JP2003073572A - Water-soluble polymer dispersion and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dispersion of a water-soluble polymer containing a dispersant for suppressing thickening at the time of polymerization and reducing the chain transfer reaction in a dispersion polymerization method in an aqueous solution of a salt in the coexistence of a high-molecular dispersant, and further to provide a method for efficiently producing the dispersion. SOLUTION: This dispersion of the water-soluble polymer contains at least one kind or more of a polymerized polymer and a natural polymer soluble in the aqueous solution of the salt as a disperser coexisting at the time of polymerization. The polymer dispersion is efficiently produced by making the polymerized polymer and the natural polymer coexist at the time of polymerization.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-soluble polymer dispersion and a method for producing the same, and more specifically, a kind selected from cationic, nonionic and amphoteric particles having a particle size of 100 μm or less in an aqueous salt solution. The present invention relates to the above water-soluble polymer fine particles and a water-soluble polymer dispersion liquid in which at least one or more of a polymer polymer and a natural polymer which are soluble in the aqueous salt solution as a dispersant coexist.

[0002]

2. Description of the Related Art Water-soluble polymers are used as flocculants for treating wastewater or as chemicals for papermaking, but since they are polymer compounds, they become highly viscous solutions when dissolved in water. Or to any product form for that is a big point in terms of commercialization. For example, in the stationary polymerization method of an aqueous solution, in order to obtain a high molecular weight polymer, the polymerization is carried out at a monomer concentration of 10% by weight or more, so that the product becomes a hydrated gel state, and in that state Since it is also difficult to dissolve, a step after polymerization is required, such as further diluting the product and marketing it as a fluid low-concentration solution. One of the countermeasures is pulverization, which many products use. However, the powder product takes a long time to dissolve when used, and a lot of energy for that is required.
Emulsion products are the solution. It is polymerized in the state of a water-in-oil emulsion, and after the polymerization, it is sold in a state in which it is easily dissolved by adding a hydrophilic surfactant. The dissolution time is shorter than that of powders, and high molecular weight polymers with high degree of polymerization can also be obtained.

However, the water-in-oil type emulsion has the disadvantage that it has flammability and wastes valuable organic solvent. Further, in suspension polymerization in a hydrophobic solvent,
Since flammable substances such as cyclohexane and toluene are used, there is a drawback that a large amount of cost is required for manufacturing equipment. In order to overcome the drawbacks of the water-in-oil emulsion polymerization method, the polyvalent anion salt aqueous solution is dissolved in the polyvalent anion salt aqueous solution, for example, acryloyloxyethylbenzyldimethyldimethylammonium chloride (co) polymer. A method has been developed for producing a dispersion in which a non-polymer is dispersed as fine particles in salt water. This is special fair 4-3
It can be produced by the method described in Japanese Patent No. 9481 or Japanese Patent Publication No. 6-51755. The former publication discloses a method of allowing a polyvalent alcohol to coexist as a dispersant during polymerization, and the latter publication allows a cationic polymer soluble in a polyvalent anion salt aqueous solution to coexist as a dispersant during polymerization. A method is disclosed.

In these publications, a (meth) acryloyloxyethylbenzyldialkylammonium chloride-based monomer such as acryloyloxyethylbenzyldimethylammonium chloride is a cation used as an essential component during the polymerization and coexisting during the copolymerization. The polymerizable monomer is N, N-dialkylaminoethyl (meth) acrylate, which is an acrylic monomer containing a tertiary amino group or a quaternary ammonium salt group. Currently, a problem is that when the copolymerization rate of the benzylic monomer is reduced or is not used at all, the viscosity at the time of polymerization is so severe that dispersion polymerization is often impossible. As a dispersant, a cationic polymer that is soluble in a polyvalent alcohol or a polyvalent anion salt aqueous solution is mainly used, but the development of a dispersant suitable for suppressing thickening is a major theme. Has become. Further, the polyvalent alcohol used as a dispersant also causes a decrease in the molecular weight of the polymer to be polymerized inevitably due to a chain transfer reaction.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to develop a water-soluble polymer dispersion liquid containing a dispersant capable of suppressing thickening during polymerization and efficiently producing water-soluble polymer molecules. It is also to investigate a dispersant suitable for polymerizing a high molecular weight polymer. Further, it is to develop a production method capable of efficiently producing the water-soluble polymer dispersion.

[0005]

[Means for Solving the Problems] In order to solve the above problems, the inventors of the present invention have made a detailed study and, as a result, arrived at the following invention. That is, the invention of claim 1 of the present invention is a cationic solution having a particle size of 100 μm or less in a salt solution,
Of one or more water-soluble polymer fine particles selected from amphoteric and nonionic, and a polymerizable cationic and / or nonionic polymer and a natural cationic polymer soluble in the salt aqueous solution as a dispersant And at least one or more of them coexist.

According to a second aspect of the present invention, the particle size is 10 in the aqueous salt solution.
One or more fine particles of water-soluble polymer selected from cationic, amphoteric and nonionic polymers of 0 μm or less, and a cationic polymer and a nonionic natural polymer which are soluble in the aqueous salt solution as a dispersant. Among them, it is a water-soluble polymer dispersion liquid in which at least one or more of them coexist.

According to a third aspect of the present invention, the water-soluble polymer dispersion is a cationic or nonionic polymerization-type polymer or a cationic natural-type polymer which is soluble in the aqueous salt solution as a dispersant. At least one or more of them are allowed to coexist, and the monomers represented by the following general formulas (1) and / or (2) are 0 to 100.
A monomer (mixture) consisting of mol%, 0 to 50 mol% of the monomer represented by (3), 0 to 100 mol% of acrylamide, and 0 to 30 mol% of a copolymerizable nonionic monomer. ,
The water-soluble polymer dispersion according to claim 1, which is produced by carrying out dispersion polymerization under stirring.

