were used in Production Example 1 In the same manner, 1,220 parts of a dispersant (c-2) made of a polymer having an Mw of 120,000 was obtained.

Production Example 3
In Production Example 1, MA-i24 1,092 parts, MA-EO9-Me 210 parts, styrene 98 parts instead of MA-i32 980 parts, MA-EO12-Me 350 parts and n-butyl methacrylate 70 parts Except having used, it carried out similarly to manufacture example 1, and obtained 1,250 parts of dispersing agents (c-3) which consist of a polymer of Mw230,000.

Production Example 4
In Production Example 1, MA-i24 1,009 parts, MA-EO9-Me 210 parts, and styrene 98 parts instead of MA-EO-i24 980 parts and methacrylate n-hexyl methacrylate 420 parts were used in the production example. In the same manner as in Example 1, 1,300 parts of a dispersant (c-4) made of a polymer having an Mw of 290,000 was obtained.

  Table 1 shows the compositions of the obtained dispersants and Mw results for Production Examples 1 to 4.

Each symbol in the table represents the following compound.
MA-i24: 2-decyltetradecyl methacrylate MA-i32: 2-tetradecyl octadecyl methacrylate MA-EO9-Me: polyethylene glycol (p = 9) monomethyl ether monomer
Taacrylate MA-EO12-Me: Polyethylene glycol (p = 12) monomethyl ether mono
Methacrylate MA-PO3-Bu: Polypropylene glycol (p = 3) monobutyl ether mono
Methacrylate MA-EO3-i24: Polyethylene glycol (p = 3) mono-2-decyltetradecyl
Ether monomethacrylate

Example 1
A mixed solution of 839 parts of a 70% aqueous solution of methyl chloride salt of N, N-dimethylaminoethyl acrylate, 108 parts of 50% aqueous solution of acrylamide and 0.33 part of mercaptoacetic acid was prepared at room temperature (20-25 ° C.). Furthermore, the pH (20 ° C.) of the aqueous monomer solution was adjusted to 3.0 using sulfuric acid while monitoring with a pH meter. The obtained mixed solution was sufficiently substituted with nitrogen (purity 99.999% or more, the same applies hereinafter) (dissolved oxygen concentration 100 ppb or less), and then 1.94 parts of a 10% aqueous solution of azobisamidinopropane hydrochloride was added. A homogeneous solution was prepared to prepare an aqueous monomer solution.
Separately, 624 parts of cyclohexane was charged into a reaction vessel equipped with a reflux dehydration pipe, a dropping funnel, a nitrogen introduction pipe and a stirring blade (Max Blend blade), and then 6.24 parts of a dispersant (c-1) was added thereto. While stirring the stirring blade at a rotation speed of 340 rpm, the inside of the reaction vessel was purged with nitrogen (gas phase oxygen concentration of 10 ppm or less), and then heated to 57 ° C. After reaching 57 ° C., the inside of the reaction vessel is depressurized (60 kPa), the entire amount of the monomer aqueous solution previously charged in the dropping funnel is charged into the reaction vessel over 120 minutes, and stirred at 57 ° C. for 120 minutes after completion of the addition. Continued reverse phase suspension polymerization.
The polymer slurry after polymerization is supplied to a vacuum filter and subjected to solid-liquid separation, and then dried in a vacuum dryer (1.3 kPa, 40 ° C. × 2 hours) to obtain a true spherical shape having a weight average particle diameter of 490 μm. 695 parts of a polymer flocculant (A1) were obtained (solid content 93.2%).

Example 2
In Example 1, a true spherical polymer having a weight average particle size of 450 μm was used in the same manner as in Example 1 except that 6.24 parts of (c-2) was used instead of 6.24 parts of (c-1). As a result, 693 parts of a flocculant (A2) (solid content: 92.6%) was obtained.

Example 3
In Example 1, a spherical high particle having a weight average particle diameter of 410 μm was obtained in the same manner as in Example 1 except that 6.24 parts of (c-3) was used instead of 6.24 parts of (c-1). As a result, 687 parts of a molecular flocculant (A3) (solid content: 93.3%) were obtained.

Example 4
In Example 1, a true spherical polymer having a weight average particle size of 390 μm was used in the same manner as in Example 1 except that 6.24 parts of (c-4) was used instead of 6.24 parts of (c-1). 689 parts of flocculant (A4) (solid content 93.1%) were obtained.

Example 5
In Example 1, instead of 839 parts of 70% aqueous solution of methyl chloride salt of N, N-dimethylaminoethyl acrylate, 904 parts of 64% aqueous solution of methyl chloride salt of N, N-dimethylaminoethyl methacrylate and 50% aqueous solution of acrylamide 50% 643 parts of a true spherical polymer flocculant (A5) having a weight average particle size of 490 μm in the same manner as in Example 1 except that 44.0 parts were used instead of 0.3 parts and 0.33 parts of mercaptoacetic acid were not used. (Solid content 93.5%) was obtained.

