JP4289880B2 - Polymer flocculant - Google Patents

Description

【００６３】
表中の記号はそれぞれ次の化合物を表す。
ＡＡｍ：アクリルアミド
ＮａＡ：アクリル酸ソーダ
ＤＡＭＱ：塩化トリメチルアミノエチルメタクリレート
【００６４】
実施例および比較例における水相中および全系中のモノマー濃度（％）および重合時の最高到達温度（℃）と、実施例および比較例で得られた高分子凝集剤の固有粘度（ｄｌ／ｇ）、曳糸長（ｍｍ）、不溶解分（％）、粒径分布［粒径１８０μｍ未満の粒子の含有量（％）および１，８００μｍを超える粒子の含有量（％）］、フラクタル次数、真球度および発塵度（ＣＰＭ）を表２に示す。
【００６５】
【表２】

【００６６】
表２より、実施例１〜９の（共）重合体は、それぞれ対応する比較例１〜３の（共）重合体と比較して、不溶解分の発生がほとんどなく、高い固有粘度で、曳糸長が小さいことがわかる。また水溶液重合と比較した場合は、同程度の固有粘度でありながら、曳糸長が小さく分子量分布が狭いこと、さらに粒径分布、フラクタル次数、真球度および発塵度の結果から微粉発生が極めて少ないことがわかる。
【００６７】
凝集剤の性能評価例１
実施例１〜５および比較例４で得た高分子凝集剤を用いて、Ｋ砂利洗浄場廃水（懸濁物質０．３５％、ｐＨ６．０）にて凝沈試験を行った。結果を表３に示す。凝沈試験は廃水３００ｍｌを栓付き３００ｍｌメスシリンダー（沈降管）に入れ、これに凝集剤の０．１％イオン交換水溶液を室温にて所定量添加した。次にこの沈降管を１０回転倒させて廃水と凝集剤水溶液とを混合させ、フロックを形成させた後、沈降管を静置してフロック層の界面の沈降速度を測定した。凝沈速度はｍ／時間で表す。
表３から、本発明の凝集剤は比較例の凝集剤に比較して、低添加量で高い凝沈速度（凝沈性）が得られることがわかる。
【００６８】
【表３】

【００６９】
凝集剤の性能評価例２
実施例６〜９および比較例３、５で得た高分子凝集剤を用いて、Ｔ下水処理場混合生汚泥（固形分濃度１．１％、ｐＨ６．９、有機分７８％）にて脱水試験を行った。結果を表４に示す。
なお、脱水試験は汚泥２００ｍｌを３００ｍｌビーカーにとり、これに凝集剤の０．１％イオン交換水溶液を室温にて所定量加え、ジャーテスターにて１８０ｒｐｍで１分間撹拌してフロックを形成させた。これを小型遠心脱水機（１，５００Ｇ）で脱水して、得られた脱水ケーキの含水率を測定した。ケーキ含水率は％で表す。
表４から、本発明の凝集剤は比較例の凝集剤に比較して、低添加量で高い脱水率（低いケーキ含水率）が得られることがわかる。
【００７０】
【表４】

【００７１】
【発明の効果】
本発明の高分子凝集剤は、つぎの効果を奏することから極めて有用である。
（１）高モノマー濃度の重合条件で得られるにも拘わらず、水への不溶解分が極めて少ない。
（２）高モノマー濃度の重合条件で得られるため乾燥が容易で、後の乾燥工程の簡略化が図れる。
（３）粒径分布が狭く、しかも微粉が極めて少ないため、水への溶解が容易であり、また微粉による作業環境の悪化をもたらすこともない。
（４）真球状で、表面が滑らかであるため、輸送時や取り扱い時に微粉を生じる可能性が低く、上記の微粉による弊害をもたらすことがない。
（５）高分子量かつ狭い分子量分布を有するため、低添加量で優れた凝集効果を発揮する。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polymer flocculant. More specifically, the present invention relates to a polymer flocculant useful for agglomeration and sedimentation of industrial wastewater, for dewatering sewage sludge, for tertiary recovery of oil, for improving drainage yield in papermaking processes, or for enhancing paper strength.
[0002]
[Prior art]
As a polymer flocculant, nonionic, anionic, cationic and amphoteric obtained by radical polymerization of ethylenically unsaturated monomer by aqueous solution polymerization method, thin film polymerization method, suspension polymerization method, precipitation polymerization method and emulsion polymerization method, etc. High molecular weight (co) polymers are known.
[0003]
[Problems to be solved by the invention]
However, in the aqueous solution polymerization method, it is difficult to control the molecular weight in high-concentration polymerization of monomers due to the difficulty of heat removal during polymerization, and the generation of insoluble components is inevitable. In other polymerization methods, it is easy to control the molecular weight in high-concentration polymerization of monomers, but in the thin film polymerization method, suspension polymerization method and precipitation polymerization method, the final product powder form is indeterminate, so fine powder is generated. The problem is that the working environment is deteriorated and the water dissolution takes a long time, and the emulsion polymerization has a problem in transportation due to the final product being liquid.
[0004]
[Means for Solving the Problems]
The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems. That is, in the present invention, the ethylenically unsaturated monomer (a) is represented by the radical polymerization initiator (b) and the following general formula (1). , (A) 100-100,000 ppm It comprises a (co) polymer (A) obtained by reverse-phase suspension polymerization at a monomer concentration of 40 to 98% by weight in the aqueous phase in the presence of a chain transfer agent (c) for radical polymerization, Polymer flocculants having a length of 60 to 120 mm for nonionic and anionic (co) polymers and 5 to 90 mm for cationic (co) polymers; and for coagulating sedimentation of industrial wastewater and dewatering of sewage sludge The above-mentioned polymer flocculant for tertiary recovery of oil, improvement of drainage yield in papermaking process, or enhancement of paper strength.
[0005]
Q [(C = O) _p (X ¹ ) _x [(X ² ) _y -A ¹ -(C = O) _q -X ^Three ] _m -T] _n (1)
[Wherein Q is an n-valent organic group; X ¹ And X ^Three Is O, S or NH; X ² Is a carbonyl group or —CONH—; at least a portion of T is of the formula — (C═O) _r -(A ² ) _t A group represented by -Z, the remainder may be H; Z is a chain transfer group; A ¹ Is an alkylene group having 1 to 8 carbon atoms or the formula -A ^Three -X ^Four -X ^Three -A ^Four A group represented by-; ^Three And A ^Four Is a divalent hydrocarbon group having 2 to 20 carbon atoms; X ^Four Is a carbonyl group or —NHCO—; A ² Is an alkylene group having 1 to 8 carbon atoms, or when Z is SH, A ² Is the formula -CH ₂ -CH (X ^Five H) -CH ₂ A group represented by-(X ^Five Is O or S); p, q, r, t, x and y are each 0 or 1; m is 0 or an integer of 1 to 50; n is an integer of 1 to 100; Inside and [] may be the same or different. ]
[0006]
In the general formula (1), the n-valent organic group Q includes a residue obtained by removing n active hydrogen atom-containing groups from an organic compound having an active hydrogen atom-containing group.
The active hydrogen atom-containing group includes a hydroxyl group, a primary or secondary amino group, a carboxyl group, a thiol group, and a combination of two or more thereof; as the residue Q, for example, a hydroxyl group-containing compound (monovalent or polyvalent) A residue obtained by removing a hydroxyl group from a monohydric alcohol or a monohydric or polyhydric phenol), a primary or secondary amino compound [a primary or secondary amine (mono or polyamine), amino alcohol, etc.] to a primary or secondary Residue excluding amino group (or amino group and / or hydroxyl group), carboxyl group-containing compound [monovalent or polyvalent carboxylic acid, hydroxy acid, amino acid, etc.] to carboxyl group (or carboxyl group and / or hydroxyl group or amino acid) And thiol group-containing compounds (monovalent or polyvalent thiol, It is a hydroxyl group, a carboxyl group and / or thiol groups (or thiol groups and / or hydroxyl groups from a thiol) having an amino group, residue and the like, excluding a carboxyl group and / or amino group).
[0007]
Examples of the alcohol include the following, and a mixture of two or more thereof.
