JP4008932B2 - Water-soluble polymer, sludge coagulation dehydrating agent and sludge coagulation dehydration method - Google Patents

Description

  The present invention relates to a water-soluble polymer, a sludge coagulation dehydrating agent, and a sludge coagulation dehydration method.

  Organic sludge such as excess sludge and coagulated sludge is generated by biological treatment of sewage, human waste or various industrial wastewater. Until now, cationic polymer has been used alone for the dewatering treatment of these sludges. Since molecular polymers have poor cohesion, the amount of sludge treatment is limited, and the treatment state is not satisfactory in terms of moisture content of dehydrated cake, SS recovery rate, peelability of cake from filter cloth, etc. There is no need for improvement.

  In order to solve these problems, various water-soluble polymer polymers having a cationic aggregation dehydrating agent and an anionic aggregation dehydrating agent in the molecule have been proposed (Patent Document 1).

The water-soluble polymer is produced by copolymerizing a cationic aggregation dehydrating agent and an anionic aggregation dehydrating agent.
As the cationic aggregating dehydrating agent, for example, N, N-dialkylaminoalkyl (meth) acrylate hydrochloride is used.
Moreover, acrylic acid, acrylic acid amide, etc. are used as said anionic aggregation dehydrating agent.

  By the way, the water-soluble polymer that has been used conventionally is added to the water in which the organic sludge is suspended, whereby the organic sludge is agglomerated and solid-liquid separated. Agglomerated flocs that are easily lumps are produced, but the strength of the agglomerated flocs is relatively weak, and thus there are problems such as insufficient peelability of the sludge cake from the filter cloth.

  In addition, in the case where N, N-dialkylaminoalkyl (meth) acrylate hydrochloride is used as the cationic coagulant dehydrating agent, a strong acid such as hydrochloric acid is used, so the problem of corrosion of the manufacturing equipment and the careful handling are important. Has the problem that it is necessary.

  Furthermore, most of the sludge cake produced by dehydration is finally incinerated, but in the case where hydrochloride is used as the cationic flocculating dehydrating agent, there is a concern that dioxins may be generated by incineration. There's a problem.

  Therefore, without corroding the production equipment, there is no concern about the generation of dioxins, etc. even if incineration, etc., and water-soluble that can be used as a coagulation dehydrating agent with good peeling performance to peel the sludge cake from the filter cloth There is a need for high molecular weight polymers.

Japanese Patent Laid-Open No. 8-71599

  In view of the above-mentioned problems, the present invention does not corrode production equipment, and there is no concern about the generation of dioxins or the like even if incineration is performed. It is an object to provide a water-soluble polymer that can be used as an agent.

  The inventor of the present invention has conducted extensive studies to solve the above problems, and as a result, has found that the above problems can be solved by the following water-soluble polymer, and has completed the present invention.

That is, the present invention reacts a saturated carboxylic acid having two or more carboxylic acid groups in one molecule with an equivalent N, N-dialkylaminoalkyl (meth) acrylate with respect to the carboxylic acid group of the saturated carboxylic acid. Tertiary amine saturated carboxylate monomer, hydroxymethyl (meth) acrylate, diethylene glycol mono (meth) acrylate, polyethylene glycol (polymerization degree 3-50) mono (meth) acrylate, polyglycerol (polymerization degree 1-10) ) Mono (meth) acrylate, (meth) acrylamide, N-methyl- (meth) acrylamide, N-isopropyl- (meth) acrylamide, N-methylol- (meth) acrylamide, acrylonitrile, N-vinyl-2-pyrrolidone, vinyl Imidazole, N-vinylsuccinimi , P-aminostyrene, N-vinylcarbazole, 2-vinylpyridine, vinylmorpholine, 2-cyanoethyl- (meth) acrylate, (meth) acrylic acid, maleic anhydride, fumaric acid, itaconic acid, vinylbenzoic acid, vinylsulfone Acid, styrenesulfonic acid, 2- (meth) acryloyloxyethanesulfonic acid, 2- (meth) acryloyloxypropanesulfonic acid, 3- (meth) acryloyloxypropanesulfonic acid, 2- (meth) acryloyloxybutanesulfonic acid, 4- (meth) acryloyloxybutanesulfonic acid, 2- (meth) acryloyloxy-2,2-dimethylethanesulfonic acid, p- (meth) acryloyloxymethylbenzenesulfonic acid, 2- (meth) acryloylaminoethanesulfonic acid , 2- (meth) a Liloylaminopropanesulfonic acid, 3- (meth) acryloylaminopropanesulfonic acid, 2- (meth) acryloylaminobutanesulfonic acid, 4- (meth) acryloylaminobutanesulfonic acid, 2- (meth) acryloylamino-2, 2-dimethylethanesulfonic acid, p- (meth) acryloylaminomethylbenzenesulfonic acid, methyl (meth) allylsulfosuccinate, (meth) acryloyl polyoxyethylene (2 to 50 ethylene oxide adduct) sulfate Provided is a water-soluble high molecular polymer obtained by copolymerizing a water-soluble monomer having one or more α, β unsaturated double bonds selected from the group .

When forming a tertiary amine salt, use of saturated carboxylic acid having two or more carboxylic acid groups in one molecule instead of hydrochloric acid eliminates corrosion of production equipment, etc., and generates dioxins during incineration There will be no.
Moreover, aggregation performance and peeling performance are improved by using saturated carboxylate instead of hydrochloride as the counter ion of the tertiary amine salt.
Furthermore, coagulation performance and peeling performance are improved by copolymerizing a water-soluble monomer having an α, β unsaturated double bond.

Since the water-soluble polymer according to the present invention does not use a strong acid such as hydrochloric acid in the production process, the production equipment is not corroded and the working efficiency can be improved.
Moreover, even if the flocs treated with the water-soluble polymer according to the present invention are incinerated, there is no concern about the generation of dioxins.
Furthermore, according to the water-soluble polymer according to the present invention, the coagulation performance with respect to organic sludge can be improved, and when the aggregated floc is dehydrated using a filter cloth, the aggregated floc is peeled off from the filter cloth. Peeling performance can be improved.

Hereinafter, the water-soluble polymer of the present invention will be described.
The water-soluble polymer of the present invention is obtained by copolymerizing a tertiary amine saturated carboxylate monomer and a water-soluble monomer having an α, β unsaturated double bond.
The tertiary amine saturated carboxylate monomer is composed of a saturated carboxylic acid having two or more carboxylic acid groups in one molecule, and an equivalent N, N-dialkylaminoalkyl (meta) to the carboxylic acid group of the saturated carboxylic acid. ) It is obtained by reacting with acrylate.