Example 6
In Example 1, instead of 839 parts of 70% aqueous solution of methyl chloride salt of N, N-dimethylaminoethyl acrylate, 344 parts of 64% aqueous solution of methyl chloride salt of N-dimethylaminoethyl methacrylate, 108 parts of 50% aqueous solution of acrylamide A spherical polymer flocculant (A6) having a weight average particle size of 430 μm was used in the same manner as in Example 1 except that 603 parts of the above were used and 2.60 parts of the mercaptoacetic acid were used instead of 0.33 parts. 556 parts (solid content 93.8%) were obtained.

Example 7
In Example 1, instead of 839 parts of 70% aqueous solution of methyl chloride salt of N, N-dimethylaminoethyl acrylate and 108 parts of 50% aqueous solution of acrylamide, 70% of methyl chloride salt of N, N-dimethylaminoethyl acrylate 152 parts of aqueous solution, 469 parts of 50% aqueous solution of acrylamide, 268 parts of 64% aqueous solution of methyl chloride salt of N, N-dimethylaminoethyl methacrylate and 59.4 parts of acrylic acid were used instead of 0.33 parts of mercaptoacetic acid. Example 1 except that 0.57 part was used, 1.7 part was used instead of 1.94 part of a 10% aqueous solution of azobisamidinopropane hydrochloride, and 11.4 parts of monosodium phosphate was used. Similarly, 627 parts of a true spherical polymer flocculant (A7) having a weight average particle diameter of 390 μm (solid content 9 .1%) was obtained.

Example 8
In Example 1, instead of 839 parts of 70% aqueous solution of methyl chloride salt of N, N-dimethylaminoethyl acrylate and 108 parts of 50% aqueous solution of acrylamide, 70% of methyl chloride salt of N, N-dimethylaminoethyl acrylate 407 parts of aqueous solution, 293 parts of 50% aqueous solution of acrylamide, 95.5 parts of 64% aqueous solution of methyl chloride salt of N, N-dimethylaminoethyl methacrylate, and 148 parts of acrylic acid were used in place of 0.33 part of mercaptoacetic acid. Except for using 3.22 parts and further using 12.8 parts of monosodium phosphate, 695 parts of a true spherical polymer aggregate (A8) having a weight average particle diameter of 380 μm (solid content) 93.7%).

Comparative Example 1
In Example 1, instead of 6.24 parts of (c-1), 6.24 parts of a copolymer of alkene (C30 or more) and maleic anhydride [Diacarna 30, trade name, manufactured by Mitsubishi Chemical Corporation] Except that it was used, in the same manner as in Example 1, 694 parts of polymer flocculant (ratio A1) that was agglomerated (with 10 or more spherical particles coalesced) (solid content 92.8%) was obtained. It was.

Comparative Example 2
(C-1) True spherical polymer agglomeration having a weight average particle diameter of 320 μm in the same manner as in Example 1 except that 18.7 parts of a copolymer of alkene and maleic anhydride were used instead of 6.24 parts. 696 parts of an agent (ratio A2) (solid content 93.0%) was obtained.

Comparative Example 3
308 parts of a 78% aqueous solution of methyl chloride salt of N, N-dimethylaminoethyl acrylate, 650 parts of a 50% aqueous solution of acrylamide, and 925 parts of ion-exchanged water were prepared at room temperature (20-25 ° C.). Furthermore, the pH (20 ° C.) of the aqueous monomer solution was adjusted to 3.0 using sulfuric acid while monitoring with a pH meter. After this monomer aqueous solution was adjusted to 10 ° C., it was charged into an adiabatic reaction vessel, and the inside of the polymerization tank was sufficiently substituted with nitrogen (gas phase oxygen concentration of 10 ppm or less). After nitrogen substitution, 11.3 parts of a 5% aqueous solution of azobisamidinopropane hydrochloride, 0.9 part of a 0.1% aqueous solution of hydrogen peroxide, and 0.8 part of a 0.1% aqueous solution of ascorbic acid were added. After about 10 minutes, the liquid temperature began to rise, and the reaction system gradually thickened to obtain a gel-like polymer. When the heat generation is no longer observed, the temperature is maintained, and after 7 hours, the gel is chopped (1 mm square), dried with hot air at 75 ° C. for 5 hours, pulverized with a mixer, and powdered polymer 608 parts of a flocculant (ratio A3) (solid content 92.8%) were obtained.