・ Monohydric alcohol
Aliphatic alcohols (C1-C8, such as methanol, ethanol, n- and i-propanol, hexanol, 2-ethylhexanol), alicyclic alcohols (C5-C10, such as cyclopentanol, cyclohexanol), Monools having aromatic fatty alcohols (7 to 20 carbon atoms such as benzyl alcohol and phenylethyl alcohol) and tertiary amino groups (1 to 10) [dihydrocarbyl alkanolamines having 6 to 15 carbon atoms (the following 2 N-hydroxyalkylated products of primary monoamines: diethylethanolamine, etc.), N-hydroxyalkylated products of aliphatic secondary amines having the following tertiary amino groups
Such].
[0008]
・ Polyvalent (2 to 100 or more, preferably 2 to 8) alcohols
Dihydric alcohols [aliphatic glycols having 2 to 20 carbon atoms (preferably 2 to 8 carbon atoms) (alkylene glycols such as ethylene glycol, 1,2- and 1,3-propylene glycol, 1,2-, 1,3- and 1,4-butanediol, 1,6-hexanediol, neopentyl glycol), alicyclic diol having 5 to 20 carbon atoms (cyclopentanediol, cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A, etc.), carbon number 8-16 araliphatic diols (such as dihydroxymethylbenzene)]; and trihydric to octahydric or higher polyols, such as (cyclo) alkane polyols (representing alkane polyols and / or cycloalkane polyols, and so on) ), Intramolecular and intermolecular Water products [C3-C12 aliphatic triols (glycerin, trimethylolpropane, trimethylolethane, hexanetriol, etc.), C4-C20 tetraols (pentaerythritol, diglycerin, sorbitan, etc.), pentitol ( Adonitol, arabitol, xylitol, etc.), hexitol (sorbitol, mannitol, iditol, tallitol, dulcitol, etc.), polyglycerin (degree of polymerization 3-10) (triglycerin, tetraglycerin, etc.), polypentaerythritol (dipentaerythritol, tripenta) Erythritol, etc.), cycloalkane polyols [tetrakis (hydroxymethyl) cyclohexanol, etc.], saccharides and their derivatives (glycosides, etc.) [monosaccharides (glucose, mannose, etc.) Fructose, sorbose, etc.), oligosaccharides (sucrose, clehalose, lactose, raffinose, etc.), and glycosides [alkyl (carbon number 1-4) glucoside (methyl glucoside, etc.)], alkylene glycol or alkane polyol (ethylene glycol, glycerin, Glucoside of trimethylolpropane, hexanetriol, etc.]], polyol having tertiary amino group (1-10) [trialkanolamine having 6 to 15 carbon atoms (such as triethanolamine), monohydrocarbyl dialkanolamine (N, N-dihydroxyalkylated products of the following primary monoamines: ethyldiethanolamine, N, N-dihydroxyethylaniline, etc.), polyN-hydroxyalkyl-substituted products of the following polyamines (N, N, N ′ N'- tetra-hydroxyethyl ethylenediamine, etc.), the degree of polymerization unsaturated alcohols of up to 100 [number 2-4 or more carbon, such as vinyl alcohol, such as polymer (polyvinyl alcohol (meth) allyl alcohol]).
[0009]
. (Poly) oxyalkylene mono- and polyols
Compound having 1 or 2 to 100 (preferably 2 to 8) active hydrogen atoms (the above monohydric alcohol, polyhydric alcohol, monohydric or polyhydric phenol, primary or secondary amine described below, Alkylene oxide adduct of a carboxyl group-containing compound and a thiol group-containing compound) or a methylene chloride-coupled product of the above polyhydric alcohol and / or alkylene oxide adduct thereof (methylene ether) And bonded through a group).
Examples of the alkylene oxide include alkylene oxides having 2 to 4 carbon atoms (hereinafter abbreviated as AO), ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), 1,2-, 2,3-, 1,3- and 1,4-butylene oxide and combinations of two or more of these (random and / or block addition) are included. The number of added moles is usually 1-50, preferably 1-10, per active hydrogen atom.
[0010]
Examples of phenol include the following and mixtures of two or more thereof.
・ Monohydric phenol
Monocyclic [C6-C20, such as (alkyl) phenol (cresol, ethylphenol, butylphenol, octylphenol, nonylphenol, dinonylphenol, etc.), alkoxy or amino-substituted phenol (methoxyethylphenol, guaiacol, aminophenol, etc.)], and Polycyclic [C10-20, such as phenylphenol, styrenated phenol, hydroxybiphenyl, naphthol].
・ Polyhydric phenol
Divalent phenol [monocyclic (C6-C16, for example, hydroquinone, resorcin), polycyclic [C13-C20, for example, bisphenol (bisphenol F, bisphenol A, bisphenol S, etc.)], trivalent to tetravalent Or more polyphenols [monocyclic (C6-C16, for example, 1,2,3-trihydroxybenzene, 1,3,5-trihydroxybenzene), polycyclic [C13-20 or more] , For example, 2,3,4-trihydroxybenzophenone, condensate of phenol and formaldehyde (novolak), polyphenol, etc.]].
[0011]
Examples of the primary or secondary amino compound include the following and a mixture of two or more thereof.
・ Primary or secondary monoamine
Primary amine [aliphatic amine (C1-C22, alkyl or alkenylamine such as methylamine, ethylamine, propylamine, pentylamine, 2,2-dimethylpropylamine, 2-ethylbutylamine, 2,2-dimethylbutylamine , Hexylamine, octylamine, 2-ethylhexylamine, n- and i-decylamine, laurylamine, oleylamine), alicyclic amine (4 to 10 carbon atoms, for example, cyclopentylamine, cyclohexylamine), aromatic amine (carbon number) 5 to 12, for example, aniline, toluidine, anisidine, aminoacetanilide, naphthylamine), araliphatic amine (carbon number 7 to 15, for example, benzylamine, phenylethylamine), carbon number having tertiary amino group (1 to 10) 4 ~ 2 Aliphatic primary amines [N, N-dialkylalkylenediamine (for example, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-diethylpropylenediamine, N, N-dimethylhexamethylenediamine, etc.), N , N, N′-trialkyldialkylenediamine (eg 1,1,4-trimethyldiethylenetriamine), tetraalkyltrialkylenetetramine (eg 1,1,4,7-tetramethyltriethylenetetramine)]]; Secondary amines [aliphatic amines (2-15 carbon atoms, dialkylamines such as dimethylamine, methylbutylamine, methyl-t-butylamine, methyl-2-ethylhexylamine, methylisodecylamine, dibutylamine, diisobutylamine, di-t -Butylami , Butylpentylamine, dipentylamine), alicyclic amine (5 to 20 carbon atoms, dicycloalkyl or alkylcycloalkylamine such as methylcyclohexylamine), aromatic amine (5 to 20 carbon atoms such as pyrrole, methyl) Pyrrole), heterocyclic amines (5 to 10 carbon atoms, for example, piperidine, pipecoline, morpholine), aliphatic secondary amines having 5 to 20 carbon atoms having a tertiary amino group (1 to 10) (N, N, N′-triethylethylenediamine, N, N, N ′, N′-tetramethyldiethylenetriamine, etc.)].
[0012]
.Primary or / and secondary polyamines
Aliphatic polyamines [diamines (2 to 12 carbon atoms, preferably 2 to 6 carbon atoms, alkylenediamines such as ethylenediamine, propylenediamine, hexamethylenediamine), poly (degree of polymerization 2 to 10) alkylene (carbon atoms 2 to 4) polyamines (diethylenetriamine) , Triethylenetetramine, etc.]], cycloaliphatic polyamines [diamines (C5-C20, such as cyclohexanediamine, isophoronediamine, cyclohexylenediamine, dicyclohexylmethanediamine, etc.)], aromatic polyamines (C6-C20, such as Phenylenediamine, toluylenediamine, methylenedianiline, diphenyl ether diamine), araliphatic polyamines (7 to 15 carbon atoms, such as xylylenediamine), heterocyclic polyamines (4 to 10 carbon atoms, such as pyridine) Razin, aminoethylpiperazine), partially alkylated (1 to 4 carbon atoms) of these polyamines, and (poly) amide polyamines [the following dicarboxylic acids (aliphatic dicarboxylic acids and / or dimer acids) and excess polyamines (alkylenes) Reaction products with diamines, polyalkylene polyamines, etc.].