[Chemical 1] General formula (1) R1 is hydrogen or a methyl group, R2 and R3 are C1 to C3 alkyl or alkoxyl groups, R4 is hydrogen, a C1 to C3 alkyl group, alkoxyl group or benzyl go, May be different, A is oxygen or N
H and B represent an alkylene group having 2 to 4 carbon atoms or an alkoxylene group, and X1 represents an anion.

[Chemical 2] Formula (2) R5 represents hydrogen or a methyl group, R6 and R7 represent an alkyl group having 1 to 3 carbon atoms, an alkoxy group or a benzyl group, and X2 represents an anion.

[Chemical 3] General formula (3) R8 is hydrogen, a methyl group or a carboxymethyl group, A is SO3, C6H4SO3, CONHC (CH3) 2CH
2SO3, C6H4COO or COO, R9 is hydrogen or COOY2, Y1 or Y2 is hydrogen or cation

According to a fourth aspect of the present invention, the water-soluble polymer dispersion is at least one of a cationic polymer and a nonionic natural polymer which are soluble in the salt aqueous solution as a dispersant. In the coexistence of 0 to 100 mol% of the monomer represented by the following general formula (1) and / or (2), 0 to 50 mol% of the monomer represented by (3), and 0 to 10% of acrylamide.
It is manufactured by carrying out dispersion polymerization of a monomer (mixture) consisting of 0 mol% and a copolymerizable nonionic monomer of 0 to 30 mol% under stirring. Is a water-soluble polymer dispersion liquid of.

According to a fifth aspect of the present invention, the polymerization type cationic and / or nonionic polymer is represented by the following general formula (4):
The water-soluble polymer dispersion according to claim 1, which has one or more structural units selected from (9).

[Chemical 4] General formula (4)

[Chemical 5] General formula (5) R10 is hydrogen or a methyl group, and R11 and R12 have 1 carbon atom.
~ 3 alkyl or alkoxyl group, R13 is hydrogen, an alkyl group having 1 to 3 carbon atoms, an alkoxyl group or benzyl go, which may be the same or different, A is oxygen or NH, B is alkylene having 2 to 4 carbons. X3 represents a group or an alkoxylene group, and X3 represents an anion, respectively. R14 and R15 are hydrogen or a methyl group, R16 and R15
17 represents an alkyl group or an alkoxy group having 1 to 3 carbon atoms, and X4 represents an anion.

[Chemical 6] Formula (6) R18 is hydrogen or methyl go, X5 is an anion

[Chemical 7] Formula (7) R18 and R19 are hydrogen or methyl go, X6 is an anion

[Chemical 8] General formula (8) R21 is hydrogen or methyl go,

[Chemical 9] General formula (9) Here, R23 is hydrogen or a methyl group, A is CONR2
4R25 (R24 and R25 are hydrogen, an alkyl group having 1 to 4 carbon atoms or an alkoxyl group), OR26 (R26
Is hydrogen or an alkyl group or alkoxyl group having 1 to 4 carbon atoms, an acyl group), NHCOR27 (R27 is hydrogen, an alkyl group or alkoxyl group having 1 to 4 carbon atoms), an alkyl group or alkoxyl group having 1 to 10 carbon atoms , Aryl group, or nonionic hetero 5-membered ring or 6-membered ring, R28 represents hydrogen or methyl group, respectively.

According to a sixth aspect of the present invention, the polymerizable cationic polymer has one or more structural units represented by the general formulas (4) to (8) and a structure represented by the general formula (9). The water-soluble polymer dispersion according to claim 2, wherein each unit has a unit.

The invention of claim 7 is characterized in that the natural cationic polymer is selected from chitosan, chitosan derivatives, starch derivatives and cellulose derivatives. It is a dispersion liquid.

The invention of claim 8 is characterized in that the nonionic natural polymer is selected from starch, starch derivatives, cellulose derivatives, guar gum and locust bean gum. The water-soluble polymer dispersion described in 2.

The invention of claim 9 is characterized in that the cationically polymerized polymer or the cationic natural polymer has an ion equivalent value of 1.5 to 22 meq / g. Is a water-soluble polymer dispersion liquid of.

According to the tenth aspect of the present invention, the weight average molecular weight of one or more water-soluble polymers selected from the cationic, nonionic and amphoteric constituents of the polymer dispersion is 2,000,000 or more and 20,000,000 or less. The water-soluble polymer dispersion according to claim 1 or 2.

The invention according to claim 11 is the water-soluble polymer dispersion according to claim 1 or 2, characterized in that the salt constituting the aqueous salt solution contains at least one polyvalent anion salt.

According to a twelfth aspect of the present invention, in a salt aqueous solution, at least one or more of a cationic or nonionic polymerization type polymer and a cationic natural type polymer which are soluble in the salt solution are used as a dispersant. 0 to 100 mol% of the monomer represented by the general formula (1) and / or (2).
A monomer (mixture) consisting of 0 to 50 mol% of the monomer represented by (3), 0 to 100 mol% of acrylamide, and 0 to 30 mol% of another copolymerizable nonionic monomer, A method for producing a water-soluble polymer dispersion having a particle diameter of 100 μm or less, which comprises performing dispersion polymerization under stirring.

According to a thirteenth aspect of the present invention, in a salt aqueous solution, at least one or more of a cationic polymer and a nonionic natural polymer which are soluble in the salt water as a dispersant are allowed to coexist. 0 to 100 mol% of the monomer represented by the general formula (1) and / or (2), 0 to 50 mol% of the monomer represented by (3), 0 to 100 mol% of acrylamide, and copolymerizable In the method for producing a water-soluble polymer dispersion having a particle size of 100 μm or less, which comprises dispersion-polymerizing a monomer (mixture) composed of 0 to 30 mol% of another nonionic monomer under stirring. is there.

According to a fourteenth aspect of the present invention, the cationic or nonionic polymer compound has the general formula (4) to
13. The method for producing a water-soluble polymer dispersion according to claim 12, which has one or more structural units selected from (9).

According to a fifteenth aspect of the present invention, the cationic polymer compound is represented by one or more structural units represented by the general formulas (4) to (8) and the general formula (9). 14. The method for producing a water-soluble polymer dispersion according to claim 13, wherein each of the structural units has a structural unit.

