JPS6326123B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an aqueous dispersion of a water-soluble polymer composite having excellent stability and fluidity, and more specifically, the present invention relates to an aqueous dispersion of a water-soluble polymer composite having excellent stability and fluidity. The present invention relates to an aqueous dispersion of a water-soluble polymer composite obtained by polymerizing a water-soluble polymer compound and a water-soluble ethylenically unsaturated monomer in a weight ratio within a specific range. Water-soluble vinyl addition polymers produced from water-soluble ethylenically unsaturated monomers can be used as polymer electrolytes, such as flocculants, fiber treatment agents, paper strength agents, antistatic agents, synthetic fiber modifiers, sludge super-aiding agent,
It is useful for fixing paper sizing agents, etc. Conventionally, the most common method for producing water-soluble vinyl addition polymers has been an aqueous solution polymerization method using water as a solvent. However, the aqueous solution polymerization method has advantages such as that it can be easily carried out using an aqueous solution of monomers in the presence of a polymerization initiator and that high polymers can be easily obtained, but on the other hand, (1 )
(2) There is a limit to the monomer concentration during polymerization (5 to 20
(% concentration), which poses a problem in improving productivity; and (3) as the reaction progresses, the viscosity increases significantly, making stirring difficult, and at high concentrations, it becomes so-called agar-like. Because it becomes a gel, it is not only extremely inconvenient to transport, store, and handle when used as is, but also requires complicated processing steps such as collection, drying, and pulverization when powdered. It has its drawbacks. In order to improve these drawbacks, precipitation polymerization methods are used in which polymerization is carried out in an organic solvent in which monomers are dissolved but polymers are not, and the resulting polymer is separated as a precipitate.
A reverse-phase suspension polymerization method, in which a mixture of a monomer and water is dispersed using a surfactant in an organic solvent in which both the monomer and the polymer are poorly soluble, is widely known. However, these methods use organic solvents, making it difficult to obtain high molecular weight polymers.
Large-scale facilities are required from the viewpoint of recovering organic solvents and safety, and water-soluble polymers are often provided as powder or granules, so it is difficult to dissolve them in water before use. , it is difficult to dissolve uniformly and tends to produce gel-like lumps. Once a gel-like mass is formed, it is difficult for water to penetrate into the gel-like mass, so it has disadvantages such as requiring a considerable amount of time for dissolution. Furthermore, after producing a water-in-oil emulsion by polymerizing a water-soluble ethylenically unsaturated monomer in a hydrophobic liquid organic dispersion medium containing a water-in-oil emulsifier,
A method has been proposed in which this is converted into an oil-in-water emulsion in the presence of water without separating the produced polymer. However, this method uses a large amount of organic solvent that is insoluble in water, so secondary contamination by the organic solvent is a problem, other surfactants are required for phase transformation, and dispersion It has the disadvantage of poor stability and condensation during storage and transportation. As a result of various studies in order to improve the drawbacks of the conventional methods, the present inventors found a specific combination of water concentration, water-soluble polymer compound concentration, and water-soluble ethylenically unsaturated monomer