. (Poly) oxyalkylene mono- and polyamines
Aminoalkyl ether of the above alcohol [monohydric alcohol, polyhydric alcohol, (poly) oxyalkylene mono- and polyol] [for example, cyanoethylated by reacting acrylonitrile and then hydrogenated to aminopropyl ether]
・ Amino alcohol
Mono- and dialkanolamines having 2 to 12 carbon atoms (monoethanolamine, diethanolamine, etc.).
[0013]
Examples of the carboxyl group-containing compound include the following and a mixture of two or more thereof.
・ Monovalent carboxylic acid
Aliphatic carboxylic acid (C1-C20, such as formic acid, acetic acid, propionic acid, 2-ethylhexanoic acid, lauric acid, oleic acid, stearic acid), alicyclic carboxylic acid (C6-C20, such as cyclopentane) Carboxylic acid, cyclohexanecarboxylic acid), aromatic carboxylic acid (carbon number 7 to 20, for example, benzoic acid, diphenylcarboxylic acid) and the like.
[0014]
・ Polyvalent (bivalent to 100 or higher) carboxylic acid
Dicarboxylic acids [aliphatic dicarboxylic acids [2 to 40 carbon atoms such as maleic acid, fumaric acid, succinic acid, adipic acid, sebacic acid, malonic acid, azelaic acid, mesaconic acid, citraconic acid, glutaconic acid, carbon number in the side chain Alkyl or alkenyl succinic acid having 4 to 35 hydrocarbon groups (such as isododecenyl succinic acid and n-dodecenyl succinic acid)], alicyclic dicarboxylic acid (having 6 to 40 carbon atoms, such as 1,3-cyclobutanedicarboxylic acid, 1,2- and 1,4-cyclohexanedicarboxylic acid 1,3- and 1,4-dicarboxymethylcyclohexane, methylmedicic acid, dimer acid), aromatic dicarboxylic acid (carbon number 8-20, such as phthalic acid, isophthalic acid) Terephthalic acid, toluene dicarboxylic acid, naphthalene dicarboxylic acid, etc.)] Carboxylic acid [aliphatic polycarboxylic acid [carbon number 7 to 20, for example, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylene Carboxypropane, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid], alicyclic polycarboxylic acid (9 to 20, for example, 1,2,4-cyclohexanetricarboxylic acid), aromatic Group polycarboxylic acid (carbon number 9-20, for example 1,2,4- and 1,2,5-benzenetricarboxylic acid, 1,2,4- and 2,5,7-naphthalenetricarboxylic acid, trimellitic acid, Pyromellitic acid, benzophenone tetracarboxylic acid, etc.)], unsaturated carboxylic acids up to a degree of polymerization of 100 ((a12-1) described below, for example (meth) a Polymers of acrylic acid], carboxymethylated aliphatic carboxylic acid [the polyamine having a tertiary amino group (1-10) (alkylenediamine, etc.) (e.g., ethylenediaminetetraacetic acid)], etc.].
. (Poly) oxyalkylene mono- and polycarboxylic acids
Carboxyalkyl ether of the above alcohol [monohydric alcohol, polyhydric alcohol, (poly) oxyalkylene mono- and polyol] [for example, carboxymethylated by reacting halocarboxylic acid (monochloroacetic acid etc.) in the presence of alkali]
[0015]
・ Hydroxy acid
Aliphatic hydroxy acids [2-20 carbon atoms such as glycolic acid, lactic acid, tartronic acid, glyceric acid, malic acid, tartaric acid, ricinoleic acid, and ω-oxycarboxylic acid (ω-oxycaproic acid, ω-oxyenanthic acid, [omega] -oxycaprylic acid, [omega] -oxypelargonic acid, [omega] -oxycapric acid, [omega] -oxyundecanoic acid, [omega] -oxidedecanoic acid, etc.]], aromatic hydroxy acids (C7-20, such as salicylic acid, p-hydroxy) Benzoic acid, tropic acid, benzylic acid, di- and tri-hydroxybenzoic acid).
·amino acid
C2-C20 aliphatic, heterocyclic and aromatic amino acids such as glycine, leucine, alanine, glutamic acid, aspartic acid, arginine, citrulline, threonine, cystine, arginine, leucine, isoleucine, lysine, serine, tyrosine, valine, Proline, hydroxyproline, threonine, valine, methionine, lysine, ornithine, tyrosine, phenylalanine, tryptophan, phenylglycine, anthranilic acid (these amino acids may be D-form and L-form each alone or a mixture of any mixing ratio), And ω-aminocarboxylic acids (ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopelargonic acid, ω-aminocapric acid, ω-aminoundecanoic acid, ω-aminododecanoic acid, etc.).
[0016]
Examples of the thiol group-containing compound include the following and a mixture of two or more thereof.
・ Monovalent thiol
Aliphatic thiol (C1-C20, for example, methanethiol, ethanethiol, propanethiol, n-octanethiol, n-dodecanethiol, hexadecanethiol, n-octadecanethiol); alicyclic thiol (C5-20, For example, cyclopentanethiol, cyclohexanethiol); araliphatic thiol (C7-20, such as toluenethiol, xylenethiol); aromatic thiol (C6-12, such as benzenethiol, thiocresol, thiolenol).
・ Multivalent thiol
Dithiol [aliphatic dithiol (C2-C40, such as ethanedithiol, n-, i- and sec-propanedithiol, 1,3- and 1,4-butanedithiol, 1,6-hexanedithiol, neopentanedithiol) , Alicyclic dithiol (C5-20, such as cyclopentanedithiol, cyclohexanedithiol), aromatic dithiol (C6-16, such as benzenedithiol, biphenyldithiol)] and the like.
[0017]
・ Thiols with hydroxyl, carboxyl and / or amino groups
C2-C20, for example, mercaptoalcohol (such as ethylene thioglycol), mercaptophenol (such as thiocatechol and mercaptonaphthol), mercaptocarboxylic acid (such as mercaptobenzoic acid, thiosalicylic acid, thioglycolic acid, and cysteine)].
[0018]
In the general formula (1), examples of the chain transfer group Z include SH and SR. ¹ , SSR ¹ , CG _Three Etc. Where R ¹ Can be substituted with 1 to 20 carbon atoms (preferably 1 to 4 hydroxyl groups, carboxyl groups, amino groups, cyano groups, nitro groups and / or halogens (Cl, Br, etc.)), (cyclo ) Represents an alkyl group, an (alkyl) aryl group, an aralkyl group, an alkoxy group or an allyloxy group; G represents a halogen (Cl, Br, etc.). Of these chain transfer groups, SH is preferable from the viewpoint of controlling the molecular weight of the obtained (co) polymer.
In general formula (1), all of T are represented by the formula-(C = O). _r -(A ² ) _t -Z is preferred, but a part of T (preferably 2 or more) is represented by the formula-(C = O). _r -(A ² ) _t The remainder of the group represented by -Z may be H.
[0019]
A in general formula (1) ¹ And A ² As the alkylene group, an alkylene group having 2 to 8 carbon atoms such as ethylene group, 1,2- and 1,3-propylene group, 1,2-, 2,3-, 1,3- and 1,4- A butylene group, an isobutylene group, a 1,2-alkylene group having 5 to 8 carbon atoms, a penta- to octa-methylene group, and a residue of the ω-oxycarboxylic acid or ω-aminocarboxylic acid (carboxyl group and hydroxyl group or amino group). A group excluding a group), a residue of the mercaptoalcohol, mercaptophenol or mercaptocarboxylic acid (a group excluding a thiol group and a hydroxyl group or a carboxyl group), and a combination of two or more of these.
When Z is SH, A ² Is -CH ₂ -CH (OH) -CH ₂ -Or -CH ₂ -CH (SH) -CH ₂ -May be sufficient.
A ¹ Of which -A ^Three -X ^Four -X ^Three -A ^Four The group represented by-has formula -A ^Three -CO-O-A ^Four -, -A ^Three -CO-SA ^Four -, -A ^Three -CO-NH-A ^Four -, -A ^Three -NH-CO-OA ^Four -, -A ^Three -NH-CO-SA ^Four -, And -A ^Three -NH-CO-NH-A ^Four A group represented by-is included. Divalent hydrocarbon group A ^Three And A ^Four Includes an alkylene group having 2 to 20 carbon atoms, a (di) cycloalkylene group and an arylene group. A ^Three As a residue of the above dicarboxylic acid (a group excluding two carboxyl groups) and a residue of the following diisocyanate (a group excluding two isocyanate groups); A ^Four The diol or dihydric phenol residue (a group excluding two hydroxyl groups), the dithiol residue (a group excluding two thiol groups) and the diamine residue (two amino acids). Group without the group).