The invention of claim 16 is characterized in that the natural cationic polymer is selected from chitosan, chitosan derivatives, starch derivatives and cellulose derivatives. It is a method for producing a dispersion liquid.

The invention of claim 17 is characterized in that the natural nonionic polymer is selected from starch, starch derivatives, cellulose derivatives, guar gum and locust bean gum. 13 is a method for producing a water-soluble polymer dispersion liquid according to item 13.

The invention of claim 18 is characterized in that the ion equivalent value of the polymerized cationic polymer or natural cationic polymer is 1.5 to 22 meq / g. Of the water-soluble polymer dispersion liquid.

The invention of claim 19 is characterized in that the salt constituting the aqueous salt solution contains at least one polyvalent anion salt, and the method for producing a water-soluble polymer dispersion according to claim 12 or 13. Is.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION One or more water-soluble polymer dispersions selected from the group consisting of cationic, amphoteric and non-ionic polymers of the present invention is a polymer-based polymer dispersant soluble in an aqueous salt solution. And a natural polymer are used in combination, and they are composed of polymer particles having a particle size of 100 μm or less produced by a dispersion polymerization method. The specific manufacturing method is as follows. An aqueous solution of a polyvalent anion salt such as ammonium sulfate is prepared, and in the case of a cationic water-soluble polymer, a (meth) acrylate-based quaternary ammonium base-containing monomer and acrylamide are used as cationic monomers, and an amphoteric water-soluble polymer. (Meth) acrylic acid is used in the case of a water-soluble polymer, and acrylamide is used in the case of a nonionic water-soluble polymer, and a polymer and a natural polymer are allowed to coexist as a dispersant before polymerization. The pH at this time is set to 2-6. After uniformly dissolving the mixture,
Oxygen in the reaction system is removed by nitrogen substitution, and a radically polymerizable initiator is added to initiate polymerization to produce a polymer. In addition, coexistence of a chain transfer agent, a cross-linking agent and the like before the start of polymerization is the same as in other polymerization methods.

First, the dispersant composed of a polymer will be described. When using a cationic or nonionic polymer as the polymer, use a cationic polymer when using a nonionic natural polymer, or use a cationic natural polymer when using a cationic natural polymer. A nonionic polymer is used together. Cationic polymerization type polymers are acrylic type, polyvinylamine type, polyvinylamidine type, polydiallylammonium type polyethyleneimine type and the like. Acrylics include polymers and copolymers such as dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, and methyldiallylamine. Examples of quaternary ammonium group-containing polymers include the tertiary amino groups mentioned above. (Meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxy-2-hydroxypropyltrimethylammonium chloride, (meth) acryloylaminopropyltrimethylammonium chloride, which is a quaternary compound containing methyl chloride or benzyl chloride of the contained monomer , (Meth) acryloyloxyethyldimethylbenzylammonium chloride, (meth) acryloyloxy 2-hydroxypropyldimethylbenzylammonium chloride, (meth) acryloylaminopropyldimethylbenzylammonium chloride Moniumu chloride copolymers and copolymers of such.

Examples of polyvinylamine polymers include:
A polymer or copolymer of N-vinylformamide or N-vinylacetamide is hydrolyzed with an acid or an alkali to be aminated. Examples of polyvinyl amidine-based polymers are N-vinylformamide and copolymers of N-vinylacetamide and acrylonitrile which are hydrolyzed with acid to form amidines. Examples of the dimethyldiallylammonium-based polymer are polymers and copolymers such as dimethyldiallylammonium chloride and diallylmethylbenzylammonium chloride. Examples of the polyethyleneimine-based polymer include polyethyleneimine and modified products obtained by crosslinking or grafting polyethyleneimine with epichlorohydrin, diepoxy compound and the like.

As an example of the polymerized nonionic polymer, an acrylic polymer is most easily available, and its monomers are (meth) acrylamide, N, N-dimethylacrylamide, vinyl acetate. , Acrylonitrile, methyl acrylate, 2-hydroxyethyl (meth) acrylate, diacetone acrylamide, N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide acryloylmorpholine, acryloylpiperazine and the like. Examples thereof include polymers of polymers and copolymers of two or more kinds. Other examples include polyvinyl alcohol and completely amidated products of butene / maleic anhydride copolymer.

The molecular weight of these cationic polymers is
5,000 to 3,000,000, preferably 50,000
˜2,000,000, more preferably 50,000 to 1,000,000. The ethyleneimine polymer has a molecular weight of 5,000 to 100,000, preferably 5,000 to 50,
It is 000. As the molecular weight of the nonionic polymer,
1,000 to 500,000, preferably 5,0
00 to 100,000.

Next, the natural polymer will be described. Examples of natural nonionic polymers include raw starch, enzyme-modified starch, hydroxyethyl cellulose and methyl cellulose.
And guar gum, locust bean gum and the like. Examples of natural cationic polymers include cation-modified starch with 2-hydroxy-3-chloropropyltrimethylammonium chloride, glycidyltrimethylammonium chloride or 2-chloroethyldimethylammonium chloride, and cations with the glycidyltrimethylammonium chloride. And a modified cellulosic derivative, chitosan, or chitosan modified with the above cationizing agent.

These polymerization type polymers and natural type polymers are a combination of a cationic or nonionic polymerization type polymer with a natural type nonionic polymer, and a polymerization type nonionic polymer is a natural type cationic polymer. It is effective to combine polymers. That is, it is appropriately selected according to the monomer to be polymerized.
In particular, when polymerizing a copolymer having a low ratio of cationic monomers or a nonionic polymer, it is effective to use a polymerizable cationic polymer and a natural cationic polymer. On the contrary, when the copolymerization ratio of the ionic monomer is high, it is effective to use the polymerized nonionic polymer and the cationic natural polymer. The dispersant of the present invention is not limited to being used in two or more types, but it is very complicated in terms of management to combine with three or four types, and usually two types or less, preferably one type.