  Examples of the N, N-dialkylaminoalkyl (meth) acrylate include N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, and N, N-diethylaminoethyl (meth). Acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-dipropylaminoethyl (meth) acrylate, N, N-dipropylaminopropyl (meth) acrylate, N-methyl, N-ethyl-aminoethyl ( (Meth) acrylate, N-methyl, N-ethyl-aminopropyl (meth) acrylate, N-methyl, N-propyl-aminoethyl (meth) acrylate, N-methyl, N-propyl-aminopropyl (meth) acrylate, N -Ethyl, N-propyl-aminoethyl (meth) acrylate, N-ethyl, N-propyl-aminopropyl (meth) acrylate It is.

The saturated carboxylic acid is not particularly limited as long as it has two or more carboxylic acid groups in one molecule.
For example, examples of the saturated carboxylic acid include those having a molecular weight of 300 or less, such as citric acid, malic acid, tartaric acid, oxalic acid, adipic acid, and succinic acid.

Examples of the water-soluble monomer having an α, β unsaturated double bond include nonionic monomers and anionic monomers.
The water-soluble monomer having an α, β unsaturated double bond is a monomer having a functional group such as a carboxylic acid group, an amide group, a sulfonic acid group, a nitrile group, a pyrrolidone group, or an imidazole group in the molecule. preferable.
The water-soluble monomer having an α, β unsaturated double bond may be used alone or in combination of two or more.

Examples of the nonionic monomer include (meth) acrylate derivatives, (meth) acrylamide derivatives, and nitrogen atom-containing vinyl monomer derivatives.
As the (meth) acrylate derivatives, hydroxymethyl (meth) acrylate, diethylene glycol mono (meth) acrylate, polyethylene glycol (polymerization degree of 3 to 50) mono (meth) acrylate, polyglycerol (polymerization degree 10) mono (meth ) acrylate and the like.
Examples of the (meth) acrylamide derivatives, (meth) acrylamide, N- methyl - (meth) acrylamide, N- isopropyl - (meth) acrylamide, N- methylol - (meth) acrylamide.
Examples of the nitrogen atom-containing vinyl monomer derivative include acrylonitrile, N-vinyl-2-pyrrolidone, vinylimidazole, N-vinylsuccinimide, p-aminostyrene, N-vinylcarbazole, 2-vinylpyridine, vinylmorpholine, 2-cyanoethyl- (Meth) acrylate is mentioned.

As said anionic monomer, unsaturated carboxylic acid, unsaturated sulfonic acid, (meth) acryloyl polyoxyalkylene (C1-C6) sulfate ester is mentioned.
Examples of the unsaturated carboxylic acid, (meth) acrylic acid, maleic acid anhydride, fumaric acid, itaconic acid, vinyl benzoic acid.
Examples of the unsaturated sulfonic acid include aliphatic unsaturated sulfonic acid having 2 to 20 carbon atoms, aromatic unsaturated sulfonic acid having 6 to 20 carbon atoms, sulfonic acid group-containing (meth) acrylate, and sulfonic acid group-containing (meth). acrylamide, alkyl (C1-20) (meth) allyl sulfosuccinate.

The aliphatic unsaturated sulfonic acid of the 2 to 20 carbon atoms, and vinyl sulfonic acid.
Examples of the aromatic unsaturated sulfonic acid of the 6 to 20 carbon atoms and styrene sulfonic acid.
Examples of the sulfonic acid group-containing (meth) acrylate, 2- (meth) acryloyloxy ethane sulfonic acid, 2- (meth) acryloyloxy-propanesulfonic acid, 3- (meth) acryloyloxy-propanesulfonic acid, 2- (meth) acryloyloxy butanoic acid, 4- (meth) acryloyloxy butanoic acid, 2- (meth) acryloyloxy-2,2-dimethyl-ethane sulfonic acid, p- (meth) acryloyloxy-methylbenzenesulfonic acid.
Examples of the sulfonic acid group-containing (meth) acrylamide, 2- (meth) acryloyl-aminoethanesulfonic acid, 2- (meth) acryloyl amino acid, 3- (meth) acryloyl amino acid, 2- (meth) acryloylamino butanoic acid, 4- (meth) acryloyl amino butanoic acid, 2- (meth) acryloyl-2,2-dimethyl-ethanesulfonic acid, p- (meth) acryloyl amino-methylbenzenesulfonic acid.
The alkyl (C1-20) (meth) allyl sulfosuccinate esters include methyl (meth) allyl sulfosuccinate.
The (meth) acryloyl polyoxyalkylene (1-6 carbon atoms) sulfate, and (meth) acrylate (ethylene oxide adduct of mole number 2-50) acryloyloxy polyoxyethylene sulfates.

The water-soluble monomer having an α, β unsaturated double bond is preferably the (meth) acrylamide derivative, the unsaturated carboxylic acid, the sulfonic acid group-containing (meth) acrylate, or the sulfonic acid-containing (meth) acrylamide. , (Meth) acrylamide, (meth) acrylic acid, 2- (meth) acryloyloxyethanesulfonic acid, 2- (meth) acryloyloxypropanesulfonic acid, 3- (meth) acryloyloxypropanesulfonic acid, 2- (meth) More preferred is acryloylaminopropanesulfonic acid, 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid.
These water-soluble monomers are frequently used from the viewpoint of availability and price.

  In the present invention, a preferable combination of the N, N-dialkylaminoalkyl (meth) acrylate, the saturated carboxylic acid and the water-soluble monomer having an α, β unsaturated double bond is 1) N, N-dimethylamino Ethyl methacrylate, (citric acid or malic acid), (meth) acrylamide, 2) N, N-dimethylaminoethyl methacrylate, (citric acid or malic acid), acrylamide, and (meth) acrylic acid, 3) N, N-dimethyl Examples include combinations of aminoethyl methacrylate, (citric acid or malic acid), acrylamide, and 2- (meth) acryloylaminopropanesulfonic acid.

  The water-soluble polymer of the present invention is obtained by copolymerizing the tertiary amine saturated carboxylate monomer and the water-soluble monomer having the α, β unsaturated double bond.

Composition ratio (mol%) of the tertiary amine saturated carboxylate monomer and the water-soluble monomer having an α, β unsaturated double bond at the time of copolymerization 99.5: 0.5 to 0.5: 99 .5, preferably 90:10 to 10:90.
When the composition ratio (mol%) is within this range, the performance of coagulating and dewatering organic sludge is excellent. In addition, when there are two or more water-soluble monomers having an α, β unsaturated double bond, it is the total value of the two or more monomers.