-A ^Three -CO-NH-A ^Four -As amide bond-containing groups in nylon salts such as nylon 6,6,6,10,6,12,11,6,11,10,11,12,12,6,12,10,12,12, A ^Three -CO-O-A ^Four Examples of-include ester bond-containing groups corresponding to these amide bond-containing groups (NH is replaced by O).
[0020]
A ^Three The diisocyanate constituting the diisocyanate is an aliphatic diisocyanate having 2 to 10 carbon atoms (excluding carbon in the NCO group; the same shall apply hereinafter) (1,6-hexane diisocyanate, 2,2,4-trimethylhexane diisocyanate, lysine diisocyanate, etc.) , Alicyclic diisocyanates having 6 to 16 carbon atoms (4,4′-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, norbornane diisocyanate, isophorone diisocyanate, etc.), araliphatic diisocyanates having 8 to 12 carbon atoms (xylylene diisocyanate) , Α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.),
C6-C16 aromatic diisocyanate (1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate, 2,4'- and 4,4'-diphenylmethane diisocyanate, naphthylene -1,5-diisocyanate, etc.), and mixtures of two or more thereof.
[0021]
In the general formula (1), y is 0 when p = 1 and / or q = 1, and r = 0 when q = 1. m is preferably 0 or 1 to 30, more preferably 0 or 1 to 10 (especially 1 to 5); and n is preferably 1 to 70, more preferably 1 to 50, particularly 2 to 10.
The chain transfer agent (c) suitable for use in the present invention includes those represented by the following formulas (1) to (6).
1) m, t, p, x, and r are 0: Q [-Z] _n [For example, the following chain transfer agent 4].
2) m is 0, t is 1, and p + r ≦ 1 is satisfied:
Q (X ¹ -A ² -Z) _n [For example, mercaptoalkyl (thio) ether (such as the following chain transfer agent 1) and mercaptoalkylamine];
Q (X ¹ -CO-A ² -Z) _n [E.g., (thio) esters of mercaptoalkanoic acid and alcohol or thiol, and amides of mercaptoalkanoic acid and amine];
Q (CO-X ¹ -A ² -Z) _n [For example, (thio) esters of carboxylic acid and mercaptoalkanol or alkanedithiol (the following chain transfer agent 2 and the like, and carboxylic acid amide of mercaptoalkylamine);
Q [CO-A ² -Z] _n [For example, mercaptoketone (mercaptoalkanone etc.)].
[0022]
3) m and t are 1 and satisfy p + y ≦ 1, q + r ≦ 1 and p + q + r−x ≦ 1 [p = x = y = q = r = 0, p = q = r = 0, x = y = 1, p = q = 0, x = y = r = 1 (the chain transfer agent 3 below), p = r = 0, x = y = q = 1, p = x = y = r = 0 and q = 1, p = x = y = q = 0, r = 1, p = y = r = 0, x = q = 1, p = y = q = r = 0, x = 1, p = x = q = r = 0, y = 1, p = x = q = 0, y = r = 1, p = x = r = 0, y = q = 1, p = 1, x = y = q = r = 0, p = x = q = 1, y = r = 0, p = x = 1, y = q = r = 0, and p = x = r = 1, y = q = 0].
4) m ≧ 2, t = 1, y = 0, satisfying q + r ≦ 1 and p + q + r−x ≦ 1 [eg, p = 1 = p = x = q = r = 0, p = x = r = 0, q = 1 P = x = q = 0, r = 1, p = r = 0, x = q = 1, p = q = r = 0, x = 1, p = 1, x = q = r = 0, p = X = q = 1, r = 0, p = x = 1, q = r = 0, p = x = r = 1, q = 0, and p = q = 0, x = r = 1].
5) m ≧ 2, t is 1, y is 1, p is 0, X ^Three Is O or S, X ² Are carbonyl groups and satisfy q + r ≦ 1 and q + r−x ≦ 1 [q = r = 0, x = 1, q = 0, x = r = 1, r = 0, x = q = 1, x = q = r = 0, x = q = 0, r = 1, and x = r = 0, q = 1].
6) m ≧ 2, t is 1, y is 1, p is 0, q is 0, X ^Three Is NH and satisfies r−x ≦ 1 [r = 0, x = 1, x = r = 1, x = r = 0, and x = 0, r = 1].
[0023]
The mercapto equivalent of the chain transfer agent (c) [molecular weight per chain transfer group Z (number average)] is usually 1,000 or less, preferably 500 or less, particularly 90 to 300.
(C) is a precursor having an active hydrogen atom-containing group (hydroxyl group, amino group, carboxyl group) other than a thiol group [in the general formula (1), all of T is H, for example, the above monovalent or polyvalent Monohydric alcohol, (poly) oxyalkylene mono- or polyol, monohydric or polyhydric phenol, primary or secondary amine, amino alcohol, monohydric or polyhydric carboxylic acid, hydroxy acid or amino acid, esterified product thereof [Lactone (the following) adduct, polycondensate of the above diol and dicarboxylic acid], amidated product [lactam (the following) adduct, polycondensate of the above dicarboxylic acid and diamine or diisocyanate]], urethane and / or urea [Diisocyanate and diol [dihydric alcohol or (poly) oxyalkyl Diol] and / or polyaddition product with diamine] is added to an alkylene sulfide (sulfide corresponding to the above AO, such as ethylene sulfide), and the hydroxyl group of the precursor having a hydroxyl group is converted into a thiol group [halogenated (for example, thionyl). Chlorinated with chloride, etc., then reacted with alkali hydrosulfide, reacted with diphosphorus pentasulfide, etc.], and the above precursor is reacted with epihalohydrin (such as epichlorohydrin) to glycidyl and then hydrogen sulfide is reacted to form a glycidyl group. Formula -CH ₂ -CH (OH) -CH ₂ Convert to -SH or further convert the hydroxyl group to a thiol group if necessary. Reactive group (hydroxyl group, carboxyl group, amino group, etc.) or reactive group (hydroxyl group, carboxyl group, amino group). Etc.) and a reactive agent [(thio) esterification, (thio) amidation], a thiol or dithiol having the above reactive group and the above precursor and a reactive coupling agent (the above diisocyanate). , Diols, dicarboxylic acids, diamines, dihalides listed below) and the like [to form a (thio) urethane bond and / or (thio) urea bond, (thio) ester bond, (thio) amide bond, ether bond, etc.]] It can be produced by introducing a chain transfer group Z by a method such as ringing. Kill.
[0024]
As the lactone, a lactone corresponding to the ω-oxycarboxylic acid (ω-oxycaproic acid, ω-oxyenanthic acid, ω-oxycaprylic acid, ω-oxypelargonic acid, ω-oxycapric acid, ω-oxyundecanoic acid, ω-oxide decanoic acid, etc.), lactam corresponding to the above ω-aminocarboxylic acid (caprolactam, enantolactam, capryllactam, laurolactam, etc.), dihalide alkylene dihalide G-A1 -G, for example methylene chloride.
[0025]
Among (c), from the viewpoint of controlling the molecular weight of the obtained (co) polymer, the chain transfer group is preferably SH and the other symbols in the general formula (1) are as follows.
Chain transfer agent 1 [p, m, r is 0, t, x is 1, X ¹ When is an oxygen atom]
Q [OA ² -SH] _n [Hydroxyl-containing compound Q (OH) _n Of mercaptoalkyl ether]
Specific examples include ethylene glycol-di-2-mercaptoethyl ether, trimethylolpropane-tri-2-mercaptoethyl ether, pentaerythritol-tetra-2-mercaptoethyl ether, and the like.
As these production methods, the hydroxyl group of a hydroxyl group-containing compound (monovalent or polyhydric alcohol or monovalent or polyhydric phenol) is chlorinated with thionyl chloride or the like and then reacted with an alkali hydrosulfide, or a hydroxyl group-containing compound ( A method in which a polyhydric alcohol or the like) is reacted with ω-mercapto-alkyl alcohol to etherify.