concentration. The aqueous dispersion of the water-soluble polymer composite obtained by polymerization within the range of 100 to 100% has improved the drawbacks of conventional methods for producing water-soluble polymers, and has excellent stability and fluidity. Therefore, the inventors discovered that it is possible to use the polymer as it is without separating and recovering it from water, leading to the present invention. That is, the present invention provides a water-soluble polymer having (A) 100 parts by weight of water and (B) at least one functional group selected from the group consisting of an ether group, a hydroxyl group, and a carboxyl group in the polymer constituent unit. Compound,
or a mixture with another water-soluble polymer compound containing at least 10% by weight of the polymer compound 1-150
In the presence of a mixed aqueous solution containing substantially parts by weight, (C) the general formula [In the formula, R ₁ represents a hydrogen atom or a methyl group,
Y is

[Formula] group or

[Formula] Indicates a group. In addition, R ₂ and R ₅ represent an alkylene group having 2 to 5 carbon atoms or a hydroxyl alkylene group having 2 to 5 carbon atoms, and R ₃ , R ₄ , R ₆ and R ₇ represent the same or different types of carbon atoms 1 to 5. represents an alkyl group, R ₈ is an alkyl group having 1 to 5 carbon atoms,

[Formula] or CH ₂ COOH, and Z represents a halogen atom, SO ₃ OCH ₃ , 1/2SO ₄ , CH ₃ SO ₃ or CH ₃ COO. ] or a mixture with other water-soluble ethylenically unsaturated monomers containing more than 50% by weight of the water-soluble ethylenically unsaturated monomer (B The present invention relates to an aqueous dispersion of a water-soluble polymer composite having excellent stability and fluidity obtained by polymerizing the weight ratio of () to (C) within the range of 10:1 to 1:10. The aqueous dispersion of the water-soluble polymer composite of the present invention has an extremely low viscosity while containing a polymer obtained from a water-soluble ethylenically unsaturated monomer at a high concentration, so it is easy to handle and requires sufficient water. It can be easily converted into a homogeneous aqueous solution by dilution with .
Furthermore, in the present invention, a dangerous and expensive organic solvent is not used when producing an aqueous dispersion of a water-soluble high molecular weight polymer, so that a high molecular weight polymer can be easily obtained. These problems include the difficulty in handling conventional water-soluble polymers, the difficulty in uniformly dissolving them in water, the high viscosity of highly concentrated solutions, and the complicated operations required to recover organic solvents. This method solves the problems all at once, and has great industrial significance. The water-soluble polymer compound used in the present invention has at least one functional group selected from the group consisting of an ether group, a hydroxyl group, and a carboxyl group in its polymer constituent unit, and specifically, , agar, gum arabic, dextran, starch, starch derivatives, cellulose derivatives, polyethylene glycol, polyethylene oxide, polypropylene glycol, copolymers of ethylene glycol and propylene glycol,
A typical example is polyvinyl alcohol. These water-soluble polymer compounds may be used alone or in combination of two or more. In addition, these water-soluble polymer compounds may contain functional groups other than ether groups, hydroxyl groups, or carboxyl groups, such as sulfone groups, sulfuric acid ester groups, amino groups, imino groups, tertiary amino groups, quaternary ammonium bases,
