JPH08143630A - (meth)acrylamide polymer having aminotriazine ring on side chain - Google Patents

Abstract

PURPOSE: To obtain a water-soluble or dispersible polymer useful as an additive for paper to improve its strength, water filterability, etc., further useful as an anchoring auxiliary agent for sizing agents, a coagulating agent, etc., by introducing an aminotriazine ring to a (meth)acrylamide group. CONSTITUTION: This polymer comprises (A) 0.05-60mol.% of aminotriazine ring derivative (salt) units of the formula [R1 is H, CH3 ; X is NH2 , NHR2 , N(Ar)2 (R2 is an alkyl; Ar is cyclohexyl, phenyl, etc.,), etc.], (B) 20-99.95 mol.3 of (meth)acrylamide structure units, and (C) 0-40mol.% of α,β-unsaturated (di) carboxylic acid (salt) structure units and/or α/β-unsaturated sulfonic acid (salt) structure units.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a (meth) acrylamide polymer having an aminotriazine derivative in its side chain.

[0002]

2. Description of the Related Art (Meth) acrylamide polymers are mainly used as papermaking additives such as paper strength enhancers and drainage improvers, and as aggregating agents for water treatment. The paper manufacturing industry is an industry that consumes a large amount of forest resources as a raw material and requires a large amount of energy in the pulp manufacturing and papermaking processes. As environmental problems at the global level have become more serious in recent years,
In such industries, sincere efforts for the environment are further required. The (meth) acrylamide polymer is used as a paper strength enhancer that maintains the product strength even if the ratio of waste paper in the raw material is increased. ing. Further, when the (meth) acrylamide polymer is used as a drainage improver, drainage of the pulp slurry on the wire is improved, and the water content of the wet sheet is reduced,
The amount of heat energy consumed in the drying process can be reduced. Further, the wastewater finally discharged from the papermaking system is treated with activated sludge, and the waste sludge is separated and clarified by a polymer flocculant composed of a (meth) acrylamide polymer.

As described above, the (meth) acrylamide polymer is a chemical which is effective in saving resources and energy and preserving the environment, but regarding environmental problems, it is a social responsibility to pay more attention to the environmental issues. Recognized and there is an ever increasing demand for higher performance chemicals.
As a method of imparting a function to a (meth) acrylamide polymer, there are two methods: a method of copolymerizing (meth) acrylamide and a functional monomer, and a method of post-modifying the (meth) acrylamide polymer to introduce a functional group. Be separated. (Meta)
Some functional groups that impart functions to acrylamide polymers have been proposed, but only a few are actually used. While higher performance is required in the future, there is a limit to the performance that can be achieved by simply combining conventional materials, and the development of functional groups with high functionality is desired.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies in order to solve these problems, and as a result, by introducing an aminotriazine ring into a (meth) acrylamide group, they were used as an additive for papermaking. The present invention was completed by discovering that various properties such as paper strength and drainage property are improved, and further that it becomes a useful polymer as a fixing aid for a sizing agent, a coagulant, and the like.

That is, the present invention is (1) a water-soluble or water-dispersible (meth) acrylamide-based polymer having an aminotriazine ring in its side chain, which comprises structural units (a) to (c): Further, (a) 0.05 to 60 mol% of the formula (1) [Chemical Formula 5], and / or the aminotriazine ring derivative unit which is an inorganic acid salt or an organic acid salt thereof.

[0006]

Embedded image _{(Wherein, R 1 = -H, -CH 3} , X = -NH 2, -N
_{HR 2, -NR 2 R 3,} -NHAr, N (Ar) 2: R
₂ , R ₃ represents a C _{1 to} C ₄ linear and / or branched alkyl group, Ar represents a cyclohexyl group, a phenyl group and / or a substituted phenyl group) (b) (meth) acrylamide structural unit 20 to 99 .95
Mol% (c) α, β-unsaturated (di) carboxylic acid (salt) structural unit and / or α, β-unsaturated sulfonic acid (salt) structural unit 0-40 mol% (2) (a)-( d) a water-soluble or water-dispersible (meth) acrylamide-based polymer having an aminotriazine ring in the side chain, and (a) a compound represented by the formula (1) Or 0.05 to 60 mol% of aminotriazine ring derivative unit which is an inorganic acid salt or an organic acid salt thereof

[0007]