[0026]
Chain transfer agent 2 [m, r is 0, p, t, x is 1, X ¹ When is an oxygen atom]
Q [COO-A ² Z] _n [Carboxyl group-containing compound Q (COOH) _n Of mercaptoalkyl ester]
Specific examples include maleic acid-di-2-mercaptoethyl ester, fumaric acid-di-2-mercaptoethyl ester, adipic acid-di-2-mercaptoethyl ester, terephthalic acid-di-2-mercaptoethyl ester, and the like. Can be mentioned.
As these production methods, a carboxyl group-containing compound (monovalent or polyvalent carboxylic acid, hydroxy acid or amino acid) or an ester-forming derivative thereof [an acid anhydride or a lower (1 to 4 carbon atoms) alkyl ester] is ω- The method of making it esterify by making it react with a mercapto-alkyl alcohol is mentioned.
[0027]
Chain transfer agent 3 [p, q is 0, m, r, t, x, y is 1, X ¹ Is an oxygen atom, X ² Is a carbonyl group, X ^Three When is an oxygen atom or NH]
Q [OCO-A ¹ -OCO-A ² -SH] _n [Hydroxyl-containing compound Q (OH) _n Mercaptocarboxylic esters of lactone adducts of] and Q [OCO-A ¹ -NH-CO-A ² -SH] _n [Hydroxyl-containing compound Q (OH) _n Lactam adduct mercaptocarboxylic amide]
Specific examples include triethanolamine-ε-caprolactone adduct-tri-3-mercaptopropionic acid ester, triethanolamine-ε-caprolactam adduct-tri-3-mercaptopropionic acid amide, and the like.
Examples of these production methods include a method of adding a lactone or lactam to a hydroxyl group-containing compound (monovalent or polyhydric alcohol or monovalent or polyhydric phenol) and then esterifying or amidating with ω-mercapto-carboxylic acid. It is done.
[0028]
Chain transfer agent 4 [when p, m, r, t, x are 0]
Q (SH) _n [Thiol group-containing compound]
Specific examples include cysteine and the like.
[0029]
The ethylenically unsaturated monomer (a) in the present invention includes the following.
(A1) Hydrophilic vinyl monomer
The following (a11) to (a14) and mixtures thereof:
(A11) Nonionic monomer
(A11-1) a (meth) acrylate monomer having a hydroxyl group and / or an oxyethylene group: (meth) acrylic acid (representing acrylic acid and / or methacrylic acid, hereinafter the same expression is used) and polyvalent ( Divalent to 12-valent or higher) alcohol (as described above) or polyoxyalkylene mono- or poly-ol (as described above, polymerization degree of 2 to 100 or higher, oxyethylene group content of 50% or higher, monovalent Or an ester with 2 to 12 or more), for example, hydroxyalkyl (2 to 4 carbon atoms) (meth) acrylate [hydroxyethyl (meth) acrylate etc.], and (poly) glycerin (degree of polymerization 1 to 10) Mono (meth) acrylate, polyethylene glycol (hereinafter abbreviated as PEG) or its monoalkyl (C1-C4) ether mono (meth) acrylate [diethylene glycol mono (meth) acrylate, PEG (polymerization degree 51-100) mono (meth) acrylate, ω-methoxy PEG (polymerization degree 2-100) (meth) Acrylate etc.];
(A11-2) (meth) acrylamide monomer: (meth) acrylamide and derivatives thereof [N-alkyl (carbon number 1 to 4) or hydroxyalkyl (carbon number 1 to 4) substituted product], for example, N-methyl (Meth) acrylamide, N-methylol (meth) acrylamide, etc .;
(A11-3) Unsaturated alcohol: alkenol (2 to 6 or more carbon atoms) and its (poly) oxyalkylene ether (2 to 4 carbon atoms of alkylene group, degree of polymerization 1 to 100)], for example, vinyl alcohol , (Meth) allyl alcohol, etc .;
(A11-4) Nitrogen atom-containing nonionic vinyl monomer: N-vinyl lactam (N-vinyl-2-pyrrolidone, etc.), N-vinyl dicarboxylic imide (N-vinyl succinimide, etc.), 2-cyanoethyl (meth) acrylate Such.
[0030]
(A12) Anionic monomer
The following acids, salts thereof [alkali metal salts, alkaline earth metal salts, ammonium salts and amine (1 to 20 carbon atoms) salts, quaternary ammonium salts, etc.], and mixtures thereof:
(A12-1) Unsaturated carboxylic acid: monocarboxylic acid [(meth) acrylic acid, (iso) crotonic acid, vinyl benzoic acid, cinnamic acid, etc.], dicarboxylic acid (anhydride) [maleic acid, fumaric acid, itacon Acids, citraconic acid, mesaconic acid and the like, and anhydrides thereof (such as maleic anhydride)];
(A12-2) Unsaturated sulfonic acid: C2-C20 aliphatic unsaturated sulfonic acid (such as vinyl sulfonic acid), C6-C20 aromatic unsaturated sulfonic acid (such as styrene sulfonic acid), sulfone Acid group-containing (meth) acrylate [sulfoalkyl (aryl) (4 to 23 carbon atoms) (meth) acrylate such as sulfopropyl (meth) acrylate, sulfoethyl (meth) acrylate, 2- (meth) acryloyloxy-2,2 -Dimethylethanesulfonic acid, p- (meth) acryloyloxymethylbenzenesulfonic acid], sulfonic acid group-containing (meth) acrylamide [sulfoalkyl (aryl) (4 to 23 carbon atoms) (meth) acrylamide such as N-sulfopropyl (Meth) acrylamide, N-sulfoethyl (meth) acrylamide, 2 -Acryloylamino-2-methylpropanesulfonic acid, p- (meth) acryloylaminomethylbenzenesulfonic acid, etc.], alkyl (1-20 carbon atoms) (meth) allyl sulfosuccinic acid ester [methyl (meth) allyl sulfosuccinic acid ester, etc. ]Such;
(A12-3) polyoxyalkylene polyol (alkylene group having 2 to 6 carbon atoms, polymerization degree of 2 to 100 or more, divalent to 12 or more) unsaturated carboxylic acid [(meth) acrylic acid, etc. ] Sulfuric acid or phosphoric acid ester of monoester: For example, (meth) acryloyl polyoxyalkylene sulfuric acid ester [(meth) acryloyl polyoxyethylene (degree of polymerization 2 to 50) sulfuric acid ester, etc.]
[0031]
(A13) Cationic monomer
The following, their salts (eg hydrochlorides, sulfates) and quaternized products (methyl chloride salts, dimethyl sulfate salts, benzyl chloride salts, etc.), and mixtures thereof:
(A13-1) Amino group-containing acrylic monomer: amino group-containing (meth) acrylate such as aminoalkyl (2 to 6 carbon atoms) (meth) acrylate and its N-alkyl or N, N-dialkyl (1 carbon atom) -4) Substrate [N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-diethylaminopropyl (meth) Acrylates, etc.], and heterocyclic amino group-containing (meth) acrylates [morpholino- or piperidino-alkyl (2 to 4 carbon atoms) (meth) acrylates: morpholinoethyl (meth) acrylates, etc.]; and amino group-containing (meth) acrylamides For example, aminoalkyl (C2-6) (Meth) acrylamide and its N-alkyl or N, N-dialkyl (C1-C4) substitution product [N, N-dimethylaminoethyl (meth) acrylamide etc.];
(A13-2) Amino group-containing vinyl compound: For example, alkenylamine [(meth) allylamine etc.], amino group-containing aromatic vinyl compound (vinylaniline etc.), heterocyclic amino group-containing vinyl compound (N-vinylcarbazole, vinyl) Imidazole, 2-vinylpyridine, vinylmorpholine, etc.).
(A14) Amineimide group-containing compound: for example, 1,1,1-trimethylamine (meth) acrylimide, 1,1-dimethyl-1-ethylamine (meth) acrylimide, 1,1-dimethyl-1- (2′-phenyl) -2'-hydroxyethyl) amine (meth) acrylimide, 1,1,1-trimethylamine (meth) acrylimide and the like.