Mixed with at least one other water-soluble polymer compound, such as polyvinylpyrrolidone, polyvinylpyridine, and polyethyleneimine, which has at least one functional group selected from the group consisting of hydrazino groups in the polymeric constituent unit. May be used. In this case, the proportion of the water-soluble polymer compound having at least one functional group selected from the group consisting of ether group, hydroxyl group, and carboxyl group in the mixture is at least 10% by weight and not more than 10% by weight. In this case, it is difficult to obtain the remarkable effects of the present invention. The blending amount of these specific water-soluble polymer compounds or mixtures of these compounds and other water-soluble polymer compounds is 1 to 150 parts by weight, preferably 5 to 125 parts by weight, and more preferably 5 to 125 parts by weight, based on 100 parts by weight of water. Preferably 10-100
Parts by weight. If the amount is less than 1 part by weight, the effect of lowering the viscosity will be small and an aqueous dispersion with excellent stability and fluidity will not be obtained. On the other hand, the blending amount is 150
If the amount exceeds 1 part by weight, it is not only difficult to dissolve in water, but also the water-soluble polymer compound itself has a high viscosity, so the viscosity of the aqueous dispersion becomes too high, and water with excellent stability and fluidity becomes difficult to dissolve. A dispersion cannot be obtained. Examples of the water-soluble ethylenically unsaturated monomers represented by the above general formula used in the present invention include CH ₂ =CHCOOC ₂ H ₄ N(CH ₃ ) ₂ , CH ₂ =
CHCOOC ₃ H ₆ N (CH ₃ ) ₂ , CH ₂ = CHCOOC ₄ H ₈ N
( _CH3 ) ₂ , _{CH2 = CHCOOC2H4N} ( _CH3 ) _{C2H5 ,}
CH ₂ = CHCOOC ₂ H ₄ N (C ₂ H ₅ ), CH ₂ =
CHCOOC ₅ H ₁₀ N(C ₂ H ₅ ) ₂ , CH ₂ =
CHCOOCH ₂ CH(OH)CH ₂ N(CH ₃ ) ₂ , CH ₃ =C
( _CH3 ) _COOC2H4N ( _CH3 ) ₂ , _CH2 = _C ( _CH3 )
COOC ₃ H ₆ N(CH ₃ ) ₂ , CH ₂ =C(CH ₃ )
COOC ₄ H ₈ N(CH ₃ ) ₂ , CH ₂ =C(CH ₃ )
COOC ₂ H ₄ N(CH ₃ )C ₂ H ₅ , CH ₂ =C(CH ₃ )
COOC ₂ H ₄ (C ₂ H ₅ ) ₂ , CH ₂ =C(CH ₃ )
COOC ₅ H ₁₀ N(C ₂ H ₅ ) ₂ , CH ₂ =C(CH ₃ )
COOCH ₂ CH (OH) CH ₂ N (CH ₃ ) ₂ , CH ₂ =
CHCOOC ₂ H ₄ N(CH ₃ ) ₃ Cl, CH ₂ =
_{CHCOOC3H6N ( CH3} ) _3Cl , _{CH2 = CHCOOC2H4N}
(C ₂ H ₅ ) ₂ CH ₂ COOHCl, CH ₂ =CHCOOCH ₂ CH
(OH) _CH2N ( _CH3 ) _3Cl , _CH2 =C( _CH3 )
COOC ₂ H ₄ N(CH ₃ ) ₃ Cl, CH ₂ =C(CH ₂ )
COOC ₃ H ₆ N(CH ₃ ) ₃ Cl, CH ₂ =C(CH ₃ )
COOCH ₂ CH (OH) CH ₂ N (CH ₃ ) ₃ Cl, CH ₂ =
CHCOOC ₂ H ₄ N(CH ₃ ) ₃ SO ₃ CH ₃ , CH ₂ =
CHCOOC ₂ H ₄ N (CH ₃ ) ₃ 1/2 SO ₄ , CH ₂ = C (CH ₃ ) COOC ₂ H ₄ N (CH ₃ ) ₃ SO ₄ CH ₃ , CH ₂ =
C( _CH3 ) _{COOC2H4N ( CH3} ) _{3CH3COO ,
CH2} =C( _CH3 ) _COOCH2CH (OH) _CH2N
(CH ₃ ) ₃ Cl, etc. These water-soluble ethylenically unsaturated monomers contain 1
You may use a species or a mixture of two or more. In addition, these water-soluble ethylenically unsaturated monomers are
It may be used in combination with other water-soluble ethylenically unsaturated monomers copolymerizable with the monomer. Examples of other water-soluble ethylenically unsaturated monomers that can be copolymerized with the water-soluble ethylenically unsaturated monomer include acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide, N.
N'-dimethylacrylamide, NN'-dimethylmethacrylamide, NN-diethylacrylamide, NN'-diethylmethacrylamide, N-
Examples include methyl-N-ethyl acrylamide, N-methyl-N-ethyl methacrylamide, acrylonitrile, N-vinylpyrrolidone, vinylpyridine, and vinyl acetate. These other water-soluble ethylenically unsaturated monomers may be used alone or in combination of two or more. When water-soluble ethylenically unsaturated monomers and other water-soluble ethylenically unsaturated monomers are mixed and used, the proportion of water-soluble ethylenically unsaturated monomers in the total monomers is 50 It is desirable that the amount is greater than % by weight. The amount of these water-soluble ethylenically unsaturated monomers or the mixture of these monomers and other water-soluble ethylenically unsaturated monomers is 1 to 1 to 100 parts by weight of water.