The method of copolymerizing the tertiary amine saturated carboxylate monomer and the water-soluble monomer having an α, β unsaturated double bond can be carried out by conventionally known thermal polymerization or photopolymerization, and is not particularly limited. However, it is preferable to carry out by the photopolymerization method described in JP-B-8-5926, for example. Hereinafter, the case of copolymerization by the photopolymerization method will be described as an example.
The copolymerization of the tertiary amine saturated carboxylate monomer and the water-soluble monomer having an α, β unsaturated double bond is carried out by solution polymerization in an aqueous solution.
In the case of solution polymerization, the concentration of a solution in which a water-soluble monomer having an α, β unsaturated double bond is added to the tertiary amine saturated carboxylate monomer is generally in the range of 65 to 80% by weight. It is preferable.
If the concentration of the solution in which the water-soluble monomer having an α, β unsaturated double bond is mixed with the tertiary amine saturated carboxylate monomer is less than 65% by weight, there is a problem that the production efficiency is lowered.
In addition, if the concentration of a solution in which a water-soluble monomer having an α, β unsaturated double bond is blended with the tertiary amine saturated carboxylate monomer exceeds 80% by weight, it becomes difficult to control the polymerization heat generation, and the product quality There is a problem that leads to a decrease.

As a polymerization initiator in the case of photopolymerization, for example, an initiator such as benzophenone, benzoin, benzoin alkyl ether or the like can be used.
The polymerization initiator is used in an amount of 0.001 to 1.0 weight based on 100 parts by weight of the mixture of the tertiary amine saturated carboxylate monomer and the water-soluble monomer having an α, β unsaturated double bond. Part is preferred.

As a device for generating light energy to be used for initiating photopolymerization, usually a commercially available xenon lamp, tungsten lamp, halogen lamp, carbon arc lamp, high-pressure mercury lamp as a mercury lamp, Low pressure mercury lamps and ultra high pressure mercury lamps are used, but high pressure mercury lamps are generally used.
The wavelength used varies somewhat depending on the type of photopolymerization initiator used, but the range of 300 to 380 nm is usually most effective.

As the polymerization method, a mixed solution of a tertiary amine saturated carboxylate monomer having a predetermined solution concentration and a water-soluble monomer having an α, β unsaturated double bond is prepared, and after adding a photopolymerization initiator, An inert gas such as nitrogen gas or carbon dioxide gas is sealed to remove dissolved oxygen.
When the mixed solution is irradiated with an ultraviolet lamp, the polymerization proceeds in a short time, and the target water-soluble polymer is obtained.

The water-soluble polymer of the present invention can be used as an aggregating dewatering agent for sludge. When used as an aggregating dewatering agent for sludge, it is necessary to have a molecular weight in an appropriate range.
In the field of sludge flocculating dehydrating agents, an appropriate range of molecular weight is often expressed using a numerical value called intrinsic viscosity.
In the water-soluble polymer of the present invention, the intrinsic viscosity is 3 dl / g or more.
In order to increase the intrinsic viscosity to 3 dl / g or more, it can be adjusted by using a chain transfer agent when copolymerizing a tertiary amine saturated carboxylate monomer and a water-soluble monomer having an α, β unsaturated double bond. As the chain transfer agent, alcohols such as isopropyl alcohol and allyl alcohol, mercaptans such as thioglycolic acid and thioglycerol, and phosphites such as sodium hypophosphite can be used.
When the intrinsic viscosity is less than 3 dl / g, the cohesive force of organic sludge and the like is weak, the coagulation flocs are small, and the dewatering performance may be reduced.
The intrinsic viscosity is measured by the method described in the examples.

The amount of the sludge coagulant dewatering agent used for the organic sludge is such that when 2.5 parts by weight of organic sludge (absolutely dry) is suspended in 100 parts by weight of water, the sludge coagulant dewatering agent is 0.002%. It is -0.1 weight part, Preferably it is 0.003-0.075 weight part.
If the sludge flocculating dehydrating agent is less than 0.002 parts by weight, the flocculated flocs are not formed, and solid-liquid separation may not be possible.
Moreover, when the coagulation dehydrating agent for sludge exceeds 0.1 parts by weight, there is a possibility that the viscosity is increased and it becomes difficult to separate and dehydrate the coagulated floc.
Here, the absolutely dry state means a state in which the organic sludge does not contain moisture.

When the sludge flocculating dehydrating agent is added to organic sludge and used, an inorganic flocculant can be used in combination as necessary.
The inorganic flocculant used in combination is not particularly limited, and examples thereof include polyiron (polyferric sulfate), aluminum sulfate, polyaluminum chloride, ferric chloride, and ferrous sulfate. When an inorganic flocculant is used in combination, it is preferable to add the flocculant dewatering agent for sludge after adding and stirring the inorganic flocculant to the organic sludge.

The amount of the inorganic flocculant used when the sludge flocculent dehydrating agent and the inorganic flocculant are used in combination is 0.01 to 0.5 weight of the inorganic flocculant with respect to 100 parts by weight of the organic sludge. Part, preferably 0.03 to 0.3 part by weight.
In the case of the sludge coagulation dewatering method when the sludge coagulation dehydrating agent is used in combination with the inorganic coagulant, when the amount of the inorganic coagulant used is less than 0.01 parts by weight, the sludge coagulation dehydrating agent is used. There is a risk that the combined use effect will not be achieved.

  Moreover, when using as a flocculent dehydrating agent for sludge, acidic substances, such as sulfamic acid and sodium hydrogen sulfate, can also be added. The acidic substance is added in order to neutralize the alkaline component in the dissolved water used for dissolving the sludge flocculating dehydrating agent. The amount of the acidic substance used can be appropriately adjusted depending on the type of water used for dissolution (for example, industrial water, city water, sewage treated water, etc.).

As the coagulation method using the sludge coagulation dehydrating agent, for example, the coagulation dehydration agent for sludge is added to and mixed with organic sludge and stirred to form a coagulation floc, and then the coagulation floc is dehydrated with a dehydrator. A method is mentioned.
This dehydration is usually performed by a gravity dehydrator, a pressure dehydrator and a centrifugal dehydrator.
Examples of the gravity dehydrator include a rotary screen.
Examples of the pressure dehydrator include a belt press, a screw press, a caterpillar type roll press, and a filter press.
Further, examples of the centrifugal dehydrator include a screw decanter and a basket decanter.
Among these, preferable dehydrators include a belt press dehydrator and a screw press centrifugal dehydrator.