The amount of the polymer dispersant added to the monomer is the total amount of the polymer and the natural polymer,
It is 1/100 to 20/100, preferably 2/100 to 15/100 with respect to the monomer. The blending ratio of these polymerized polymer and natural polymer is 8: 1 to 1: 8, preferably 5: 1 to 1: 5, and is appropriately selected according to the monomer to be polymerized.

One characteristic of the cationic natural polymer dispersant used in the present invention is that the molecular weight of the produced polymer is high. Although there is an example in which alcohol is conventionally used alone as a dispersant, alcohols are chain transfer agents and easily affect the polymerization reaction, resulting in a decrease in molecular weight. On the other hand, synthetic polymers that have been conventionally used also have a relatively active portion in the molecule and may cause chain transfer. In contrast, naturally-occurring macromolecules have relatively low chemical activity relatively. Therefore, it is presumed that the chain transfer reaction is unlikely to occur and the molecular weight does not decrease.

The reason why the dispersant of the present invention becomes very effective by combining a polymer of a polymer and a natural polymer cannot be elucidated in many theoretically unknown parts. Then it is considered as follows. That is, as the polymerization proceeds in a salt aqueous solution, the concentration of the produced polymer becomes equal to or higher than the solubility and precipitation of polymer particles begins, but before that, the polymer itself (polymerization system) is not formed because the polymer is dissolved. The viscosity also increases, and the dissolved polymer and precipitated particles coexist. After this, the ratio of the precipitated polymer increases,
The viscosity of the polymer gradually decreases, and the polymer changes to a dispersed state.
In this coexistence state, the slip between the precipitated particles and the gelled dissolved polymer is improved, and the phase change from the thickened state before the phase change to the dispersed state is smoothly transferred. It is considered to be the main role of the agent. The cationic groups ionize the surface of the particles and prevent the particles from coagulating. On the other hand, natural polymers have a strong tendency to be incompatible with synthetic polymers whose polymerization is proceeding. It also has a lower ionicity and is relatively hydrophobic compared to synthetic polymers, and surrounds the deposited particles adsorbed by a hydrophobic bond and causes microscopic phase separation between the deposited particles and the dissolved gel-like polymer. . Therefore, in terms of their roles, the polymer of the polymer type is ionized on the surface of the particle, and the polymer of the natural type is important in that it causes microscopic phase separation. It is presumed that this effect lowers the viscosity around the particles, improves the slip between the precipitated particles and the dissolved gelled polymer, and achieves a smooth phase change. In a combination of a nonionic polymer and a nonionic natural polymer, it is presumed that the above action is basically obtained, but in this case, both are not ionic and the surface of the deposited particles is It is presumed that the microscopic phase-separated structure covering only the particles suppresses the aggregation between particles.

The water-soluble polymer which is dispersion-polymerized in the salt aqueous solution may be cationic, amphoteric or nonionic. When polymerizing a cationic water-soluble polymer, a cationic monomer is used, and examples thereof include dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, and methyldiallylamine. Examples of the quaternary ammonium group-containing monomer include (meth) acryloyloxyethyl trimethylammonium chloride and (meth) acryloyl which are quaternized products of the tertiary amino-containing monomer with methyl chloride or benzyl chloride. Oxy-2-hydroxypropyltrimethylammonium chloride, (meth) acryloylaminopropyltrimethylammonium chloride, (meth) acryloyloxyethyldimethylbenzylammonium chloride,
(Meth) acryloyloxy 2-hydroxypropyldimethylbenzylammonium chloride, (meth) acryloylaminopropyldimethylbenzylammonium chloride, dimethyldiallylammonium chloride and the like.

When the amphoteric water-soluble polymer is polymerized, an anionic monomer is used in combination with the above-mentioned cationic monomer, examples of which include vinyl sulfonic acid, vinyl benzene sulfonic acid and 2-acrylamido-2-methyl. Propane sulfonic acid, methacrylic acid, acrylic acid, itaconic acid, maleic acid, p-carboxystyrene and the like.
Further, nonionic monomers such as (meth) acrylamide, N, N-dimethylacrylamide, vinyl acetate,
Acrylonitrile, methyl acrylate, 2-hydroxyethyl (meth) acrylate, diacetone acrylamide, N-vinylpyrrolidone, N-vinylformamide,
Examples thereof include N-vinylacetamide, which can be copolymerized with one kind or two or more kinds. In the case of producing a nonionic polymer, acrylamide may be used to copolymerize the above nonionic monomer in the range of 0 to 30 mol%.

In the case of a cationic water-soluble polymer, the above-mentioned cationic monomer is copolymerized or polymerized at 1 mol% or more to 100 mol%, preferably 10 mol% to 100 mol%. In the case of an amphoteric water-soluble polymer, the anionic monomer is copolymerized in an amount of 1 mol% or more to 50 mol%, preferably 5 mol% to 30 mol%.

The polymerization conditions are usually determined appropriately depending on the monomers used and the mol% of the copolymerization, and the temperature is 0-10.
Perform in the range of 0 ° C. A radical polymerization initiator is used to initiate the polymerization. These initiators may be either oil-soluble or water-soluble, and can be polymerized by any of azo type, peroxide type and redox type. Examples of oil-soluble azo initiators include 2,2′-azobisisobutyronitrile,
1,1'-azobis (cyclohexanecarbonitrile), 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2-methylpropione-
G), 4,4-azobis (4-methoxy-2,4dimethyl) valeronitrile, etc., which are dissolved in a water-miscible solvent and added.

Examples of water-soluble azo initiators include:
2'-azobis (amidinopropane) dihydrochloride,
2,2'-Azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 4,4 '
-Azobis (4-cyanovaleric acid) and the like. Further, examples of the redox system include a combination of ammonium peroxodisulfate and sodium sulfite, sodium hydrogen sulfite, trimethylamine, tetramethylethylenediamine and the like. Further examples of peroxides include ammonium or potassium peroxodisulfate,
Examples thereof include hydrogen peroxide, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, succinic peroxide, t-butylperoxy 2-ethylhexanoate and the like. Most preferred of these initiators are water-soluble azo initiators2,
2'-azobis (amidinopropane) dihydrochloride,
2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride.