150 parts by weight, preferably 10 to 100 parts by weight, and the ratio between the water-soluble polymer compound and the water-soluble ethylenically unsaturated monomer, or between this monomer and another water-soluble ethylenically unsaturated monomer. The weight ratio of mixed monomers is 10:1 ~
The ratio is 1:10, preferably 5:1 to 1:5, more preferably 2.5:1 to 1:2.5. If the amount is less than 1 part by weight, a high polymer cannot be obtained due to the low concentration. On the other hand, if the blending amount is 150 parts by weight or more, it is difficult to reduce the viscosity of the aqueous dispersion, and an aqueous dispersion with excellent stability and fluidity cannot be obtained. In addition, the weight ratio of water-soluble polymer compound to water-soluble ethylene monomer is
If polymerization is carried out outside the range of 10:1 to 1:10, a rich aqueous solution of a water-soluble polymer compound or a polymer obtained from a water-soluble ethylene monomer will result. Since the viscosity is controlled by the viscosity of the aqueous solution, an aqueous dispersion with excellent stability and fluidity cannot be obtained. The aqueous dispersion of the water-soluble polymer composite of the present invention can be obtained by polymerizing the water-soluble ethylenically unsaturated monomer represented by the above general formula in the presence of water and a water-soluble polymer compound. . The polymerization reaction can be carried out by simply applying heat, but
Preferably, radical initiators, ultraviolet light or radiation are used. In practicing the present invention, water-soluble radical initiators such as hydrogen peroxide, potassium persulfate, ammonium persulfate, etc.
Alternatively, it is preferable to polymerize in the presence of a so-called redox initiator, which is a combination of these and a reducing agent such as an amine or sodium sulfite. The amount of initiator used is 0.005 to 10% by weight based on the weight of the water-soluble ethylenically unsaturated monomer, and the addition method is as follows:
The entire amount may be added at the beginning of the polymerization, or a portion may be added and the remaining amount may be added as the polymerization progresses. The reaction temperature is between 10 and 100°C, especially between 40 and 70°C. Moreover, the polymerization time is within the range of 3 to 10 hours. The polymerization reaction can be carried out either batchwise or continuously. When producing the aqueous dispersion of the present invention, nonionic surfactants such as polyethylene glycol and higher alcohols; aliphatic salts;
Anionic surfactants such as higher alcohol sulfate ester salts, liquid fatty oil sulfate esters, aliphatic amines, aliphatic amide sulfates, and aliphatic alcohol phosphate esters; aliphatic amine salts;
Cationic surfactants such as quaternary ammonium salts and alkylpyridinium salts may be added, and in particular, nonionic surfactants such as copolymers of propylene glycol and ethylene glycol are preferably added. These surfactants may be used alone or in combination of two or more, and the amount used is 0.05 to 50 parts by weight per 100 parts by weight of water.