  Examples of the organic sludge to be used with the sludge coagulation dehydrating agent include raw sludge such as sewage excreta and industrial wastewater, sludge generated by microbial treatment (excess sludge, digested sludge), and mixed sludges thereof. it can.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited at all by these Examples.
In the following examples, N, N-dimethylaminoethyl methacrylate tertiary amine citrate is DM citrate, N, N-dimethylaminoethyl methacrylate tertiary amine malate is DM malate, N, N-dimethylaminoethyl methacrylate tertiary amine hydrochloride is DM hydrochloride, N, N-diethylaminoethyl methacrylate tertiary amine citrate is DE citrate, N, N-diethylaminoethyl methacrylate tertiary amine apple The acid salt is represented as DE malate, N, N-diethylaminoethyl methacrylate tertiary amine hydrochloride as DE hydrochloride, acrylamide as AAm, acrylic acid as AAc, and 2-acryloylaminopropanesulfonic acid as ATBS. .

(Measurement method of infrared spectrophotometry)
Measurement was performed using FTS-135 manufactured by BIO-RAD.
The liquid composition was measured by being sandwiched between KBr crystal plates, and the solid composition was measured by pulverizing and mixing with KBr powder and tableting with a tablet molding machine.

(Flock diameter measurement method)
The diameter of the flocculated floc produced by adding and stirring the sludge flocculating dehydrating agent to the organic sludge was measured visually.

(Measurement method of moisture content of sludge cake)
The weight of the sludge cake immediately after pressing was measured, and the sludge cake was placed in a dryer at 105 ° C. to remove moisture. When the weight after drying became constant, the weight was measured to determine the water content.

(Measurement method of transparency)
The clarity of the filtrate was measured using a fluorometer. The sample was put into a fluorometer, and the height of the water layer in which the double line of the sign board placed on the bottom through the water layer became clear was measured.

(Measurement method of intrinsic viscosity)
1) Preparation of sample solution for measurement About 0.2g of sample (water-soluble polymer) is weighed into a 200ml stoppered Erlenmeyer flask and dissolved by adding pure water so that the evaporation residue is 0.2%. The mixture was stirred at 300 rpm for 1 hour and sealed. The solution was allowed to stand overnight (about 15 to 24 hours) and then stirred at 300 rpm for 1 hour using a magnetic stirrer.
This 0.2% aqueous solution was gently filtered using a glass filter (3G-1) to remove insoluble matters.
The filtrate was taken into a 100 ml stoppered Erlenmeyer flask with a 25 ml hole pipette, and 25 ml of 2N-sodium nitrate solution was added with a whole pipette. This made a 0.1% -1N-sodium nitrate solution.
Using this 0.1% -1N-sodium nitrate solution as a mother liquor and 1N-sodium nitrate solution as a diluent, 0.08%, 0.06%, 0.04%, and 0.02% sample solutions were prepared in a 100 ml stoppered Erlenmeyer flask.
2) Preparation of viscometer (Canon Fenceke type) The viscometer was washed 5 times or more with pure water using an aspirator, and the inside was dried (more than 10 minutes) through acetone.
3) Viscometer blank measurement Cannon Fenceke viscometer is set vertically in a thermostat previously adjusted to 30 ± 0.1 ° C, and 10 ml of 1N sodium nitrate solution is put into it with a whole pipette and left for 20 to 30 minutes. After that, the measurement was performed. For measurement, after raising the liquid level to about 10 to 15 mm above the marked line of the viscometer using a rubber spoid, the liquid is allowed to flow naturally, and the time for the liquid level to pass between the upper and lower marked lines of the viscometer is measured. It was measured. This was repeated twice or more, and the measurement was continued until the difference between the measured values was within 0.2 seconds. The average value was used as a viscometer blank (T0).
4) Viscosity measurement In the same manner as in 3) above, 10 ml of each sample solution having a sample concentration of 0.08%, 0.06%, 0.04%, and 0.02% was placed in a viscometer with a whole pipette, and the flow time was measured.
5) Calculation of Intrinsic Viscosity Using the concentration of the sample solution on the X axis and the reduced viscosity on the Y axis, a linear equation was calculated by the least square method, and the value of Y when X = 0 was obtained. This value is the intrinsic viscosity.
The reduced viscosity was calculated from the equation ηsp / C = (ηrel−1) / C. Here, ηrel = T / T0, ηsp = ηrel−1, T: flow time of sample solution (second), T0: flow time of blank (second), ηrel: relative viscosity, ηsp: specific viscosity, C: sample solution Concentration (%), ηsp / C: Reducing viscosity (dl / g).

(Synthesis Example 1)
N, N-dimethylaminoethyl methacrylate 520.6 g (3.316 mol), citric acid 212.2 g (1.105 mol), acrylamide 26.1 g (0.368 mol), thiourea 1.52 g, polyoxyalkylene alkyl ether (HLB about 11) 0.076 g, 0.049 g of sodium hypophosphite was added to 279.5 g of deionized water in order and stirred to synthesize a mixture of DM citrate monomer and AAm having a solid content (73.0%) (composition ratio 90 mol%: 10 mol%). . Table 1 shows the amount of raw materials used.

(Synthesis Example 2)
A mixture of DM citrate monomer having a solid content concentration (70.0%) and AAm (composition ratio 40 mol%: 60 mol%) was synthesized using the same method as in Synthesis Example 1. Table 1 shows the amount of raw materials used.

(Synthesis Example 3)
Using the same method as in Synthesis Example 1, a mixture (composition ratio 10 mol%: 90 mol%) of DM citrate monomer having a solid content concentration (65.0%) and AAm was synthesized. Table 1 shows the amount of raw materials used.

(Synthesis Example 4)
A mixture of DM citrate monomer having a solid content concentration (65.0%), AAm, and AAc (composition ratio 30 mol%: 60 mol%: 10 mol%) was synthesized using the same method as in Synthesis Example 1. Table 1 shows the amount of raw materials used.

(Synthesis Example 5)
A mixture of DM citrate monomer having a solid content concentration (65.0%), AAm and AAc (composition ratio: 25 mol%: 45 mol%: 30 mol%) was synthesized using the same method as in Synthesis Example 1. Table 1 shows the amount of raw materials used.

(Synthesis Example 6)
A mixture of DM citrate monomer having a solid content concentration (65.0%), AAm and ATBS (composition ratio 35 mol%: 60 mol%: 5 mol%) was synthesized using the same method as in Synthesis Example 1. Table 1 shows the amount of raw materials used.