The salt to be used is a salt of an alkali metal ion such as sodium or potassium or an ammonium ion with a halide ion, a sulfate ion, a nitrate ion or a phosphate ion, but a salt with a polyvalent anion. Is more preferable. The salt concentration of these salts is 7% by weight to
Can be used up to saturation concentration.

The water-soluble polymer composed of the polymer dispersion of the present invention is used for dehydration of pulp sludge in the paper industry, other wastewater treatment of food industry, metal and petroleum refining, and treatment of gravel washing wastewater related to building materials. It can be applied to mixed sludge including organic sludge and coagulated sludge generated in general industrial wastewater treatment. As a particularly effective target, it exerts an excellent effect on sewage, digested sludge of human waste, or excess sludge of food industry wastewater. These sludges are dehydrated by a dehydrator such as a belt press, a filter press, a decanter or a screw press after the water-soluble polymer dispersion of the present invention is dissolved in water to form an aqueous solution, which is added and coagulated. To do. The amount to be added varies depending on the type of drainage, the concentration of suspended matter, etc.
It is about pm. Moreover, it is 0.1 to 3 weight% with respect to sludge ss.

(Synthesis Example-1 Synthesis Example of Acrylic and Diallylamine Polymers) Acryloyl oxyethyltrimethylammonium chloride homopolymer (dispersant 1) and acroyl oxyethyltrimethylammonium in molar ratios shown in Table 1. A chloride / acrylamide copolymer (dispersant 2) was synthesized. 20% by weight aqueous solution of each monomer 300
g and adjust the pH to 5.0 with sulfuric acid, then 42 ℃
After nitrogen substitution for 30 minutes at room temperature, 3 g of a 2% aqueous solution of 2,2-azobisamidinopropane dihydrochloride is used as an initiator.
(0.1% by weight per monomer) was added to initiate polymerization. After keeping the temperature at 42 ° C. for 15 hours, the heating was stopped to terminate the polymerization. Then, the weight average molecular weight was measured with a molecular weight measuring device (DLS-7000 manufactured by Otsuka Electronics) by the static light scattering method, and the cation equivalent value (meq / g) of the polymer was measured by the colloid titration method. The results are shown in Table 1.

(Synthesis Example-2 Synthesis Example of Amidine Polymer)
In a 50 ml four-necked flask equipped with a stirrer, a nitrogen inlet tube, and a condenser tube, 6.0 g and 34.0 g of a mixture of acrylonitrile and N-vinylformamide containing acrylonitrile in the mole fraction shown in Table 1 was added. Demineralized water was added. After the temperature was raised to 60 ° C. with stirring in a nitrogen gas stream, 0.12 g of a 10% 2,2′-azobis-2-amidinopropane dihydrochloride aqueous solution was added. 4 at 45 ° C
After stirring and holding for a time, the temperature was raised to 60 ° C., and the temperature was further held for 3 hours to obtain a suspension in which a polymer was precipitated in water. 20 g of water was added to the suspension, and then 2 equivalents of concentrated hydrochloric acid was added to the formyl group in the polymer, and the mixture was kept at 100 ° C. for 4 hours while stirring to polymerize the polymer. The obtained polymer solution was added to acetone to cause precipitation, which was vacuum dried to obtain Sample-1 to Sample-5.

With respect to Sample-1 to Sample-5, the composition and the weight average molecular weight by the light scattering method were measured by the following methods. The results are shown in Table-1.

(Composition Analysis Method) The composition of each raw material polymer before the amidination was determined by 13 C-NMR spectrum (13 C-
It was calculated from the integrated value of the absorption peak corresponding to each monomer unit of the magnetic resonance spectrum). The composition of each of the polymers A to E after amidation was calculated from the integrated value of the absorption peak corresponding to each repeating unit of the 13 C-NMR spectrum. The repeating units (1) and (2) are not distinguished,
It was calculated as the total amount. The repeating units (8) and (9) were also calculated as the total amount without distinction.

Further, repeating units (1) and (2),
The absorption peaks of (6) and (8) and (9) are 170 to 18
Since it is found in a very close position around 5 ppm,
The structure corresponding to each absorption peak was assigned by the following method. That is, the weight balance was confirmed by elemental analysis of the polymer and measurement of the water content, and further the IR spectrum was measured in addition to the 13 C-NMR spectrum of the polymer, and the spectrum of the polymer and the amidine group, amide group and lactam group were measured. It employs a method for comparing and examining the spectrum of a known compound having the above.

(Measurement of Molecular Weight) For Sample-1 to Sample-5, a molecular weight measuring device (DL manufactured by Otsuka Electronics Co., Ltd.) by a static light scattering method was used.
S-7000) to measure the weight average molecular weight. The above results are shown in Table 1.

(Synthesis Example-3 Synthesis Example of Vinylamine Polymer) In a 50 ml four-necked flask equipped with a stirrer, a nitrogen introducing tube, and a cooling tube, 6.0 g and 34.0 g of N-vinylformamide were removed. I added salt water. In a nitrogen gas stream, the temperature was raised to 60 ° C. with stirring, and then 10% 2,2′-azobis-2-amidinopropane dihydrochloride aqueous solution 0.1%
2 g was added. After stirring and holding at 45 ° C. for 6 hours, 6
The temperature was raised to 0 ° C., and the temperature was further maintained for 2 hours to obtain an N-vinylformamide polymer aqueous solution. 20 g of water was added to the suspension, and then 2 equivalents of concentrated hydrochloric acid was added to the formyl group in the polymer, and the mixture was kept at 100 ° C. for 4 hours while stirring to polymerize the polymer. The resulting polymer solution was added to acetone to cause precipitation, and this was vacuum dried to give a sample-
Got 6. The degree of cationization was measured by the colloid titration method, and the molecular weight was measured by the light scattering method. The results are shown in Table-1.