[Chemical 6] _{(Wherein, R 1 = -H, -CH 3} , X = -NH 2, -N
_{HR 2, -NR 2 R 3,} -NHAr, N (Ar) 2: R
₂ , R ₃ represents a C _{1 to} C ₄ linear and / or branched alkyl group, Ar represents a cyclohexyl group, a phenyl group and / or a substituted phenyl group) (b) (meth) acrylamide structural unit 20 to 99 .9 mol% (c) α, β-unsaturated (di) carboxylic acid (salt) structural unit and / or α, β-unsaturated sulfonic acid (salt) structural unit 0-40 mol% (d) (meth) Acrylonitrile and / or (meth)
Acrylic ester structural unit 0.05-40 mol% (3) Acrylic compounds of (a)-(c) are radically polymerized in an aqueous medium, and have an aminotriazine ring in the side chain (meta ) A method for producing an acrylamide polymer, and (a) a (meth) acrylic monomer having an aminotriazine ring represented by the formula (2) [Chemical formula 7], and / or an inorganic acid salt thereof, Or organic acid salt 0.05-60 mol%

[0008]

[Chemical 7] _{(Wherein, R 1 = -H, -CH 3} , X = -NH 2, -N
_{HR 2, -NR 2 R 3,} -NHAr, N (Ar) 2: R
₂ , R ₃ represents a C _{1 to} C ₄ linear and / or branched alkyl group, Ar represents a cyclohexyl group, a phenyl group and / or a substituted phenyl group) (b) (meth) acrylamide 20 to 99.95 Mol% (c) α, β-unsaturated (di) carboxylic acid (salt) and / or α, β-unsaturated sulfonic acid (salt) 0 to 40 mol% (4) (a) to (d) acrylic A method for producing a (meth) acrylamide-based polymer having an aminotriazine ring in a side chain, which comprises radically polymerizing a base compound in an aqueous medium, and further comprising (a) formula (2) (Meth) acrylic monomer having an aminotriazine ring represented by and / or its inorganic acid salt or organic acid salt 0.05 to 60 mol%

[0009]

Embedded image _{(Wherein, R 1 = -H, -CH 3} , X = -NH 2, -N
_{HR 2, -NR 2 R 3,} -NHAr, N (Ar) 2: R
₂ , R ₃ represents a C ₁ -C ₄ linear and / or branched alkyl group, Ar represents a cyclohexyl group, a phenyl group and / or a substituted phenyl group) (b) (meth) acrylamide 20-99.9 Mol% (c) α, β-unsaturated (di) carboxylic acid (salt) and / or α, β-unsaturated sulfonic acid (salt) 0-40 mol% (d) (meth) acrylonitrile and / or (meth) )
Acrylic ester 0.05-40 mol% (5) A papermaking additive comprising the (meth) acrylamide polymer according to any one of (1) to (4), and (6) (1). To (4), a drainage improver comprising the (meth) acrylamide-based polymer, and (7) (1) to (4) (meth) acrylamide-based polymer. The present invention relates to a fixing aid for a sizing agent, which is formed by uniting, and also relates to a polymer flocculant made of the (meth) acrylamide polymer according to any one of (8), (1) to (4).

The method for producing a (meth) acrylamide polymer having an aminotriazine ring in the side chain of the present invention is (1)
The method is roughly classified into a method of copolymerizing (meth) acrylamide and monomers having an aminotriazine ring, and (2) a method of reacting a dicyanamide compound or a biguanide compound with a (meth) acrylamide polymer. Of these, the method (1) is more preferable because it can be produced by radical polymerization under a normal condition using a known monomer having an aminotriazine ring.

Examples of the monomer having an aminotriazine ring used in the present invention include 2,4-diamino-6-vinyl-1,
3,5-triazine [hereinafter referred to as acryloguanamine, wherein R ₁ = -H and X = -NH ₂ in formulas (1) and (2)], 2,4-diamino-6-isopropenyl-1,3, 5-triazine (hereinafter methacryloguanamine, also R ₁ = -CH
₃ , X = -NH ₂ ], 2-amino-4-N-methylamino-6-vinyl-1,3,5-triazine, 2-amino-4-N-ethylamino-6-vinyl-1 , 3,5-triazine, 2-amino-4-N
-Isopropylamino-6-vinyl-1,3,5-triazine,
2-amino-4-anilino-6-vinyl-1,3,5-triazine,
2-Amino-4-N-methylanilino-6-vinyl-1,3,5-triazine, 2-amino-4-o-toluidino-6-vinyl-1,3,5-
Triazine, 2-amino-4-N, N-dimethylamino-6-vinyl-1,3,5-triazine, 2-amino-4-N-cyclohexylamino-6-vinyl-1,3,5-triazine, 2-amino-4-N-
Methylamino-6-isopropenyl-1,3,5-triazine,
2-Amino-4-N-ethylamino-6-isopropenyl-1,3,5
-Triazine, 2-amino-4-N-isopropylamino-6
-Isopropenyl-1,3,5-triazine, 2-amino-4-anilino-6-isopropenyl-1,3,5-triazine, 2-amino-4-N-methylanilino-6-isopropenyl-1, 3,5-triazine, 2-amino-4-o-toluidino-6-isopropenyl-1,3,5-triazine, 2-amino-4-N, N-dimethylamino-6-isopropenyl-1,3 , 5-triazine, 2-amino-4
-N- cyclohexylamino-6-isopropenyl-1,3,5-
Examples include triazine.