(Synthesis Example 7)
A mixture of DM malate monomer having a solid content concentration (70.0%) and AAm (composition ratio 40 mol%: 60 mol%) was synthesized using the same method as in Synthesis Example 1. Table 1 shows the amount of raw materials used.

(Synthesis Example 8)
Using a method similar to that in Synthesis Example 1, a mixture (composition ratio 40 mol%: 60 mol%) of DM hydrochloride monomer having a solid content concentration (67.0%) and AAm was synthesized. Table 1 shows the amount of raw materials used.

(Synthesis Example 9)
In the same manner as in Synthesis Example 1, a mixture of DM hydrochloride monomer having a solid content concentration (67.0%), AAm and AAc (composition ratio 30 mol%: 60 mol%: 10 mol%) was synthesized. Table 1 shows the amount of raw materials used.

(Synthesis Example 10)
A mixture of DE citrate monomer having a solid content concentration (73.0%) and AAm (composition ratio 90 mol%: 10 mol%) was synthesized using the same method as in Synthesis Example 1. Table 1 shows the amount of raw materials used.

(Synthesis Example 11)
A mixture of DE citrate monomer having a solid content concentration (70.0%) and AAm (composition ratio 40 mol%: 60 mol%) was synthesized using the same method as in Synthesis Example 1. Table 1 shows the amount of raw materials used.

(Synthesis Example 12)
A mixture of DE citrate monomer having a solid content concentration (65.0%) and AAm (composition ratio 10 mol%: 90 mol%) was synthesized using the same method as in Synthesis Example 1. Table 1 shows the amount of raw materials used.

(Synthesis Example 13)
A mixture of DE citrate monomer having a solid content concentration (65.0%), AAm and AAc (composition ratio 30 mol%: 60 mol%: 10 mol%) was synthesized using the same method as in Synthesis Example 1. Table 1 shows the amount of raw materials used.

(Synthesis Example 14)
A mixture of DE citrate monomer having a solid content concentration (65.0%), AAm, and AAc (composition ratio: 25 mol%: 45 mol%: 30 mol%) was synthesized using the same method as in Synthesis Example 1. Table 1 shows the amount of raw materials used.

(Synthesis Example 15)
A mixture of DE citrate monomer having a solid content concentration (65.0%), AAm and ATBS (composition ratio 35 mol%: 60 mol%: 5 mol%) was synthesized using the same method as in Synthesis Example 1. Table 1 shows the amount of raw materials used.

(Synthesis Example 16)
Using a method similar to that in Synthesis Example 1, a mixture of DE malate monomer having a solid content concentration (70.0%) and AAm (composition ratio 40 mol%: 60 mol%) was synthesized. Table 1 shows the amount of raw materials used.

(Synthesis Example 17)
A mixture of DE hydrochloride monomer having a solid content concentration (67.0%) and AAm (composition ratio 40 mol%: 60 mol%) was synthesized using the same method as in Synthesis Example 1. Table 1 shows the amount of raw materials used.

(Synthesis Example 18)
A mixture of DE hydrochloride monomer having a solid content concentration (67.0%), AAm and AAc (composition ratio 30 mol%: 60 mol%: 10 mol%) was synthesized using the same method as in Synthesis Example 1. Table 1 shows the amount of raw materials used.

＊１：HLB約11
＊２：（モノマー重量＋使用した酸の重量）÷合計

* 1: About 11 HLB
* 2: (monomer weight + used acid weight) ÷ total

(Synthesis of DM citrate-AAm (composition ratio 90 mol%: 10 mol%) copolymer)
The reaction tank has a square shape with a side of 25 cm provided with a cooling jacket, and the upper part of the reaction tank is covered with a glass plate, and an ultraviolet lamp is installed on the glass plate. The reaction tank was purged with an inert gas (nitrogen gas) to adjust the oxygen concentration in the reaction tank to 0.2 vol% or less.
Nitrogen gas was introduced into 940 g of the mixture solution of DM citrate monomer and AAm obtained in Synthesis Example 1, and the oxygen concentration in the solution was adjusted to 1 mg / l or less to prepare a polymerization initiator solution (5% benzoin isopropyl (Methanol solution of ether) (4.23 g) was added and mixed, and poured into the reaction vessel. While cooling the reaction vessel, the ultraviolet ray intensity was adjusted to the monomer solution so that the ultraviolet ray intensity at the bottom of the reaction vessel was 10 W / m ² , and the ultraviolet ray was irradiated for 60 minutes. The obtained polymer gel was crushed into chips, crushed to about 1 mm with a crusher, dried for 1 hour with a hot air drier at 80 ° C., and DM citrate-AAm (composition ratio 90 mol). %: 10 mol%) copolymer was obtained. The intrinsic viscosity of the copolymer was 5.71 dl / g. Intrinsic viscosity values are shown in Table 2.

(Synthesis of DM citrate-AAm (composition ratio 40 mol%: 60 mol%) copolymer)
The mixture obtained in Synthesis Example 2 was polymerized using the same method as the synthesis of the copolymer to obtain a DM citrate-AAm (composition ratio 40 mol%: 60 mol%) copolymer. The intrinsic viscosity of the copolymer was 6.27 dl / g. Intrinsic viscosity values are shown in Table 2.
Results of IR measurement: Absorption of 1596 cm ⁻¹ (carboxylate), 1669 cm ⁻¹ (amide bond), and 1727 cm ⁻¹ (ester bond) was confirmed.

(Synthesis of DM citrate-AAm (composition ratio 10 mol%: 90 mol%) copolymer)
The mixture obtained in Synthesis Example 3 was polymerized using the same method as the synthesis of the copolymer to obtain a DM citrate-AAm (composition ratio 10 mol%: 90 mol%) copolymer. The intrinsic viscosity of the copolymer was 6.35 dl / g. Intrinsic viscosity values are shown in Table 2.

(Synthesis of DM citrate-AAm-AAc (composition ratio 30 mol%: 60 mol%: 10 mol%) copolymer)
DM citrate-AAm-AAc (composition ratio 30 mol%: 60 mol%: 10 mol%) copolymer was obtained by polymerizing the mixture obtained in Synthesis Example 4 using the same method as the synthesis of the copolymer. Obtained.
The intrinsic viscosity of the copolymer was 5.97 dl / g. Intrinsic viscosity values are shown in Table 2.
Results of IR measurement: Absorption of 1619 cm ⁻¹ (carboxylate), 1665 cm ⁻¹ (amide bond), and 1728 cm ⁻¹ (ester bond) was confirmed.