(Other dispersants) PEI is P-1050 (molecular weight 50,000), butene / produced by Nippon Shokubai Co., Ltd.
Isoban (manufactured by Kuraray Co., Ltd.) was used as the completely amidated maleic anhydride copolymer. The physical properties are shown in Table-1.

[0049]

[Table 1] DMQ: acryloyloxyethyltrimethylammonium chloride DD: diallyldimethylammonium chloride NVF: N-vinylformamide, ACM: acryloylmorpholine Molecular weight: 10,000 units, cation equivalent: meq / g

(Natural Polymer) As the natural dispersant, the following polymers were used.

[Table 2]

[0051]

Example 1 A five-necked separable flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube was charged with the polymer NO. 3 (30% aqueous solution), 16.7 g (4.0% for monomer), Locust bean gum NO. 11 (15% aqueous solution), 41.6 g (5.0% of monomer), ion-exchanged water 140.0 g, ammonium sulfate 115.0 g, acrylamide 50% aqueous solution 6
Charge 7.4 g and acryloyloxyethyl trimethyl ammonium chloride, 115.0 g 80% aqueous solution,
It was completely dissolved. The internal temperature was maintained at 33 to 35 ° C., and after substituting with nitrogen for 30 minutes, 2,2′-azobis [2-
(5-Methyl-2-imidazolin-2-yl) propane] 1.9 g of a 1% aqueous solution of dihydrochloride (0.015% based on the monomer) was added to initiate polymerization. 2.5 hours after the start of the reaction, a slight increase in the viscosity of the reaction product was observed, but the state was maintained for 20 minutes, but then it stayed and transferred to the dispersion liquid. After 8 hours from the start, 0.5 g of the above initiator solution was added, and polymerization was further performed for 8 hours. The resulting dispersion has a swelling monomer concentration of 25.0% and a polymer particle size of 10
The viscosity of the dispersion was 200 mPa · s or less.
In addition, a molecular weight measuring device by a static light scattering method (Otsuka Electronics D
The weight average molecular weight was measured by LS-7000).
This sample is referred to as prototype-1. The results are shown in Table 4.

[0052]

Example 2 A polymer NO. Prepared in Synthesis Example 3 was placed in a five-neck separable flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube. 4 (20% aqueous solution), 37.5 g (6.0% with respect to monomer), chitosan derivative NO. 15 (15% aqueous solution), 29.2 g (to 3.5% of monomer), ion-exchanged water 146.0 g, ammonium sulfate 115.0 g, acrylamide 50% aqueous solution 66.
2 g, methacryloyloxyethyltrimethylammonium chloride 80% aqueous solution, 40.3 g and acryloyloxyethyltrimethylammonium chloride, 80% aqueous solution 75.1 g were charged and completely dissolved. Internal temperature 3
After maintaining the temperature at 3-35 ° C. and substituting with nitrogen for 30 minutes, 1% aqueous solution of 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride as an initiator 2. Polymerization was initiated by adding 5 g (0.02% of monomer). 2.5 hours after the start of the reaction, a slight increase in the viscosity of the reaction product was observed, but the state was maintained for 20 minutes, but then it stayed and transferred to the dispersion liquid. After 8 hours from the start, 1.3 g of the above initiator solution was added, and polymerization was further performed for 8 hours. The concentration of the ingested monomer in the obtained dispersion is 25.0%,
Polymer particle size is less than 10 μm, dispersion viscosity is 240 m
It was Pa · s. This sample is referred to as prototype-2. The results are shown in Table 4.

[0053]

Examples 3 to 10 Using a dispersant system in which the polymer of Table 1 and the polymer of Table 2 are combined with the polymer of Table 2 by the same operation as in Example 1, the addition amount and the monomer shown in Table 3 are used. Prototypes 3 to 10 were synthesized according to the composition. The results are shown in Table 4.

[0054]

[Embodiment 11] In a five-neck separable flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube, 59.0 g of acrylamide 50% aqueous solution and acrylic acid 60% aqueous solution 2
5.0g was added and 35% sodium hydroxide aqueous solution 2
An equivalent amount of acrylic acid was neutralized with 3.8 g. In addition to this, the polymer type polymer 1 (20% aqueous solution) 28.8 g
(Vs. the amount of 5.0%), cationized cellulose NO. 16 (20% aqueous solution) 28.8 g (versus monomer 5.0%), ion-exchanged water 120.0 g, ammonium sulfate 115.0 g, and acryloyloxyethyltrimethylammonium chloride, 80% aqueous solution 10
0.6 g was charged and completely dissolved. Internal temperature is 33 to 3
Keep the temperature at 5 ° C and replace with nitrogen for 30 minutes.
Polymerization was initiated by adding 1.9 g of 1% aqueous solution of 2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride to 0.015% of the amount. It was After 1 hour and 45 minutes from the start, a slight increase in the viscosity of the reaction product was observed, but this state continued for 30 minutes, and then the reaction product stopped and transferred to the dispersion liquid. After 8 hours from the start, 0.9 g of the above initiator solution was added, and polymerization was further performed for 8 hours. The concentration of the incorporated monomer in the obtained dispersion was 23%, the particle size of the polymer was in the range of 1 to 20 μm, and the viscosity of the dispersion was 180 mPa · s. The results are shown in Table 4.

[0055]

Examples 12 to 18 Using the dispersant system in which the polymer of Table 1 and the polymer of Table 2 and the natural polymer are combined by the same operation as in Example 11, the addition amount and the monomer shown in Table 3 are used. Prototype-12 to Prototype-18 were synthesized according to the composition. The results are shown in Table 4.