Regarding the method (2), (meta)
Examples thereof include a method of reacting a dicyandiamide compound with a copolymer of acrylamide and (meth) acrylonitrile, or a method of reacting a (meth) acrylamide with a (meth) acrylic acid ester compound and a biguanide compound.

The amount of aminotriazine ring used in the present invention is in the range of 0.05 to 60 mol%. If it is less than 0.05 mol%, the effect of the present invention is small, and if it exceeds 60 mol%, the effect brought by the (meth) acrylamide group is reduced, which is not preferable.

Examples of α, β-unsaturated carboxylic acids (salts) which may be used in the present invention include acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, angelic acid, tiglic acid, 2-pentenoic acid, acids such as β-methylcrotonic acid, β-methyltiglic acid, α-methyl-2-pentenoic acid, β-methyl-2-pentenoic acid and alkali metal salts thereof,
Examples include monocarboxylic acids (salts) such as ammonium salts and organic amine salts. Examples of unsaturated dicarboxylic acids (salts) include maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, α-dihydromuconic acid, 2,3-dimethylmaleic acid, 2-methylglutaconic acid, Examples thereof include acids such as 3-methylglutaconic acid, 2-methyl-α-dihydromuconic acid and 2,3-dimethyl-α-dihydromuconic acid and their alkali metal salts, ammonium salts, organic amine salts and the like. Examples of α, β-unsaturated sulfonic acids include vinyl sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, styrene sulfonic acid, 2-acrylamide.
-2-Phenylpropanesulfonic acid, 2-acrylamide-2
Examples thereof include acids such as methylpropanesulfonic acid and their alkali metal salts, ammonium salts, and organic amine salts. The amount of such anionic monomer used is in the range of 0 to 40 mol% with respect to all the monomers, and one or more of the above-mentioned monomers can be used.

Further, in the present invention, (meth) acrylonitrile and / or (meth) acrylic acid ester may be used. Examples of (meth) acrylic acid esters used in the present invention include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate,
Examples thereof include hydroxypropyl acrylate and various methoxypolyethylene glycol (meth) acrylates. The amount used is in the range of 0.05 to 40 mol%, and one or more kinds may be used.

The (meth) acrylamide polymer of the present invention may be copolymerized with one or more unsaturated monomers which are copolymerizable in addition to the above components. Examples of the copolymerizable monomer include a hydrophilic monomer, a lipophilic monomer, a cationic monomer, a divinyl compound and the like, and one or more kinds of these monomers can be applied.

Specific examples of the hydrophilic monomer include diacetone acrylamide, N, N-dimethyl acrylamide, N, N-dimethyl methacrylamide, N-ethyl methacrylamide, N-ethyl acrylamide and N, N-diethyl amide. Examples thereof include acrylamide, N-propylacrylamide, N-acryloylpyrrolidine, N-acryloylpiperidine, N-acryloylmorpholine, N-vinyl-2-pyrrolidone and the like.

Examples of the lipophilic monomer include N, N-di-n-
Propyl acrylamide, Nn-butyl acrylamide,
Nn-hexyl acrylamide, Nn-hexyl methacrylamide, Nn-octyl acrylamide, Nn-octyl methacrylamide, N-tert-octyl acrylamide, N-
N-alkyl (meth) acrylamide derivatives such as dodecyl acrylamide and Nn-dodecyl methacrylamide, N, N-
Diglycidyl acrylamide, N, N-diglycidyl methacrylamide, N- (4-glycidoxybutyl) acrylamide, N- (4-glycidoxybutyl) methacrylamide, N-
N- (ω-glycidoxyalkyl) (meth) acrylamide derivatives such as (5-glycidoxypentyl) acrylamide, N- (6-glycidoxyhexyl) acrylamide, methyl acrylate, ethyl acrylate, butyl acrylate, lauryl acrylate , 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, lauryl methacrylate,
2-Ethylhexyl methacrylate, glycidyl (meth) acrylate and other (meth) acrylate derivatives, vinyl acetate, vinyl chloride, vinylidene chloride, ethylene, propylene, butene and other olefins, styrene, α-methylstyrene, butadiene, isoprene, etc. I can give you. The amount of the above-mentioned unsaturated monomer used for the copolymerization varies depending on the type of the unsaturated monomer and the combination thereof, and cannot be said to be unequivocal, but it is generally 0 for all the monomers.
Is in the range of 50% by weight.