(Synthesis of DM citrate-AAm-AAc (composition ratio 25 mol%: 45 mol%: 30 mol%) copolymer)
DM citrate-AAm-AAc (composition ratio 25 mol%: 45 mol%: 30 mol%) copolymer was polymerized by polymerizing the mixture obtained in Synthesis Example 5 using the same method as the synthesis of the copolymer. Obtained.
The intrinsic viscosity of the copolymer was 5.88 dl / g. Intrinsic viscosity values are shown in Table 2.
Results of IR measurement: Absorption of 1619 cm ⁻¹ (carboxylate), 1665 cm ⁻¹ (amide bond), and 1728 cm ⁻¹ (ester bond) was confirmed.

(Synthesis of DM citrate-AAm-ATBS (composition ratio 35 mol%: 60 mol%: 5 mol%) copolymer)
DM citrate-AAm-ATBS (composition ratio 35 mol%: 60 mol%: 5 mol%) copolymer was polymerized by polymerizing the mixture obtained in Synthesis Example 6 using the same method as the synthesis of the copolymer. Obtained.
The intrinsic viscosity of the copolymer was 5.86 dl / g. Intrinsic viscosity values are shown in Table 2.
IR measurement results: Absorption of 1603 cm ^-1 (carboxylate), 1665 cm ^-1 (amide bond), 1730 cm ^-1 (ester bond), and 1040 cm ^-1 (sulfonic acid) was confirmed.

(Synthesis of DM malate-AAm (composition ratio 40 mol%: 60 mol%) copolymer)
The mixture obtained in Synthesis Example 7 was polymerized using the same method as the synthesis of the copolymer to obtain a DM malate-AAm (composition ratio 40 mol%: 60 mol%) copolymer. The intrinsic viscosity of the copolymer was 6.32 dl / g. Intrinsic viscosity values are shown in Table 2.
Results of IR measurement: Absorption of 1598 cm ⁻¹ (carboxylate), 1667 cm ⁻¹ (amide bond), and 1728 cm ⁻¹ (ester bond) was confirmed.

(Synthesis of DM hydrochloride-AAm (composition ratio 40 mol%: 60 mol%) copolymer)
The mixture obtained in Synthesis Example 8 was polymerized using the same method as the synthesis of the copolymer to obtain a DM hydrochloride-AAm (composition ratio 40 mol%: 60 mol%) copolymer. The intrinsic viscosity of the copolymer was 6.19 dl / g. Intrinsic viscosity values are shown in Table 2.

(Synthesis of DM hydrochloride-AAm-AAc (composition ratio 30 mol%: 60 mol%: 10 mol%) copolymer)
The mixture obtained in Synthesis Example 9 was polymerized using the same method as the synthesis of the copolymer to obtain a DM hydrochloride-AAm-AAc (composition ratio 30 mol%: 60 mol%: 10 mol%) copolymer. It was. The intrinsic viscosity of the copolymer was 5.94 dl / g. Intrinsic viscosity values are shown in Table 2.

(Synthesis of DE citrate-AAm (composition ratio 90 mol%: 10 mol%) copolymer)
The mixture obtained in Synthesis Example 10 was polymerized using the same method as the synthesis of the copolymer to obtain a DE citrate-AAm (composition ratio 90 mol%: 10 mol%) copolymer. The intrinsic viscosity of the copolymer was 5.64 dl / g. Intrinsic viscosity values are shown in Table 2.

(Synthesis of DE citrate-AAm (composition ratio 40 mol%: 60 mol%) copolymer)
The mixture obtained in Synthesis Example 11 was polymerized using the same method as the synthesis of the copolymer to obtain a DE citrate-AAm (composition ratio 40 mol%: 60 mol%) copolymer. The intrinsic viscosity of the copolymer was 6.03 dl / g. Intrinsic viscosity values are shown in Table 2.

(Synthesis of DE citrate-AAm (composition ratio 10 mol%: 90 mol%) copolymer)
The mixture obtained in Synthesis Example 12 was polymerized using the same method as the synthesis of the copolymer to obtain a DE citrate-AAm (composition ratio 10 mol%: 90 mol%) copolymer. The intrinsic viscosity of the copolymer was 5.94 dl / g. Intrinsic viscosity values are shown in Table 2.

(Synthesis of DE citrate-AAm-AAc (composition ratio 30 mol%: 60 mol%: 10 mol%) copolymer)
The mixture obtained in Synthesis Example 13 was polymerized using the same method as the synthesis of the copolymer to obtain a DE citrate-AAm-AAc (composition ratio 30 mol%: 60 mol%: 10 mol%) copolymer. Obtained.
The intrinsic viscosity of the copolymer was 5.63 dl / g. Intrinsic viscosity values are shown in Table 2.

(Synthesis of DE citrate-AAm-AAc (composition ratio 25 mol%: 45 mol%: 30 mol%) copolymer)
The mixture obtained in Synthesis Example 14 was polymerized using the same method as the synthesis of the copolymer to obtain a DE citrate-AAm-AAc (composition ratio 25 mol%: 45 mol%: 30 mol%) copolymer. Obtained.
The intrinsic viscosity of the copolymer was 5.72 dl / g. Intrinsic viscosity values are shown in Table 2.

(Synthesis of DE citrate-AAm-ATBS (composition ratio 35 mol%: 60 mol%: 5 mol%) copolymer)
The mixture obtained in Synthesis Example 15 was polymerized using the same method as the synthesis of the copolymer to obtain a DE citrate-AAm-ATBS (composition ratio 35 mol%: 60 mol%: 5 mol%) copolymer. Obtained.
The intrinsic viscosity of the copolymer was 5.55 dl / g. Intrinsic viscosity values are shown in Table 2.

(Synthesis of DE malate-AAm (composition ratio 40 mol%: 60 mol%) copolymer)
The mixture obtained in Synthesis Example 16 was polymerized using the same method as the synthesis of the copolymer to obtain a DE malate-AAm (composition ratio 40 mol%: 60 mol%) copolymer. The intrinsic viscosity of the copolymer was 5.97 dl / g. Intrinsic viscosity values are shown in Table 2.

(Synthesis of DE hydrochloride-AAm (composition ratio 40 mol%: 60 mol%) copolymer)
The mixture obtained in Synthesis Example 17 was polymerized using the same method as the synthesis of the copolymer to obtain a DE hydrochloride-AAm (composition ratio 40 mol%: 60 mol%) copolymer. The intrinsic viscosity of the copolymer was 5.86 dl / g. Intrinsic viscosity values are shown in Table 2.