[0056]

[Example 19] Polymerization meter polymer NO. Was placed in a 5-neck separable flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube. 10 (20% aqueous solution), 26.3 g (5.0% of monomer), natural polymer NO. 15 (20% aqueous solution), 31.5 g (6.0% of monomer), 120.0 g of ion-exchanged water, 115.0 g of ammonium sulfate and 210 g of 50% aqueous solution of acrylamide were charged and completely dissolved. After maintaining the internal temperature at 29 to 33 ° C. and substituting with nitrogen for 30 minutes, 1% of 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride as an initiator was used. 1.1 g of aqueous solution (0.010% of monomer)
Was added to initiate polymerization. After 2 hours from the start, a slight increase in the viscosity of the reaction product was observed, and this state was maintained for 40 minutes, but then it settled and transferred to the dispersion liquid. After 8 hours from the start, 0.5 g of the above initiator solution was added, and polymerization was further performed for 8 hours. The concentration of the swelling monomer in the obtained dispersion was 21.
The polymer particle size was 0%, the polymer particle size was 10 μm or less, and the viscosity of the dispersion liquid was 100 mPa · s. Prototype of this sample-11
And The results are shown in Table 4.

[0057]

Example 20 A dispersant system obtained by combining the polymer of Table 1 with the polymer of Table 2 and the natural polymer was used in the same manner as in Example 19, and the addition amount and the monomer composition shown in Table 3 were used. Prototype-20 was synthesized. The results are shown in Table 4.

[0058]

[Comparative Example 1] Polymerized polymer N was placed in a 5-neck separable flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube.
O. 3 (30% aqueous solution), 16.7 g (to monomer 4.0)
%), Ion-exchanged water 186.4 g, ammonium sulfate 1
15.0 g, 67.4 g of 50% aqueous acrylamide solution, 115.0 g of 80% aqueous solution of acryloyloxyethyltrimethylammonium chloride were charged and completely dissolved. After maintaining the internal temperature at 33 to 35 ° C. and substituting with nitrogen for 30 minutes, 1% of 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride was used as an initiator. Aqueous solution 1.9g (0.015% of monomer)
Was added to initiate polymerization. After 1 hour and 50 minutes from the start, the reaction became viscous and the reaction continued. After that, the viscosity decreased over a period of one period, and the viscosity changed to a dispersion liquid. After 8 hours from the start, 0.9 g of the above initiator solution was added, and polymerization was further performed for 8 hours. The results are shown in Table 4.

[0059]

Comparative Examples 2 to 6 By the same operation as in Comparative Example 1, the polymerized polymer alone or the natural polymer alone shown in Table 1 or 2 was used as a dispersant, and the addition amount and the monomer composition shown in Table 3 were used. Comparative-2 to Comparative-6 were synthesized. The results are shown in Table 4.

[0060]

[Table 3] DMQ: Acryloyloxyethyltrimethylammonium chloride DMC: Methacryloyloxyethyltrimethylammonium chloride ABC: Acryloyloxyethylbenzylbenzyldimethylammonium chloride DMPQ: Acryloylaminopropyltrimethylammonium chloride AAC: Acrylic acid, IA: Itaconic acid, AAM: Acrylamide

[0061]

[Table 4] Addition amount: mass% of monomer, dispersion viscosity: mPa · s, molecular weight: 10,000

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08F 20/52 C08F 20/52 20/60 20/60 28/02 28/02 F term (reference) 4D015 BA05 BA09 BA10 BA11 BB06 CA04 CA05 CA11 CA12 DB04 DB05 DB09 DB16 DB30 DB32 DB33 DB35 DC02 DC06 DC07 DC08 EA02 EA32 FA03 FA19 4J002 AA031 AB012 AB042 AB052 BC101 BC121 BG011 BG071J0101 BG071 JQ01 BJ001 BJ001 BJ001 BJ001 BJ001 BJ002 BJ001 BJ002 BJ001 BJ002 001. 4J100 AB07R AG04S AJ02R AJ08R AJ09R AL03S AL08Q AL08S AM02S AM15P AM15S AM21Q AM21R AN04S AN14Q AP01R AQ08S BA03Q BA03S BA13S BA14S BA16R BA33Q BA43Q BA56R CA04 CA05 CA06 DA38 EA06 FA18 FA03 FA03

Claims (19)