Examples of the cationic monomer include N, N-dimethylaminoethyl methacrylate, N, N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl methacrylate, N, N-diethylaminoethyl acrylate and N, N-dimethyl. Monomers having tertiary amino groups such as aminopropylacrylamide, N, N-dimethylaminopropylmethacrylamide, N, N-diethylaminopropylacrylamide, N, N-diethylaminopropylmethacrylamide and / or their organic acids, inorganic A quaternary compound is obtained by reacting an acid salt and a cationic monomer having a tertiary amino group such as methacrylamidopropyltrimethylammonium chloride with methyl chloride, benzyl chloride, methyl iodide, ethyl bromide, dimethyl sulfate, epichlorohydrin, etc. Monomers, monoallylamine, Allylamine, triallylamine, diallyl dimethyl ammonium chloride and the like. The amount of the cationic monomer used is in the range of 0 to 30 mol% with respect to all the monomers, and one or more of the above-mentioned monomers can be used.

Examples of the divinyl compound include bis (meth) acrylamides such as N, N'-methylenebisacrylamide (hereinafter referred to as MBA), N, N'-ethylenebisacrylamide and N, N'-hexamethylenebisacrylamide, ethylene glycol. Di (meth) acrylates of ethylene glycol oligomers such as diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, divinyl adipate, divinyl sebacate, etc. Esters, divinylbenzene,
Examples thereof include divinyl compounds such as epoxy acrylates and urethane acrylates. The divinyl compound is used in an amount of 0 to 2.0 mol% based on all monomers.

In the present invention, the above-mentioned monomers are polymerized to produce an acrylamide polymer. The polymerization method is preferably a radical polymerization method, and the polymerization solvent is water, methanol, ethanol, propanol, butanol, Alcohols such as methyl cellosolve, ethyl cellosolve and butyl cellosolve, and polar solvents miscible with water such as formamide, dimethylformamide and dimethylsulfoxide are applicable. The monomer concentration is 2 to 40% by weight, preferably 5 to 30% by weight.

The polymerization initiator is not particularly limited as long as it is water-soluble. Specifically, examples of the peroxide type include ammonium persulfate, potassium persulfate, hydrogen peroxide, tert-butyl peroxide and the like. In this case, although it can be used alone, it can also be used as a redox polymerizing agent in combination with a reducing agent. As the reducing agent, for example, sulfite, bisulfite, iron, copper, salts of lower ions such as cobalt, hypophosphorous acid, hypophosphite, N, N, N ', N'-tetramethyl Examples thereof include organic amines such as ethylenediamine, and reducing sugars such as aldose and ketose. As the azo compound, 2,2'-azobis-2-amidinopropane hydrochloride, 2,2'-azobis-2,4-dimethylvaleronitrile, 4,4'-azobis-4-cyanovaleic acid and salts thereof Etc. can be used. Furthermore, it is also possible to use two or more of the above-mentioned polymerization initiators in combination. The amount of the initiator added is in the range of 0.0001 to 10% by weight, preferably 0.01 to 8% by weight, based on the monomers. In the case of a redox system, the amount of the reducing agent added to the initiator is 0.01 to 100%, preferably 0.2 to 8 on a molar basis.
It is 0%.

If necessary, a chain transfer agent such as isopropyl alcohol, allylsulfonic acid (salt), methallylsulfonic acid (salt), allyl alcohol, α-thioglycerol, mercaptosuccinic acid, thioglycolic acid, triethylamine, etc. may be used. It can also be used as appropriate.

The monomers, the polymerization initiator, the solvent, the chain transfer agent and the like to be used for the polymerization may be charged into the reaction vessel at once at the time of starting the polymerization, but depending on the progress of the polymerization, one kind or The above components may be added individually or as a mixture with a solvent or the like.