[0032]
(A2) Hydrophobic vinyl monomer
The following (a21) to (a26), and mixtures thereof:
(A21) (meth) acrylic acid ester having 4 to 23 carbon atoms: aliphatic, alicyclic, aromatic or epoxy group-containing alcohol having 1 to 20 carbon atoms (alkanol, alkenol, cycloalkanol, benzyl alcohol, glycidol, (Meth) acrylates such as tetrahydrofurfuryl alcohol), for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate, cyclohexyl (meth) acrylate, Glycidyl (meth) acrylate and the like;
[0033]
(A22) Polyoxyalkylene polyol (the above-mentioned, degree of polymerization of 2 to 100 or more, oxyethylene group content less than 50%) (divalent to 12 or higher) or a partial hydrocarbyl ether [monoalkyl Unsaturated carboxylic acid [(C1-20) ether, monocycloalkyl (C3-12) ether, monoaralkyl (C7-20) ether or monoaryl (C6-20) ether] [Meth) acrylic acid, etc.] Monoester: For example, polyoxypropylenediol (polymerization degree 2-50) [polypropylene glycol (hereinafter abbreviated as PPG), dihydric alcohol (ethylene glycol, etc.) or dihydric phenol (bisphenol A, etc.) PO Adduct] mono (meth) acrylate, and polio Xylpropylene monool (degree of polymerization 2 to 50) [monohydric alcohol (alkanol having 1 to 20 carbon atoms, cycloalkanol having 3 to 12 carbon atoms, benzyl alcohol, etc.) or monohydric phenol (phenol, alkylphenol having 7 to 20 carbon atoms) Etc.), such as 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 -Cyclohexyloxy PPG mono (meth) acrylate, ω-phenoxy PPG mono (meth) acrylate, etc .;
[0034]
-(A23) C3-C20 unsaturated nitrile: (meth) acrylonitrile etc .;
(A24) C2-C30 unsaturated hydrocarbon: aliphatic unsaturated hydrocarbon [eg alkene (ethylene, propylene, nonene etc.), alkadiene (butadiene etc.)], and aromatic unsaturated hydrocarbon [styrene, And its homologues (such as 1-methylstyrene)];
-(A25) Esters of unsaturated alcohol [above (a11-3): vinyl alcohol, (meth) allyl alcohol, etc.] and carboxylic acid (C2-C20 fatty acid, benzoic acid, etc.): for example, vinyl acetate;
(A26) Halogen-containing monomer: For example, vinyl chloride.
[0035]
Among these monomers (a), from the viewpoint of water solubility of the obtained (co) polymer, (a1) is preferable, and (a11-1) and (a11) among (a11) are more preferable. -2), (a12-1) of (a12), (a12-2) and salts thereof, and one kind selected from the group consisting of (a13-1) and salts thereof of (a13) Or it is 2 or more types. Particularly preferred is one containing 50 mol% or more of acrylamide.
[0036]
The above preferred monomers may be used in combination with other monomers as necessary. In this case, the proportion of other monomers in the total monomers is usually 50 mol% or less, preferably 40 mol% or less, 0.5 mol% or more, particularly 1 mol% or more.
[0037]
As the radical polymerization initiator (b) in the present invention, known ones such as water-soluble azo initiators [azobisamidinopropane (salt), azobiscyanovaleric acid (salt), etc.], oil-soluble azo initiators (azo Biscyanovaleronitrile, azobisisobutyronitrile, azobiscyclohexanecarbonitrile, etc.), water-soluble peroxides (hydrogen peroxide, peracetic acid, etc.), oil-soluble peroxides (benzoyl peroxide, cumene hydroxy peroxide, etc.) ), And inorganic peroxides (ammonium persulfate, sodium persulfate, etc.).
The above peroxides may be used as a redox initiator in combination with a reducing agent. Examples of reducing agents include bisulfites (sodium bisulfite, potassium bisulfite, ammonium bisulfite, etc.), tertiary amines (dimethylaminobenzoic acid (salt), dimethylaminoethanol, etc.), and amine complexes of transition metal salts [ A pentamethylenehexamine complex of cobalt (III) chloride, a diethylenetriamine complex of copper (II) chloride, and the like. The azo initiator, peroxide initiator, and redox initiator may be used alone or in combination.
[0038]
The amount of (b) used is preferably 0.01 to 100,000 ppm, more preferably 0.05 to 50,000 ppm, based on the weight of the monomer (a), from the viewpoint of the molecular weight of the (co) polymer. is there.
[0039]
The amount of the chain transfer agent (c) used is preferably 0.001 to 100,000 ppm based on the weight of the ethylenically unsaturated monomer (a) from the viewpoint of controlling the molecular weight of the obtained (co) polymer. Preferably it is 0.01-50,000 ppm, Most preferably, it is 0.1-30,000 ppm.
[0040]
The polymerization method of the (co) polymer in the present invention is not particularly limited, but is easy to remove heat during polymerization, sharpness of molecular weight distribution, and uniform particle size of particles obtained by drying the (co) polymer. From the viewpoints of properties, sphericity (major axis / minor axis ratio), smoothness of particle surface (expressed by fractal order described later), and simplification or omission of (co) polymer drying step Preferred is reverse phase suspension polymerization.
[0041]
The reaction system in the reverse phase suspension polymerization is composed of an aqueous phase and an oil phase, the aqueous phase is mainly composed of monomers and water, and the oil phase is mainly composed of a dispersion medium. The weight ratio of water phase / oil phase is usually 70/30 to 9/91, preferably 65/35 to 20/80.
[0042]
The monomer concentration in the entire system based on the total weight of the aqueous phase and the oil phase is preferably 5 to 65%, more preferably 15 to 60%, particularly 25 to 55% from the viewpoint of maintaining the dispersion. The monomer concentration in the aqueous phase is preferably 20 to 98%, more preferably 30 to 95%, from the viewpoint of production efficiency. Above and below,% represents% by weight.
[0043]
Examples of the dispersion medium constituting the oil phase include hydrocarbon solvents such as aliphatic hydrocarbons (having 5 to 12 carbon atoms such as n-hexane, n-heptane, n-octane, and n-dodecane), alicyclic hydrocarbons ( C5-C12, for example, cyclopentane, cyclohexane, cycloheptane, methylcyclohexane, cyclooctane), aromatic hydrocarbon (C6-C12, for example, benzene, toluene, xylene, ethylbenzene), etc. are mentioned. The amount of the dispersion medium used is preferably 40 to 1,000%, more preferably 55 to 400% based on the weight of the monomer from the viewpoint of stabilizing the suspended particle dispersion.
[0044]
As the dispersant in the reverse phase suspension polymerization, a commonly used dispersant, for example, cellulose (ethylcellulose, hydroxyethylcellulose, ethylhydroxyethylcellulose, cellulose acetate butyrate, etc.), oil-soluble surfactant [sorbitan fatty acid ester (sorbitan stearate) , Sorbitan oleate, etc.). The amount of the dispersant used is preferably 0.01 to 10%, particularly 0.1 to 5% based on the weight of the dispersion medium from the viewpoint of stabilizing the dispersion of the suspended particles.
[0045]
The pH of the aqueous phase at the time of polymerization is preferably 2 to 10, particularly 3 to 8, from the viewpoint of the performance of the (co) polymer produced. The pH can be adjusted usually using a mineral acid (sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid, etc.), caustic alkali (sodium hydroxide, potassium hydroxide, etc.), amine (triethanolamine, etc.) and the like.
[0046]
Specifically, the reverse phase suspension polymerization in the present invention can be performed, for example, by the following procedure.
That is, the inert gas in the vessel is passed through an inert gas (such as nitrogen) to the dispersion medium in which the dispersant is dissolved, and the temperature is usually adjusted to 10 to 80 ° C., preferably 30 to 70 ° C. in advance. When the initiator (b) is water-soluble, an aqueous solution of the monomers (a), (b) and the chain transfer agent (c) [monomer concentration is usually 20 to 95%, preferably 40 to 90%, (b) The concentration of is usually 0.1 to 30%, preferably 0.2 to 20%, and the amount of (c) used is the above-mentioned amount based on the weight of the monomer] after the inert gas substitution, and then polymerized by dropping. it can. When (b) is oil-soluble, the dispersion medium solution (b) [concentration of (b) is usually 0.1 to
30%, preferably 0.2 to 20%], and aqueous solutions of (a) and (c) [the concentration of (a) and the amount used of (c) are the same as described above] Can be polymerized by simultaneously dropping them into the dispersant solution.