  For Examples 1 to 8 and Comparative Examples 1 to 3, the results of adhesion rate, coalescence rate, weight average particle diameter, intrinsic viscosity, string length and water-insoluble content of the obtained polymer flocculant are shown in Table 1. Show. In Comparative Example 3, for comparison with the reverse phase suspension polymerization of the present invention, the results of the weight average particle diameter, intrinsic viscosity, string length and water-insoluble content of the polymer flocculant obtained by aqueous solution polymerization. Indicates.

(* 1): α-olefin / maleic anhydride copolymer [trade name “Diacarna 30”,
[Mitsubishi Chemical Corporation]

Each symbol in the table represents the following compound.
DAA: methyl chloride salt of N, N-dimethylaminoethyl acrylate DAM: methyl chloride salt of N, N-dimethylaminoethyl methacrylate AAM: acrylamide AAC: acrylic acid

  From Table 2, it can be seen that in Examples 1 to 8, both the adhesion rate and the coalescence rate are small and the weight average particle diameter of the polymer flocculant is large compared to Comparative Examples 1 to 3. In addition, it can be seen that the polymer flocculants of Examples 1 to 8 are less likely to agglomerate compared to the polymer flocculant of Comparative Example 2 although the amount of dispersant used is small. Furthermore, Example 2 shows that the molecular weight distribution is sharp, and the aqueous phase concentration is high and the productivity is high, since the string length is shorter than that of Comparative Example 3 having the same intrinsic viscosity.

Example 9, Comparative Example 4
(A1) and (Ratio A1) were each dissolved in ion-exchanged water to obtain an aqueous solution having a solid content of 0.2%. 200 g of excess sludge [pH 4.5, TS 2.9%, organic content 78.3%] collected from the T treatment plant was placed in a 300 ml beaker, and each of the aqueous solutions 15, 17 and 20 g of (A1) and (Ratio A1). Is added to each sludge (the solid content at this time is 0.5, 0.6, 0.7% / TS, respectively) and thoroughly stirred and mixed with a hand mixer. The diameter, filtrate amount, filter cloth peelability and cake moisture content were measured. The results are shown in Table 2.
From Table 3, in Example 9, compared to Comparative Example 4, flocs having a large particle diameter were formed, and the flocs once formed were not easily broken even under high agitation (300 rpm) (the floc strength was high). It can be seen that an excellent effect in peelability and dewaterability (cake water content) is exhibited, and that the agglomeration performance is less dependent on the added amount.

The polymer flocculant of the present invention exhibits an unprecedented flocculation performance, so it is suitable as a polymer flocculant for dewatering organic sludge such as sewage and human waste, or inorganic wastewater such as factory wastewater. Used.
In addition to the above-described polymer flocculants, the polymer flocculants of the present invention include drilling, muddy water flocculants, papermaking agents (formation aids for paper industry, drainage yield improvers, drainage improvements Agent, paper strength enhancer, valuable water recovery agent in white water), crude oil production additive (crude oil secondary and tertiary recovery additive), dispersant, scale inhibitor, coagulant, decolorizer, thickener , Antistatic agents, fiber treating agents, and the like. More preferred are polymer flocculants and papermaking agents.
Even when the polymer flocculant of the present invention is used as a papermaking agent, it can be suitably used due to the same effect as the polymer flocculant. That is, by adding the water-soluble polymer of the present invention to the pulp slurry in the papermaking process, a stronger cohesive force between the pulps can be realized, thereby improving dewaterability (drainage) and pulp yield during the papermaking process. A stronger paper strength enhancing effect (burst strength, folding strength, tensile strength) can be obtained.

Claims (3)

A water-soluble (co) polymer (A) obtained by reverse-phase suspension polymerization using a water-soluble unsaturated monomer (a), a hydrophobic dispersion medium (b) and a dispersant (c), A polymer flocculant comprising a polymer obtained by (co) polymerizing a monomer represented by the following general formula (1).
[Wherein, R ¹ represents H or a methyl group, A represents an alkylene group having 2 to 4 carbon atoms, n represents 0 or an integer of 1 to 20, and R ² represents a branched alkyl group having 16 to 44 carbon atoms. ] In the method for producing a polymer flocculant comprising a water-soluble (co) polymer (A), a dispersed phase comprising a water-soluble unsaturated monomer (a) and a radical polymerization initiator (d), and a hydrophobic dispersion medium (B) and reverse phase suspension polymerization using a continuous phase containing a dispersing agent (c) comprising a polymer obtained by (co) polymerizing monomers represented by the following general formula (1): A method for producing a polymer flocculant.
[Wherein, R ¹ represents H or a methyl group, A represents an alkylene group having 2 to 4 carbon atoms, n represents 0 or an integer of 1 to 20, and R ² represents a branched alkyl group having 16 to 44 carbon atoms. ] A method for treating sludge or wastewater, wherein the polymer flocculant according to claim 1 is added to and mixed with sludge or wastewater to form a floc, and solid-liquid separation is performed.