The polymerization temperature is generally 30 to 90 ° C. in the case of a single polymerization initiator, lower than that in the case of a redox type polymerization initiator, and generally -5 to 50 in the case of carrying out polymerization in a batch.
C., and in the case of sequential addition, it is approximately 30 to 90.degree. Further, it is not necessary to keep the same temperature during the polymerization, and it may be appropriately changed as the polymerization proceeds, and the temperature is generally raised by the heat of polymerization generated with the progress of the polymerization. At this time, if the polymerization is carried out at a high concentration, the polymerization may be carried out while removing heat, if necessary. The atmosphere in the polymerization vessel is not particularly limited, but it is preferable to replace with an inert gas such as nitrogen gas in order to carry out the polymerization rapidly. The pH of the polymerization solution is not particularly limited, but when the solubility of the monomer having an aminotriazine group in the aqueous solvent is limited, the pH is 6 or less, preferably 4 or less. The polymerization time is not particularly limited, but is generally 1 to 20 hours.

When the reaction of the (meth) acrylamide copolymer with the dicyandiamide compound is utilized, the polymer containing the (meth) acrylonitrile polymerized by the above method is treated with potassium hydroxide, sodium hydroxide, 1-1 at 80-150 ° C with strong base such as lithium hydroxide as catalyst
By reacting for 0 hour, an aminotriazine ring can be formed. Further, the reaction of the (meth) acrylamide-based polymer with the biguanide compound is carried out by using a polymer containing the (meth) acrylic acid ester polymerized by the above-mentioned method, potassium hydroxide, sodium hydroxide, lithium hydroxide, 2 in the presence of a base catalyst such as sodium methoxide
An aminotriazine ring can be formed by reacting at a temperature of 0 to 120 ° C. for 1 to 24 hours. Examples of biguanide compounds include biguanide, methyl biguanide, ethyl biguanide, isopropyl biguanide, n-butyl biguanide, phenyl biguanide, cyclohexyl biguanide, dimethyl biguanide, diethyl biguanide, diphenyl biguanide, and the like.

As a method of introducing a carboxylic acid (salt) structure into a (meth) acrylamide polymer, a method of hydrolyzing an amide group or an ester group contained in the polymer with an acid or an alkali can be applied.

The (meth) acrylamide polymer of the present invention has a viscosity of an aqueous polymer solution having a concentration of 10 to 30% by weight at 25 ° C. in the range of 1 to 500 poise. (Meta)
The aminotriazine group in the acrylamide polymer exhibits a cationic property in an acidic aqueous solution, so that quantitative analysis by colloid titration is possible. The cation value determined by colloid titration is in the range of about 0.1 to 5.5 meq./g. Similarly, the anion component in the polymer can be determined by colloid titration, and is generally in the range of 0 to 5.0 meq./g.

The presence of the aminotriazine ring can be confirmed by having an absorption maximum at 240 to 300 nm in the ultraviolet absorption spectrum. In the infrared absorption spectrum, characteristic absorption band derived from the amino triazine ring 1500～1600Cm ^-1 and 800 ^～820Cm-1 is observed.

The (meth) acrylamide polymer having an aminotriazine ring produced by the present invention exhibits excellent effects as an additive for papermaking, a drainage improver, a fixing aid for sizing agents, a flocculant and the like. In addition, it can be applied to fields in which water-soluble polymers are used, and can be used, for example, as a filler / pulp fiber yield improving agent, a chelating agent, a scale inhibitor, a fiber treating agent, and a dye fixing agent.

The action and effect of the polymer of the present invention in such a field are considered to be brought about by the aminotriazine group introduced into the side chain. Although its exact action is of course unknown, it is likely that these functional groups have high hydrogen-bonding ability, so introduction into a polymer involves structural changes due to hydrogen-bonding ability between side-chain functional groups, etc. , Pulp fibers, sizing agents, sludge particles, etc.
It is presumed that electrostatic interaction or interaction through hydrogen bond works.

[0032]

EXAMPLES The present invention will now be specifically described by dividing it into production examples and application examples, but the present invention is not necessarily limited to the following examples and application examples. In the following,% means% by weight unless otherwise specified. [Example 1] 40% acrylamide 22.7 in a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen gas inlet tube.
g (128 mmol) and acryloguanamine 0.92 g (6.7 mmol) and pure water
After charging 74.7 g and adjusting the pH to 3.0 with 35% hydrochloric acid,
The internal temperature was raised to 80 ° C. while blowing nitrogen gas, and ammonium persulfate was added with stirring to start polymerization. The polymerization reaction was completed 2 hours after the initiation of the polymerization. Nonvolatile matter 10.3%, Brookfield viscosity at 25 ℃ 1,88
A copolymer with 0 cps and a cation value of 0.8 meq./g was obtained. When the residual monomer in the aqueous solution of the copolymer was measured by liquid chromatography to determine the polymerization rate, acrylamide was
It was 99.9% or higher, and acryloguanamine was 96.9%.