When the blending amount is 0.05 parts by weight or less, there is no noticeable difference in the effect compared to the case where no additive is added. On the other hand, if the blending amount is 50 parts by weight or more, not only the improvement effect by addition is no longer observed, but also stability may be impaired in some cases, which is not preferable. The surfactant may be added in its entirety at the beginning of the polymerization, or a portion may be added during the polymerization and the remainder may be added appropriately as the polymerization progresses. Further, these surfactants may be added at the end of polymerization. Furthermore, when producing the aqueous dispersion of the present invention, inorganic salts having a solubility in water of at least 1% by weight may be added as necessary. Inorganic salts include chlorides, nitrates, sulfates, and phosphates of alkali metals, alkaline earth metals, and ammonia, and typical examples include sodium chloride, calcium chloride, calcium nitrate, sodium nitrate, ammonium nitrate, and sulfuric acid. Examples include potassium and calcium phosphate. These inorganic salts may be used alone or in a mixture of two or more, and the amount added is at least 0.5 parts by weight per 100 parts by weight of water. It should be kept within the range that dissolves in the water. The inorganic salts may be added all at once during polymerization, or may be added intermittently during any period from the start of polymerization to the end of polymerization. Further, these inorganic salts may be added at the end of polymerization. Furthermore, an organic solvent having a solubility in water of at least 2% by weight may be added to the aqueous dispersion of the present invention, if necessary. Examples of organic solvents include alcohol solvents such as methyl alcohol, ethyl alcohol, propyl alcohol, ethylene glycol, and glycerin, ketone solvents such as acetone and methyl ethyl ketone, ether solvents such as tetrahydrofuran and dioxane, and amides such as dimethylformamide and dimethylacetamide. Examples include solvents. These organic solvents may be used alone or in a mixture of two or more, and can be added in any amount within the range of dissolution in water, but preferably 1 to 50 parts by weight per 100 parts by weight of water. %.
The organic solvent is preferably added at the end of the reaction in order to prevent a decrease in the degree of polymerization due to chain transfer to the solvent during polymerization. The aqueous dispersion of the present invention may contain stabilizers, colorants, pigments, dyes, fragrances and other additives. The aqueous dispersion of the present invention can be used not only in fields such as polymer flocculants, paints, adhesives, paper processing agents, textile processing agents, pharmaceuticals, and cosmetics, but also for various products by taking advantage of the characteristics of the aqueous dispersion of the present invention. It is also useful as a sticky agent and dispersant. The present invention will be explained in more detail below with reference to Examples. Example 1 Equipped with a stirrer, reflux condenser and nitrogen inlet tube
Add 100g of water and 20g of polyethylene glycol (molecular weight 20,000) to a 300ml flask, mix and dissolve, then add 36g of dimethylaminoethyl methacrylate.
was added, and while purging with nitrogen gas, 5 ml of a 1% aqueous solution of ammonium persulfate and 5 ml of a 6% aqueous solution of triethanolamine were added.
Polymerization was carried out at .degree. C. with stirring. As the polymerization progressed, the reaction system became turbid and the viscosity gradually increased, but it was sufficiently stirrable. Polymerization was stopped after 3 hours, and the residual monomer was quantified by liquid chromatography, and the residual monomer was 0.015%.
The polymerization rate was 99% or more. The viscosity of the obtained aqueous dispersion was measured at 30°C using a rotational viscometer and was found to be 25,000 cps. When this aqueous dispersion was diluted 30 times with water (1% polydimethylaminoethyl methacrylate concentration), it quickly became a homogeneous aqueous solution, and the viscosity measured by a rotational viscometer was
It was 450cps (30℃). In addition, this aqueous dispersion is
The condition remained stable even after one month had passed. Comparative Example 1 In Example 1, polymerization was carried out under the same conditions as in Example 1 except that polyethylene glycol was not used.
After ~5 minutes, the viscosity of the system increased rapidly and a Weisenberg effect occurred, making stirring impossible. Example 2 Into a flask similar to Example 1, 100 g of water, 20 g of polyethylene glycol (molecular weight 20,000), and 5 g of soluble starch were mixed and dissolved, and then 6 g of dimethylaminoethyl methacrylate and 4 g of acrylamide were added. Hereinafter, polymerization was carried out under the same conditions as in Example 1. As the polymerization progressed, the reaction solution became turbid and a slight increase in viscosity was observed, but it could be stirred sufficiently. Polymerization was stopped after 3 hours, and the viscosity of the product was measured and found to be 30,000 cps. Furthermore, when this aqueous dispersion was diluted 8 times with water, it became a homogeneous aqueous solution, and its viscosity was
It was 750cps. Comparative Example 2 In Example 2, polyethylene glycol 20
Polymerization was carried out under the same conditions as in Example 1 using the same composition as in Example 2, except that g and 5 g of soluble starch were not used. The amount increased rapidly, and after 10 minutes, it became agar-like and stirring was impossible. Example 3 In a flask similar to Example 1, 100 g of water, 5 g of polyvinyl alcohol, and 20 g of polyvinylpyrrolidone were added.