(Synthesis of DE hydrochloride-AAm-AAc (composition ratio 30 mol%: 60 mol%: 10 mol%) copolymer)
The mixture obtained in Synthesis Example 18 was polymerized using the same method as the synthesis of the copolymer to obtain a DE hydrochloride-AAm-AAc (composition ratio 30 mol%: 60 mol%: 10 mol%) copolymer. It was. The intrinsic viscosity of the copolymer was 5.52 dl / g. Intrinsic viscosity values are shown in Table 2.

(Sewage sludge evaluation test)
Example 1
Take 200 ml of sludge (TS = 2.3% (solid content concentration in the sludge in a completely dry state), pH = 6.5, mixture of raw and surplus sludge) in a 300 ml beaker, DM citrate-AAm (composition ratio 90 mol%: 10 mol%) A 0.2 wt% copolymer aqueous solution was added in various amounts of 10.0 ml, 12.5 ml, and 15.0 ml, and the mixture was stirred at 200 rpm for 30 seconds using a stirrer equipped with turbine blades.
After stirring, after measuring the floc diameter of the generated sludge, Nutsche Roth (diameter 7cm) laid with nylon filter cloth (Nippon Filcon Co., Ltd., trade name: Lh4085, air permeability 155cc / cm ² / sec) The agglomerated sludge was poured into the mixture, naturally filtered, and the amount of filtrate after 30 seconds was measured.
Moreover, the clarity of the filtrate at this time was evaluated with a fluorometer.
The aggregated sludge after filtration is taken on a filter cloth for a belt press, pressed at 1 kg / cm ² and 2 kg / cm ² for 1 minute each, and the peelability from the filter cloth of the sludge cake after pressing is visually evaluated. The moisture content of the sludge cake was measured. The results are shown in Table 3.
The water content of the sludge cake was determined by the method described above.

(Example 2)
The same operation as in Example 1 was performed using a DM citrate-AAm (composition ratio: 40 mol%: 60 mol%) copolymer. The results are shown in Table 3.

(Example 3)
The same operation as in Example 1 was performed using a DM citrate-AAm (composition ratio 10 mol%: 90 mol%) copolymer. The results are shown in Table 3.

(Example 4)
The same operation as in Example 1 was performed using a DM citrate-AAm-AAc (composition ratio 30 mol%: 60 mol%: 10 mol%) copolymer. The results are shown in Table 3.

(Example 5)
The same operation as in Example 1 was performed using a DM citrate-AAm-AAc (composition ratio 25 mol%: 45 mol%: 30 mol%) copolymer. The results are shown in Table 3.

(Example 6)
The same operation as in Example 1 was performed using a DM citrate-AAm-ATBS (composition ratio 35 mol%: 60 mol%: 5 mol%) copolymer. The results are shown in Table 3.

(Example 7)
The same operation as in Example 1 was performed using a DM malate-AAm (composition ratio: 40 mol%: 60 mol%) copolymer. The results are shown in Table 3.

(Example 8)
The same operation as in Example 1 was performed using a DE citrate-AAm (composition ratio 90 mol%: 10 mol%) copolymer. The results are shown in Table 3.

Example 9
The same operation as in Example 1 was performed using a DE citrate-AAm (composition ratio: 40 mol%: 60 mol%) copolymer. The results are shown in Table 3.

(Example 10)
The same operation as in Example 1 was performed using a DE citrate-AAm (composition ratio: 10 mol%: 90 mol%) copolymer. The results are shown in Table 3.

(Example 11)
The same operation as in Example 1 was performed using a DE citrate-AAm-AAc (composition ratio 30 mol%: 60 mol%: 10 mol%) copolymer. The results are shown in Table 3.

(Example 12)
The same operation as in Example 1 was performed using a DE citrate-AAm-AAc (composition ratio 25 mol%: 45 mol%: 30 mol%) copolymer. The results are shown in Table 3.

(Example 13)
The same operation as in Example 1 was performed using a DE citrate-AAm-ATBS (composition ratio 35 mol%: 60 mol%: 5 mol%) copolymer. The results are shown in Table 3.

(Example 14)
The same operation as in Example 1 was performed using a DE malate-AAm (composition ratio: 40 mol%: 60 mol%) copolymer. The results are shown in Table 3.

(Comparative Example 1)
The same operation as in Example 1 was performed using the DM hydrochloride-AAm (composition ratio: 40 mol%: 60 mol%) copolymer. The results are shown in Table 3.

(Comparative Example 2)
The same operation as in Example 1 was performed using the DM hydrochloride-AAm-AAc (composition ratio 30 mol%: 60 mol%: 10 mol%) copolymer. The results are shown in Table 3.

(Comparative Example 3)
The same operation as in Example 1 was performed using the DE hydrochloride-AAm (composition ratio: 40 mol%: 60 mol%) copolymer. The results are shown in Table 3.

(Comparative Example 4)
The same operation as in Example 1 was performed using the DE hydrochloride-AAm-AAc (composition ratio 30 mol%: 60 mol%: 10 mol%) copolymer. The results are shown in Table 3.

（＊１）剥離性評価
○：きれいに剥離
○△：１０％程度付着
△：３０％程度付着
×：５０％程度付着

(* 1) Peelability evaluation ○: Cleanly peeled ○ △: About 10% adhesion △: About 30% adhesion ×: About 50% adhesion

(Polyiron combined sewage sludge evaluation test)
(Example 15)
Take 200 ml of sludge (TS = 2.3%, pH = 6.5, mixture of raw and surplus sludge) in a 300 ml beaker, add 0.1 ml of polyiron (Fe = 11 wt%) and mix uniformly, then DM citrate-AAm (Composition ratio 90 mol%: 10 mol%) 10.0 ml of a 0.2 wt% aqueous solution of the copolymer was added, and the mixture was stirred at 200 rpm for 30 seconds using a stirrer equipped with turbine blades.
After stirring, after measuring the floc diameter of the generated sludge, Nutsche Roth (diameter 7cm) laid with nylon filter cloth (Nippon Filcon Co., Ltd., trade name: Lh4085, air permeability 155cc / cm ² / sec) The agglomerated sludge was poured into the solution, naturally filtered, and the filtrate amount after 30 seconds was measured.
Moreover, the clarity of the filtrate at this time was evaluated with a fluorometer.
The aggregated sludge after filtration is taken on a filter cloth for a belt press, pressed at 1 kg / cm ² and 2 kg / cm ² for 1 minute each, and the peelability from the filter cloth of the sludge cake after pressing is visually evaluated. The moisture content of the sludge cake was measured. The measurement was performed by changing the amount of polyiron added to 0.2 ml and 0.3 ml. The results are shown in Table 4.