[Claims] 1. A salt aqueous solution containing one or more fine particles of water-soluble polymer selected from cationic, amphoteric and nonionic particles having a particle size of 100 μm or less, and a polymeric cationic polymer soluble as a dispersant in the salt aqueous solution. And / or a water-soluble polymer dispersion in which a nonionic polymer and at least one or more of natural cationic polymers coexist. 2. One or more fine particles of water-soluble polymer selected from cationic, amphoteric and nonionic particles having a particle size of 100 μm or less in a salt aqueous solution, and a cationic polymerization system soluble as a dispersant in the salt aqueous solution. A water-soluble polymer dispersion in which a polymer and at least one or more of a nonionic natural polymer coexist. 3. The water-soluble polymer dispersion is at least one or more of a polymerizable cationic and / or nonionic polymer and a natural cationic polymer soluble in the salt aqueous solution as a dispersant. And the following general formula (1) and /
Or 0 to 100 mol% of the monomer represented by (2), (3)
The monomer represented by 0 to 50 mol%, acrylamide 0 to
100 mol% and copolymerizable nonionic monomer 0-3
The water-soluble polymer dispersion liquid according to claim 1, which is produced by dispersion-polymerizing a monomer (mixture) consisting of 0 mol% in an aqueous salt solution with stirring. [Chemical 1] General formula (1) R1 is hydrogen or a methyl group, R2 and R3 are C1 to C3 alkyl or alkoxyl groups, R4 is hydrogen, a C1 to C3 alkyl group, alkoxyl group or benzyl go, May be different, A is oxygen or N
H and B represent an alkylene group having 2 to 4 carbon atoms or an alkoxylene group, and X1 represents an anion. [Chemical 2] Formula (2) R5 represents hydrogen or a methyl group, R6 and R7 represent an alkyl group having 1 to 3 carbon atoms, an alkoxy group or a benzyl group, and X2 represents an anion. General formula (3) R8 is hydrogen, a methyl group or a carboxymethyl group, A is SO3, C6H4SO3, CONHC (CH3) 2CH
2SO3, C6H4COO or COO, R9 is hydrogen or COOY2, Y1 or Y2 is hydrogen or cation 4. The water-soluble polymer dispersion is allowed to coexist with at least one of a polymerizable cationic polymer and a natural nonionic polymer soluble in the salt aqueous solution as a dispersant, 0 to 100 mol% of the monomer represented by the general formula (1) and / or (2), 0 to the monomer represented by (3)
It is produced by dispersion-polymerizing a monomer (mixture) consisting of 50 mol%, acrylamide 0 to 100 mol% and a copolymerizable nonionic monomer 0 to 30 mol% under stirring in an aqueous salt solution. The water-soluble polymer dispersion liquid according to claim 2, wherein 5. The polymerized cationic and / or nonionic polymer component has one or more structural units selected from the following general formulas (4) to (9).
The water-soluble polymer dispersion described in. [Chemical 4] General formula (4) R10 is hydrogen or a methyl group, and R11 and R12 have 1 carbon atom.
~ 3 alkyl or alkoxyl group, R13 is hydrogen, an alkyl group having 1 to 3 carbon atoms, an alkoxyl group or benzyl go, which may be the same or different, A is oxygen or NH, B is alkylene having 2 to 4 carbons. X3 represents a group or an alkoxylene group, and X3 represents an anion, respectively. [Chemical 5] Formula (5) R14 and R15 represent hydrogen or a methyl group, R16 and R17 represent an alkyl group having 1 to 3 carbon atoms, an alkoxy group or a benzyl group, and X4 represents an anion. Formula (6) R18 is hydrogen or methyl go, X5 is an anion, Formula (7) R19 and R20 are hydrogen or methyl go, X6 is an anion General formula (8) R21 is hydrogen or methyl go, General formula (9) Here, R23 is hydrogen or a methyl group, A is CONR2
4R25 (R24 and R25 are hydrogen, an alkyl group having 1 to 4 carbon atoms or an alkoxyl group), OR26 (R26
Is hydrogen or an alkyl group or alkoxyl group having 1 to 4 carbon atoms, an acyl group), NHCOR27 (R27 is hydrogen, an alkyl group or alkoxyl group having 1 to 4 carbon atoms), an alkyl group or alkoxyl group having 1 to 10 carbon atoms , Aryl group, or nonionic hetero 5-membered ring or 6-membered ring, R28 represents hydrogen or methyl group, respectively. 6. The polymerizable cationic polymer component has one or more structural units represented by the general formulas (4) to (8) and the general formula (9), respectively. Item 2
The water-soluble polymer dispersion described in. 7. The water-soluble polymer dispersion according to claim 1, wherein the natural cationic polymer is selected from chitosan, chitosan derivatives, starch derivatives, and cellulose derivatives. 8. The natural nonionic polymer is starch, a starch derivative, a cellulose derivative, guar gum,
The water-soluble polymer dispersion according to claim 2, which is selected from locust bean gum. 9. The ion equivalent value of the polymerized cationic polymer or natural cationic polymer is 1.5 to 22 m.
It is eq / g, The water-soluble polymer dispersion liquid of Claim 1 or 2 characterized by the above-mentioned. 10. A cationic that constitutes a polymer dispersion,
The water-soluble polymer dispersion according to claim 1 or 2, wherein one or more water-soluble polymers selected from nonionic and amphoteric have a weight average molecular weight of 2,000,000 or more and 20,000,000 or less. . 11. The water-soluble polymer dispersion liquid according to claim 1, wherein the salt constituting the aqueous salt solution contains at least one polyvalent anion salt. 12. In a salt aqueous solution, as a dispersant, at least one or more of a polymerizable cationic and / or nonionic polymer and a natural cationic polymer soluble in the salt aqueous solution are allowed to coexist. 5 to 100 mol% of the monomer represented by the general formula (1) and / or (2), 0 to 50 mol% of the monomer represented by (3), and 0 to 100 mol% of acrylamide.
And 0 to 30 mol% of other non-ionic copolymerizable monomer
A method for producing a water-soluble polymer dispersion liquid having a particle size of 100 μm or less, which comprises subjecting a monomer (mixture) consisting of to a dispersion polymerization under stirring. 13. In the aqueous salt solution, at least one of a polymerizable cationic polymer and a natural nonionic polymer soluble in the aqueous salt solution as a dispersant is allowed to coexist, and the compound represented by the general formula (1) ) And / or the monomer represented by (2) 0 to 1
00 mol%, the monomer represented by (3) 0 to 50 mol%,
A particle size of 1, characterized in that a monomer (mixture) consisting of 0 to 100 mol% of acrylamide and 0 to 30 mol% of another copolymerizable nonionic monomer is dispersed and polymerized under stirring.
A method for producing a water-soluble polymer dispersion having a size of 00 μm or less. 14. The polymerized cationic and / or nonionic polymer has one or more structural units selected from the general formulas (4) to (9).
2. The method for producing the water-soluble polymer dispersion described in 2. 15. The polymerizable cationic polymer has one or more structural units represented by the general formulas (4) to (8) and a structural unit represented by the general formula (9), respectively. 14. The method for producing a water-soluble polymer dispersion according to claim 13. 16. The method for producing a water-soluble polymer dispersion according to claim 11, wherein the natural cationic polymer is selected from chitosan, chitosan derivatives, starch derivatives and cellulose derivatives. . 17. The water-soluble solution according to claim 12, wherein the natural nonionic polymer is selected from starch, starch derivatives, cellulose derivatives, guar gum, and locust bean gum. For producing a water-soluble polymer dispersion. 18. The ion equivalent value of the polymerized cationic polymer or natural cationic polymer is 1.5 to 22.
It is meq / g, The manufacturing method of the water-soluble polymer dispersion liquid of Claim 12 or 13 characterized by the above-mentioned. 19. The method for producing a water-soluble polymer dispersion according to claim 12, wherein the salt constituting the aqueous salt solution contains at least one polyvalent anion salt.