Examples 2 to 4 Polymerization was carried out in the same manner as in Example 1 except that the copolymerization ratio of acrylamide and acryloguanamine was changed as shown in Table 1. The nonvolatile content, Brookfield viscosity at 25 ° C. and cation value of the obtained copolymer are summarized in Table 1.

Example 5 40% acrylamide 22.7 g (128 mmol) and acryloguanamine 0.92 g were placed in a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen gas inlet tube.
(6.7 mmol) and 74.7 g of pure water were charged, and the pH was adjusted to 3.0 with 35% hydrochloric acid.
After adjusting to, adjust the internal temperature to 80 while blowing nitrogen gas.
The temperature was raised to ° C, and 2,2'-azobis-2-amidinopropane hydrochloride was added with stirring to initiate polymerization. Polymerization start 2
After a period of time, the polymerization reaction was completed. After lowering the temperature to 60 ° C, add 40% NaOH 2.02g (20.2mmol) (including the neutralized amount of acryloguanamine) and continue the reaction for 2 hours at this temperature. Nonvolatile content 10.3%, at 25 ° C Brookfield viscosity 920 cps, cation value 0.7 meq./g, anion value 1.0 m
An eq./g amphoteric polymer was obtained.

[Example 6] 20.6 g (116 mmol) of 40% acrylamide and 1.77 g of acryloguanamine were placed in a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen gas inlet tube.
(12.8 mol) and pure water 77.6 g were charged, and the pH was adjusted to 3.0 with 35% hydrochloric acid.
After adjusting to, adjust the internal temperature to 80 while blowing nitrogen gas.
The temperature was raised to ° C, and 2,2'-azobis-2-amidinopropane hydrochloride was added with stirring to initiate polymerization. Polymerization start 2
After a period of time, the polymerization reaction was completed. After lowering the temperature to 60 ° C, add 40% NaOH 2.58g (25.8mmol) (including the neutralized amount of acryloguanamine) and continue the reaction for 2 hours at this temperature, nonvolatile content 10.5%, at 25 ° C. Brookfield viscosity 1,190 cps, cation value 0.9 meq./g, anion value 0.
An amphoteric polymer of 9 meq./g was obtained.

Example 7 40% acrylamide 18.6 (105 mmol) and acryloguanamine 2.54 g were placed in a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen gas inlet tube.
(18.5mmol) and pure water 75.9g were charged and the pH was adjusted with 35% hydrochloric acid.
After adjusting to 3.0, blow nitrogen gas to adjust the internal temperature to 8
The temperature was raised to 0 ° C., and 2,2′-azobis-2-amidinopropane hydrochloride was added with stirring to initiate polymerization. The polymerization reaction was completed 2 hours after the initiation of the polymerization. After the temperature was lowered to 60 ° C., 1.56 g (15.0 mmol) of 35% hydrochloric acid was added, and the reaction was continued for another 2 hours at this temperature. Nonvolatile matter 10.2%, Brookfield viscosity at 25 ° C., 1,780 cps, cation value 1.3 meq. /
An amphoteric polymer having an anion value of 1.0 meq./g was obtained.

[Example 8] 40% acrylamide 16.9 g (95 mmol) and acryloguanamine 3.25 g were placed in a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen gas inlet tube.
(23.7 mmol) and pure water 79.8 g were charged, and the pH was adjusted with 35% hydrochloric acid.
After adjusting to 3.0, blow nitrogen gas to adjust the internal temperature to 8
The temperature was raised to 0 ° C., and 2,2′-azobis-2-amidinopropane hydrochloride was added with stirring to initiate polymerization. The polymerization reaction was completed 2 hours after the initiation of the polymerization. After the temperature was lowered to 60 ° C., 1.50 g (14.4 mmol) of 35% hydrochloric acid was added, and the reaction was continued for another 2 hours at this temperature. Nonvolatile content 10.3%, Brookfield viscosity at 25 ° C. 1,490 cps, cation value 1.8 meq. /
An amphoteric polymer having an anion value of 0.9 meq./g was obtained.