(Example 16)
The same operation as in Example 15 was performed using a DM citrate-AAm (composition ratio: 40 mol%: 60 mol%) copolymer. The results are shown in Table 4.

(Example 17)
The same operation as in Example 15 was performed using a DM citrate-AAm (composition ratio 10 mol%: 90 mol%) copolymer. The results are shown in Table 4.

(Example 18)
The same operation as in Example 15 was performed using a DM citrate-AAm-AAc (composition ratio 30 mol%: 60 mol%: 10 mol%) copolymer. The results are shown in Table 4.

Example 19
The same operation as in Example 15 was performed using a DM citrate-AAm-AAc (composition ratio 25 mol%: 45 mol%: 30 mol%) copolymer. The results are shown in Table 4.

(Example 20)
The same operation as in Example 15 was performed using a DM citrate-AAm-ATBS (composition ratio 35 mol%: 60 mol%: 5 mol%) copolymer. The results are shown in Table 4.

(Example 21)
The same operation as in Example 15 was performed using a DM malate-AAm (composition ratio: 40 mol%: 60 mol%) copolymer. The results are shown in Table 4.

(Example 22)
The same operation as in Example 15 was performed using a DE citrate-AAm (composition ratio 90 mol%: 10 mol%) copolymer. The results are shown in Table 4.

(Example 23)
The same operation as in Example 15 was performed using a DE citrate-AAm (composition ratio: 40 mol%: 60 mol%) copolymer. The results are shown in Table 4.

(Example 24)
The same operation as in Example 15 was performed using a DE citrate-AAm (composition ratio: 10 mol%: 90 mol%) copolymer. The results are shown in Table 4.

(Example 25)
The same operation as in Example 15 was performed using a DE citrate-AAm-AAc (composition ratio 30 mol%: 60 mol%: 10 mol%) copolymer. The results are shown in Table 4.

(Example 26)
The same operation as in Example 15 was performed using a DE citrate-AAm-AAc (composition ratio 25 mol%: 45 mol%: 30 mol%) copolymer. The results are shown in Table 4.

(Example 27)
The same operation as in Example 15 was performed using a DE citrate-AAm-ATBS (composition ratio 35 mol%: 60 mol%: 5 mol%) copolymer. The results are shown in Table 4.

(Example 28)
The same operation as in Example 15 was performed using a DE malate-AAm (composition ratio: 40 mol%: 60 mol%) copolymer. The results are shown in Table 4.

(Comparative Example 5)
The same operation as in Example 15 was performed using the DM hydrochloride-AAm (composition ratio: 40 mol%: 60 mol%) copolymer. The results are shown in Table 4.

(Comparative Example 6)
The same operation as in Example 15 was performed using the DM hydrochloride-AAm-AAc (composition ratio 30 mol%: 60 mol%: 10 mol%) copolymer. The results are shown in Table 4.

(Comparative Example 7)
The same operation as in Example 15 was performed using the DE hydrochloride-AAm (composition ratio: 40 mol%: 60 mol%) copolymer. The results are shown in Table 4.

(Comparative Example 8)
The same operation as in Example 15 was performed using the DE hydrochloride-AAm-AAc (composition ratio 30 mol%: 60 mol%: 10 mol%) copolymer. The results are shown in Table 4.

（＊１）剥離性評価
○：きれいに剥離
○△：１０％程度付着
△：３０％程度付着
×：５０％程度付着

(* 1) Peelability evaluation ○: Cleanly peeled ○ △: About 10% adhesion △: About 30% adhesion ×: About 50% adhesion

  In Examples 1 to 28, the filtrate clarity and peelability were improved.

Claims (4)

A tertiary amine obtained by reacting a saturated carboxylic acid having two or more carboxylic acid groups in one molecule with an equivalent N, N-dialkylaminoalkyl (meth) acrylate to the carboxylic acid group of the saturated carboxylic acid. A saturated carboxylate monomer;
Hydroxymethyl (meth) acrylate, diethylene glycol mono (meth) acrylate, polyethylene glycol (degree of polymerization 3-50) mono (meth) acrylate, polyglycerol (degree of polymerization 1-10) mono (meth) acrylate, (meth) acrylamide, N -Methyl- (meth) acrylamide, N-isopropyl- (meth) acrylamide, N-methylol- (meth) acrylamide, acrylonitrile, N-vinyl-2-pyrrolidone, vinylimidazole, N-vinylsuccinimide, p-aminostyrene, N -Vinylcarbazole, 2-vinylpyridine, vinylmorpholine, 2-cyanoethyl- (meth) acrylate, (meth) acrylic acid, maleic anhydride, fumaric acid, itaconic acid, vinylbenzoic acid, vinylsulfonic acid, styrene Sulfonic acid, 2- (meth) acryloyloxyethanesulfonic acid, 2- (meth) acryloyloxypropanesulfonic acid, 3- (meth) acryloyloxypropanesulfonic acid, 2- (meth) acryloyloxybutanesulfonic acid, 4- ( (Meth) acryloyloxybutanesulfonic acid, 2- (meth) acryloyloxy-2,2-dimethylethanesulfonic acid, p- (meth) acryloyloxymethylbenzenesulfonic acid, 2- (meth) acryloylaminoethanesulfonic acid, 2- (Meth) acryloylaminopropanesulfonic acid, 3- (meth) acryloylaminopropanesulfonic acid, 2- (meth) acryloylaminobutanesulfonic acid, 4- (meth) acryloylaminobutanesulfonic acid, 2- (meth) acryloylamino- 2,2-dimension From the group consisting of ruethanesulfonic acid, p- (meth) acryloylaminomethylbenzenesulfonic acid, methyl (meth) allylsulfosuccinate, (meth) acryloyl polyoxyethylene (ethylene oxide adduct having 2 to 50 moles) sulfate A water-soluble polymer obtained by copolymerizing a selected water-soluble monomer having one or more α, β unsaturated double bonds.   The composition ratio (mol%) of the tertiary amine saturated carboxylate monomer and the water-soluble monomer is 99.5: 0.5 to 0.5: 99.5, The water-soluble polymer as described.   A flocculent dewatering agent for sludge, comprising the water-soluble polymer according to claim 1 or 2.   A sludge coagulation dehydration method comprising using the coagulation dehydration agent for sludge according to claim 3 and an inorganic coagulant together.