Here, in dropping the solution (aqueous solution or dispersion medium solution) of (a) and (b), (a) and (b) may be added together, or (a) and (b) may be added separately. After preparing it as a solution, it may be mixed immediately before dropping, or may be separately dropped simultaneously.
The dropping time varies depending on the concentration of (a) and the calorific value of the polymerization reaction, but is usually 0.5 to 10 hours, preferably 1 to 5 hours.
[0047]
The progress and end point of the polymerization reaction can be confirmed by measuring the monomer content in the suspension using gas chromatography or the like.
[0048]
The (co) polymer after polymerization is usually obtained as a hydrous gel having a diameter of 0.1 to 2 mm. The water-containing gel is usually subjected to solid-liquid separation by filtration or centrifugation and then heat-dried (drying temperature is usually 30 to 150 ° C., preferably 35 to 130 ° C.), but the dispersion medium used at the time of polymerization is combined with water. In the case of boiling, it is not necessary to heat and dry them, and the solvent may be removed after the solid-liquid separation.
Examples of the method for drying the hydrogel include hot air drying, infrared drying, indirect heating drying (vacuum drying, screw conveyor, drum dryer), and solvent removal. From the viewpoint of the high heat transfer rate and the particle size of the particles, indirect heating drying, particularly screw conveyors and drum dryers are preferred. Although the drying temperature in the case of drying with a screw conveyor and a drum dryer is not specifically limited, 60-130 degreeC especially 70-110 degreeC is preferable.
The water content of the (co) polymer particles after drying is usually 0.1 to 15%, preferably 0.1 to 10%.
[0049]
From the viewpoint of solubility in water, the (co) polymer particles obtained by drying are preferably those having a particle size of less than 50 μm and not more than 0.1% of the total particle size and exceeding 2,000 μm. 0.1% or less of all particles, more preferably 0.1% or less of all particles having a particle size of less than 180 μm, and 0.1% or less of all particles having a particle size exceeding 1,800 μm. The particle size distribution can be confirmed using a sieve.
The sphericity of the (co) polymer particles is preferably 1.1 to 1, particularly 1.06 to 1, from the viewpoint of suppressing fine powder. Here, the sphericity represents a ratio [major axis / minor axis] of the major axis (μm) and minor axis (μm) of the particle, and is 1 for a perfect sphere.
Further, the fractal order of the (co) polymer particles is preferably 1.9 to 2, particularly 1.95 to 2, from the viewpoint of suppressing fine powder. Here, the fractal order is a numerical value representing the smoothness of the particle surface, which is obtained by a method described later, and is 2 on a completely smooth surface.
[0050]
In the present invention (invention according to claim 2), the particles obtained by drying the (co) polymer having the monomer (a) as a structural unit are those having a particle size of less than 50 μm and 0.1% or less of the total particles, The particle size exceeding 2,000 μm is 0.1% or less of the total particle. Those having a particle size of less than 180 μm are preferably 0.1% or less of all particles, and those having a particle size of more than 1,800 μm are preferably 0.1% or less of all particles.
[0051]
The particles obtained by drying the (co) polymer having the monomer (a) as a structural unit in the present invention (the invention according to claim 3) have a sphericity of 1.1 to 1, and 1.06 ~ 1 are preferred.
Further, the particles obtained by drying the (co) polymer having the monomer (a) as a structural unit in the present invention (the invention according to claim 4) have a fractal order of 1.9 to 2, and The thing of 95-2 is preferable.
The (co) polymer in the present invention (the invention according to claims 2 to 4) is obtained by subjecting the monomer (a) to reverse phase suspension polymerization in the presence of a polymerization initiator (b) and a chain transfer agent (c). Can be manufactured.
[0052]
The molecular weight of the (co) polymer in the present invention (the invention according to claims 1 to 4) is represented by an intrinsic viscosity, which is usually 15 to 32 dl / in for nonionic and anionic (co) polymers. g, preferably 18-30 dl / g, for cationic (co) polymers, usually 3-20 dl / g, preferably 4-15 dl / g, for amphoteric (co) polymers, usually 3-15 dl / g, preferably Is 4-12 dl / g.
Here, the intrinsic viscosity is a value measured at 30 ° C. in a 1N sodium nitrate aqueous solution.
[0053]
Further, the molecular weight distribution of the (co) polymer is represented by the thread length, and the smaller the value, the narrower the molecular weight distribution. For nonionic and anionic (co) polymers, it is usually 60 to 120 mm, preferably 60 to 100 mm, and for cationic (co) polymers, it is usually 5 to 90 mm, preferably 5 to 80 mm.
Here, the string length is a value (unit: mm) measured by a method described later.
[0054]
Since the polymer flocculant of the present invention has excellent flocculation performance, it is used for flocculation and precipitation of industrial wastewater, for dewatering sewage sludge, for tertiary recovery of oil, for improving drainage yield in papermaking processes, or for paper Widely used for power enhancement.
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to this. The part in an Example is a weight part.
Further, the string length, insoluble matter, fractal order, and degree of dust generation were measured by the following methods.
[0055]
<Yarn thread length>
The measurement is based on the silk thread length measuring device [manufactured by Kyowa Science Co., Ltd.] The specific measurement method is as follows.
The (co) polymer is dissolved in ion-exchanged water to make a 0.2% aqueous solution (liquid temperature 25 ° C.), and a glass sphere (diameter 7 mm) is immersed in this so that the bottom of the glass sphere has a depth of 11 mm. When the glass sphere is pulled up at a speed of 16 mm / second after being immersed for about 3 seconds, the lifting distance until the thread (string) of the (co) polymer aqueous solution formed between the glass sphere and the liquid surface is cut is measured. This is the yarn length (mm). The glass sphere is a glass sphere with a glass rod of about 10 mm to which a lifting thread is attached.
[0056]
<Insoluble matter>
In a 1 L beaker, 500 g of a 0.1% sodium chloride aqueous solution was added, and this was stirred with a motor equipped with a stirring blade having a length of 50 mm and a width of 20 mm at 2.5 rpm, and 2.5 g of a sample [(both ) Polymer, the same applies hereinafter] and dissolve over 2 hours. The solution is filtered through a 100 μm stainless steel mesh weighed in advance. The residue is placed on an aluminum dish together with a wire mesh and dried in a constant temperature bath at 120 ° C. for 2 hours. The residue after drying is cooled to room temperature in a desiccator together with a wire mesh, weighed and the weight obtained by subtracting the weight of the stainless steel wire mesh is taken as [residue amount after drying], and the insoluble content is obtained from the following formula.
Insoluble content (%) = [residue amount after drying (g) / sample amount at dissolution (g)] × 100%
[0057]
<Fractal order>
Scanning electron micrographs of one spherical sample are taken at respective magnifications of 20, 40, 80, 150 and 300 times. For each of these photographs, the particle contour length and the particle projected area are determined. Next, the points (5 points) obtained from each photograph are plotted on the XY coordinates where the common logarithm of the particle contour length is the X axis and the common logarithm of the particle projected area is the Y axis, and the points are obtained by the least square method. Draw a straight line.
A straight line is drawn in the same manner as described above for each of the further five resin particles taken out at random, and the average value of the slope is defined as the fractal order.
[0058]
<Dust generation>
The suction port of a 1 L suction bottle and the suction port of a digital dust meter (made by Shibata Kagaku: MODEL P-5) are connected by a glass tube having an inner diameter of 7 mm and a length of 10 cm (the connecting portion is a rubber tube). From the spout at the top of the suction bottle, 20 g of the sample is dropped into the suction bottle using a funnel (diameter 120 mm, foot inner diameter 15 mm, foot length 50 mm). The number of fine particles generated per minute from the dropped sample was measured using a digital dust meter, and this value was determined as the degree of dust generation (unit: CPM, 1 CPM = 0.001 mg / m). ^Three , Measurement range 0.01-100mg / m ^Three ).
[0059]
The chain transfer agents used in the examples and comparative examples are shown below.