Comparative Example 1 22.4 g (126 mmol) of 40% acrylamide and 1.04 g of dimethylaminoethyl methacrylate (hereinafter DM) were placed in a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen gas inlet tube. 6.6 mmol) and 74.9 g of pure water were charged, the pH was adjusted to 5.0 with 35% hydrochloric acid, the internal temperature was raised to 80 ° C. while blowing nitrogen gas, and ammonium persulfate was added with stirring to start polymerization. did. The polymerization reaction was completed 2 hours after the initiation of the polymerization. Nonvolatile content 10.4%,
A copolymer having a Brookfield viscosity at 25 ° C of 1,900 cps and a cation value of 0.6 meq./g was obtained.

[Comparative Examples 2 to 4] Polymerization was carried out in the same manner as in Comparative Example 1 except that the copolymerization ratio of acrylamide and DM was changed as shown in Table 1. The nonvolatile content, Brookfield viscosity at 25 ° C. and cation value of the obtained copolymer are summarized in Table 1.

Comparative Example 5 40% acrylamide 20.0 g (113 mol) and DM 1.04 g (6.6 mmol), 80% in a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen gas inlet tube.
Acrylic acid 1.19 g (13. mmol) and pure water 76.1 g were charged, and 35
After adjusting the pH to 5.0 with% hydrochloric acid, the internal temperature was raised to 80 ° C. while blowing nitrogen gas, and ammonium persulfate was added with stirring to start polymerization. The polymerization reaction was completed 2 hours after the initiation of the polymerization. Nonvolatile matter 10.4%, Brookfield viscosity at 25 ° C 950cps, anion number 1.3me
An amphoteric polymer having a q./g and a cation value of 0.6 meq./g was obtained.

[Comparative Examples 6 to 8] Acrylamide and DM,
Polymerization was carried out in the same manner as in Comparative Example 5 except that the copolymerization ratio of acrylic acid was changed as shown in Table 1. The nonvolatile content, Brookfield viscosity at 25 ° C., cation value, and anion value of the obtained copolymer are summarized in Table 1.

[0042]

[Table 1]

[Papermaking Example 1] 370 ml of CSF was beaten.
To a 1% pulp slurry of L-BKP / N-BKP = 6/4, first, 1.0% of a sulfuric acid band was added to pulp (same as below on a dry weight basis) and stirred for 1 minute. To this 1% pulp slurry, a commercially available emulsion type rosin sizing agent was added to 0.5% of the pulp.
After the addition, stirring was carried out for 1 minute, and then a 1% aqueous solution of the polymer prepared in Example 1 was added so as to be 0.50% based on the pulp, and stirring was carried out for 1 minute. According to JIS-P-8121, using a portion of the pulp slurry obtained by adjusting the pH to 6.0,
The Canadian standard freeness (CSF) was measured. Further, a part of the paper was made by a tappy standard sheet machine, pressed at 3.5 kg / cm ² for 10 minutes, and then dried by a drum dryer at 110 ° C. Then 20 ° C
Seasoned in a constant temperature and humidity room with a relative humidity of 65% and basis weight
100 g / m ² of handmade paper was obtained. Bursting strength of this paper according to JIS-P-8112, Z-axis strength with an internal bond tester from Kumagai Riki Kogyo Co., Ltd., breaking length according to JIS-P-8113,
Furthermore, the Steckigt sizing degree was measured according to JIS-P-8122. Papermaking Examples 2 to 7 use the polymers produced in Examples 2 to 8 and Papermaking Comparative Examples 1 to 8 use the polymers produced in Comparative Examples 1 to 8 in the same operating method as in Papermaking Example 1. The test was conducted. The results of the above papermaking examples and papermaking comparative examples are shown in Table 2.

[0044]

[Table 2]

[Agglomeration Example 1] 150 ml of human waste mixed sludge (digested sludge / excess sludge = 1/3, solid content 1.35%) was placed in a 300 ml beaker, and a 1% aqueous solution of the polymer prepared in Example 5 was used.
After adding 20 ml and stirring for 1 minute, the flocculated flocs were subjected to natural filtration with a Buchner funnel (filtration area 100 cm ² , filter cloth 60 mesh Tetron), and the gravity dehydration filtrate amount was measured.
It was 116 ml. Further, the water content of the dehydrated cake obtained by centrifuging the flocculated flocs after the gravity dehydration at 3000 rpm for 5 minutes was 82%. Aggregation Examples 2-4 use the polymers produced in Examples 6-8, and Aggregation Comparative Examples 1-4 use the polymers produced in Comparative Examples 5-8,
Aggregation A coagulation test was conducted in the same manner as in Example 1. Table 3 shows the results of the above aggregation examples and comparative aggregation examples.