After adding and mixing and dissolving 18.8 g of diethylaminoethyl acrylate. Below, Example 1
Polymerization was carried out in the same manner as above to obtain an aqueous dispersion with a viscosity of 34,000 cps. When this aqueous dispersion was diluted 15 times with water, the viscosity of the aqueous solution was 300 cps. Example 4 In a flask similar to Example 1, 100 g of water, 16 g of polyethylene glycol (molecular weight 11,000), and 1 g of polyethylene oxide (molecular weight 100,000) were added and mixed and dissolved, and then 33 g of β-methacroyloxyethyltrimethylammonium chloride was added. . Thereafter, polymerization was carried out under the same conditions as in Example 1 to obtain an aqueous dispersion having a viscosity of 45,000 cps. When this aqueous dispersion was diluted 22 times with water, the viscosity of the aqueous solution was 270 cps.
It was hot. Example 5 In a flask similar to Example 1, 100 g of water, 12.5 g of polyethylene glycol (molecular weight 20,000), and 1 g of polyethylene oxide (molecular weight 1,000,000 to 1,700,000).
After mixing and dissolving, add 20g of β-methacroyloxyethyltrimethylammonium chloride.
Then, 1 ml of a 0.75% aqueous solution of hydrogen peroxide and 3 ml of a 2% aqueous solution of sodium bisulfite were added while purging with nitrogen gas, and polymerization was carried out for 4 hours with stirring at 45°C under a nitrogen gas atmosphere. Summer. Immediately after the start of polymerization, the system became milky and the viscosity gradually increased, but sufficient stirring was possible. The resulting aqueous dispersion had a viscosity of 53,000 cps. Also,
The viscosity of an aqueous solution obtained by diluting this aqueous dispersion 25 times with water was 800 cps. Example 6 Add 100 g of water, 15 g of polyethylene glycol (molecular weight 6000), and 2 g polyethylene oxide (molecular weight 500,000) to the same flask as in Example 1, mix and dissolve, and then add 3 g of surfactant (Amit 208, Emulgen pp290). Added. Then 20 g of dimethylaminoethyl methacrylate and 10 g of methacrylamide were added. Thereafter, polymerization was carried out under the same conditions as in Example 1 to obtain an aqueous dispersion having a viscosity of 45,000 cps. When this aqueous dispersion was diluted 22 times with water, the viscosity of the aqueous solution was 850 cps.

Claims (1)

[Claims] 1. (A) 100 parts by weight of water and (B) a water-soluble polymer having at least one functional group selected from the group consisting of an ether group, a hydroxyl group, and a carboxyl group in the polymer constituent unit. (C) General formula: [In the formula, R ₁ represents a hydrogen atom or a methyl group,
Y represents a [formula] group or a [formula] group. Note that R ₂ and R ₅ represent an alkylene group having 2 to 5 carbon atoms or a hydroxyalkylene group having 2 to 5 carbon atoms, and R ₃ , R ₄ , R ₆ and R ₇ represent the same or different types of carbon atoms 1 to 5. represents an alkyl group,
R ₈ is an alkyl group having 1 to 5 carbon atoms,
[Formula] or -CH ₂ COOH, Z represents a halogen atom, SO ₃ OCH ₃ , 1/2SO ₄ , CH ₃ SO ₃ or CH ₃ COO. ] or a mixture with other water-soluble ethylenically unsaturated monomers containing more than 50% by weight of the water-soluble ethylenically unsaturated monomer (B )
An aqueous dispersion of a water-soluble polymer composite having excellent stability and fluidity obtained by polymerization at a weight ratio of (C) in the range of 10:1 to 1:10.