Chain transfer agent 1-1 Ethylene glycol-di-2-mercaptoethyl ether
Chain transfer agent 2-1 Maleic acid-di-2-mercaptoethyl ester
Chain transfer agent 3-1 Triethanolamine-ε-caprolactone adduct-tri-3-mercaptopropionic acid ester
Chain transfer agent 4-1 Cysteine
[0060]
Examples 1-9 and Comparative Examples 1-3
207 parts of cyclohexane and 1.04 part of ethyl hydroxyethyl cellulose (0.5% / dispersion medium) were charged into the reaction vessel, nitrogen gas was passed through to sufficiently purge the inside of the vessel, and the liquid temperature was adjusted to 50 ° C. A total of 311 parts of monomer (parts), chain transfer agent [amount (monomer) relative to monomer] and ion-exchanged water shown in Table 1 were adjusted to pH 7, and 0.070 part of azobisamidinopropane hydrochloride was dissolved in the aqueous solution. The whole amount was charged into the dispersion medium by a dropping funnel over 2 hours. After completion of the polymerization, the polymerization solution was poured into acetone with stirring, and further decanted to take out the (co) polymer. The obtained (co) polymer was spread evenly on an aluminum pan and dried in a circulating drier (40 ° C.) for 2 hours to obtain a weight-average particle size of 0.8 mm and a water content of 8.5% (both ) A polymer flocculant comprising a polymer was obtained.
[0061]
Comparative Examples 4 and 5
A total of 455 parts of the monomer (same as above), chain transfer agent (same as above) and ion-exchanged water shown in Table 1 were charged into an adiabatic reaction vessel, and nitrogen gas was blown into the liquid at 20 ° C. for 20 minutes. Subsequently, 0.5 parts of 10% aqueous solution of azobisamidinopropane hydrochloride, 0.02 part of 10% aqueous solution of hydrogen peroxide, and 0.01 part of 10% aqueous solution of ascorbic acid were sequentially added. Nitrogen blowing was stopped after the addition. After about 10 minutes, the liquid temperature began to rise, and the reaction system gradually thickened to a block-like (co) polymer. The block obtained after 7 hours was shredded, dried in a circulating dryer at 75 ° C. for 5 hours, and then pulverized with a mixer to obtain a polymer flocculant composed of a powdery (co) polymer.
[0062]
[Table 1]

[0063]
Each symbol in the table represents the following compound.
AAm: Acrylamide
NaA: Sodium acrylate
DAMQ: Trimethylaminoethyl methacrylate chloride
[0064]
In the examples and comparative examples, the monomer concentration (%) in the aqueous phase and the whole system and the maximum temperature reached during polymerization (° C.), and the intrinsic viscosity (dl / g), string length (mm), insoluble content (%), particle size distribution [content of particles having particle size of less than 180 μm (%) and content of particles exceeding 1,800 μm (%)], fractal order Table 2 shows the sphericity and the degree of dust generation (CPM).
[0065]
[Table 2]

[0066]
From Table 2, the (co) polymers of Examples 1 to 9 are almost free from insoluble matter compared to the corresponding (co) polymers of Comparative Examples 1 to 3, respectively, and have a high intrinsic viscosity. It can be seen that the silk thread length is small. Compared with aqueous solution polymerization, although it has the same intrinsic viscosity, fine yarn is generated from the results of particle size distribution, fractal order, sphericity, and dust generation degree, as well as a narrow yarn length and narrow molecular weight distribution. It turns out that it is very few.
[0067]
Example 1 of performance evaluation of flocculant
Using the polymer flocculants obtained in Examples 1 to 5 and Comparative Example 4, a coagulation test was conducted in K gravel washing field wastewater (suspension material 0.35%, pH 6.0). The results are shown in Table 3. In the coagulation test, 300 ml of waste water was placed in a 300 ml graduated cylinder (settling tube), and a predetermined amount of a 0.1% ion exchange aqueous solution of a flocculant was added thereto at room temperature. Next, the sedimentation tube was turned 10 times to mix the waste water and the flocculant aqueous solution to form a floc, and then the sedimentation tube was allowed to stand and the sedimentation rate at the interface of the floc layer was measured. The sedimentation rate is expressed in m / hour.
From Table 3, it can be seen that the flocculant of the present invention can provide a high sedimentation rate (coagulation property) at a low addition amount as compared with the flocculant of the comparative example.
[0068]
[Table 3]

[0069]
Flocculant performance evaluation example 2
Using the polymer flocculants obtained in Examples 6 to 9 and Comparative Examples 3 and 5, dewatering was performed with T sludge treatment plant mixed raw sludge (solid content concentration 1.1%, pH 6.9, organic content 78%). A test was conducted. The results are shown in Table 4.
In the dehydration test, 200 ml of sludge was placed in a 300 ml beaker, a predetermined amount of a 0.1% ion exchange aqueous solution of a flocculant was added thereto at room temperature, and the mixture was stirred at 180 rpm for 1 minute to form a floc. This was dehydrated with a small centrifugal dehydrator (1,500 G), and the moisture content of the obtained dehydrated cake was measured. The moisture content of the cake is expressed in%.
From Table 4, it can be seen that the flocculant of the present invention provides a high dehydration rate (low cake moisture content) at a low addition amount as compared with the flocculant of the comparative example.
[0070]
[Table 4]

[0071]
【The invention's effect】
The polymer flocculant of the present invention is extremely useful because of the following effects.
(1) Despite being obtained under polymerization conditions with a high monomer concentration, there is very little insoluble matter in water.
(2) Since it is obtained under polymerization conditions with a high monomer concentration, drying is easy, and the subsequent drying process can be simplified.
(3) Since the particle size distribution is narrow and the amount of fine powder is extremely small, it is easy to dissolve in water, and the working environment is not deteriorated by the fine powder.
(4) Since it is spherical and has a smooth surface, it is unlikely to generate fine powder during transportation or handling, and does not cause any adverse effects due to the fine powder.
(5) Since it has a high molecular weight and a narrow molecular weight distribution, it exhibits an excellent aggregating effect with a low addition amount.

Claims (6)

The ethylenically unsaturated monomer (a) is represented by the radical polymerization initiator (b) and the following general formula (1), and the chain transfer agent for radical polymerization (c) is 100 to 100,000 ppm with respect to (a). (Co) polymer (A) obtained by reverse-phase suspension polymerization at a monomer concentration of 40 to 98% by weight in the aqueous phase, and (A) the yarn length is nonionic and anionic (covalent). ) A polymer flocculant having a polymer of 60 to 120 mm and a cationic (co) polymer of 5 to 90 mm.
_{Q [(C = O) p} (X 1) x ^{_{[(X 2) y -A 1 -}} (C = O) q -X 3 ] _m -T] _n (1)
[Wherein Q is an n-valent organic group; X ¹ and X ³ are O, S or NH; X ² is a carbonyl group or —CONH—; at least part of T is represented by the formula — (C═O) _r — ( A ² ) is a group represented by _t- Z, and the remainder may be H; Z is a chain transfer group; A ¹ is an alkylene group having 1 to 8 carbon atoms or a formula -A ³ -X ⁴ -X - ³ -A ⁴ groups represented by; a ³ and a ⁴ is a divalent hydrocarbon group having 2 to 20 carbon atoms; X ⁴ is carbonyl or -NHCO-; a ² is an alkylene group having 1 to 8 carbon atoms Or when Z is SH, A ² may be a group of the formula —CH ₂ —CH (X ⁵ H) —CH ₂ — (X ⁵ is O or S); p, q, r, t, x and y are each 0 or 1; m is 0 or an integer of 1 to 50; n is an integer of 1 to 100; But it can be different. ]   It is composed of particles obtained by drying (A), and the content of particles having a particle size of less than 180 μm is 0.1% by weight or less, and the content of particles exceeding 1,800 μm is 0.1% by weight or less, Item 5. The polymer flocculant according to Item 1.   The polymer flocculant according to claim 1, comprising particles obtained by drying (A), wherein the sphericity of the particles is 1.1 to 1.   The polymer flocculant according to claim 1, comprising particles obtained by drying (A), wherein the particles have a fractal order of 1.9 to 2. The polymer flocculant according to any one of claims 1 to 4 , wherein the monomer concentration in the entire system of the monomer (a) is 5 to 65% by weight. The polymer according to any one of claims 1 to 5 , which is used for the coagulation and precipitation of industrial wastewater, for the dewatering of sewage sludge, for the third recovery of oil, for the improvement of drainage yield in the papermaking process or for the enhancement of paper strength. Flocculant.