[0046]

[Table 3]

[0047]

INDUSTRIAL APPLICABILITY The polymer of the present invention can greatly improve the paper strength performance as compared with the conventionally known acrylamide polymer.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display area C08F 222/02 MLU 226/06 MNL D21H 17/37

Claims (8)

[Claims] 1. A water-soluble or water-dispersible (meth) acrylamide-based polymer having an aminotriazine ring in its side chain, which comprises the structural units (a) to (c). (a) Formula (1) [Chemical Formula 1], and / or an amino acid salt or an organic acid salt thereof, which is an aminotriazine ring derivative unit 0.05 to 60 mol% _{(Wherein, R 1 = -H, -CH 3} , X = -NH 2, -N
_{HR 2, -NR 2 R 3,} -NHAr, N (Ar) 2: R
₂ , R ₃ represents a C _{1 to} C ₄ linear and / or branched alkyl group, Ar represents a cyclohexyl group, a phenyl group and / or a substituted phenyl group) (b) (meth) acrylamide structural unit 20 to 99 .95
Mol% (c) α, β-unsaturated (di) carboxylic acid (salt) structural unit and / or α, β-unsaturated sulfonic acid (salt) structural unit 0-40 mol% 2. A water-soluble or water-dispersible (meth) acrylamide-based polymer having an aminotriazine ring in its side chain, which comprises the structural units (a) to (d). (a) Formula (1) [Chemical Formula 2] and / or its amino acid or organic acid salt, an aminotriazine ring derivative unit, 0.05 to 60 mol% _{(Wherein, R 1 = -H, -CH 3} , X = -NH 2, -N
_{HR 2, -NR 2 R 3,} -NHAr, N (Ar) 2: R
₂ , R ₃ represents a C _{1 to} C ₄ linear and / or branched alkyl group, Ar represents a cyclohexyl group, a phenyl group and / or a substituted phenyl group) (b) (meth) acrylamide structural unit 20 to 99 .9 mol% (c) α, β-unsaturated (di) carboxylic acid (salt) structural unit and / or α, β-unsaturated sulfonic acid (salt) structural unit 0-40 mol% (d) (meth) Acrylonitrile and / or (meth)
Acrylic ester structural unit 0.05-40 mol% 3. A method for producing a (meth) acrylamide polymer having an aminotriazine ring in a side chain, which comprises radically polymerizing the acrylic compounds (a) to (c) in an aqueous medium. (a) A (meth) acrylic monomer having an aminotriazine ring represented by the formula (2) [Chemical Formula 3] and / or its inorganic acid salt or organic acid salt 0.05 to 60 mol% 3] _{(Wherein, R 1 = -H, -CH 3} , X = -NH 2, -N
_{HR 2, -NR 2 R 3,} -NHAr, N (Ar) 2: R
₂ , R ₃ represents a C _{1 to} C ₄ linear and / or branched alkyl group, Ar represents a cyclohexyl group, a phenyl group and / or a substituted phenyl group) (b) (meth) acrylamide 20 to 99.95 Mol% (c) 0,40 mol% of α, β-unsaturated (di) carboxylic acid (salt) and / or α, β-unsaturated sulfonic acid (salt) 4. A method for producing a (meth) acrylamide polymer having an aminotriazine ring in its side chain, which comprises radically polymerizing the acrylic compounds (a) to (d) in an aqueous medium. (a) (meth) acrylic monomer having an aminotriazine ring represented by the formula (2) [Chemical Formula 4], and / or its inorganic acid salt or organic acid salt 0.05 to 60 mol% 4] _{(Wherein, R 1 = -H, -CH 3} , X = -NH 2, -N
_{HR 2, -NR 2 R 3,} -NHAr, N (Ar) 2: R
₂ , R ₃ represents a C ₁ -C ₄ linear and / or branched alkyl group, Ar represents a cyclohexyl group, a phenyl group and / or a substituted phenyl group) (b) (meth) acrylamide 20-99.9 Mol% (c) α, β-unsaturated (di) carboxylic acid (salt) and / or α, β-unsaturated sulfonic acid (salt) 0-40 mol% (d) (meth) acrylonitrile and / or (meth) )
Acrylic ester 0.05-40 mol% 5. The (meta) according to claim 1.
An additive for papermaking consisting of an acrylamide polymer. 6. The (meth) according to any one of claims 1 to 4.
A drainage improver composed of an acrylamide polymer. 7. The (meta) according to claim 1.
A fixing aid for sizing agents, which consists of an acrylamide polymer. 8. The (meth) according to any one of claims 1 to 4.
A polymer flocculant composed of an acrylamide polymer.