JPS63225608A - Manufacture of water-soluble copolymer - Google Patents

Abstract

PURPOSE:To produce a water-soluble copolymer, by adding continuously an acrylamide compound to an aqueous solution containing a diallylamine derivative monomer during the polymerization reaction thereby reacting almost all of the inactive diallylamine derivative monomer. CONSTITUTION:In the method of preparing a cationic copolymer by copolymerization of a diallylamine derivative monomer (e.g., diallylmethylamine hydrochlide, etc.) of the formula I (wherein R1 and R2 are each H or CH3; R3 and R4 are each H or 1-6C alkyl; and X is an anion of an organic acid or an inorganic acid) with an acrylamide compound (acrylamide or methacrylamide) of the formula II (wherein R5 is H or CH3), a compound of the formula II is added continuously to an aqueous solution containing a compound of the formula I during the polymerization. According to the above reaction, the compound of the formula I which can not be reacted by the prior method can be reacted almost all to produce a water-soluble copolymer in a high yield.

Description

Detailed Description of the Invention <Industrial Application Field> The present invention relates to a cationic copolymer obtained by copolymerizing an acrylamide compound and a diallylamine derivative monomer, and an acrylamide compound α.

The present invention relates to a method for producing an amphoteric copolymer obtained by copolymerizing a β-unsaturated carboxylic acid and a diallylamine derivative monomer.

<Prior art and its problems> Diallylamine derivative monomers undergo a cyclization reaction to give a polymer having a cyclic structure, as described in various literature, but allylamine derivatives are present in the molecule. group, so-called allylic destructive chain transfer'('
allylic degradative chain
-transfer), and the polymerization activity is not necessarily high.

This is more noticeable in copolymerization reactions with other monomers. For example, J, Polym, Sci, Pol
ym, chem.

6d,], 29-36 (1986), in the copolymerization reaction of diallyldimethylammonium chloride (DADMAC), which is one of diallylamine derivative monomers, and acrylamide, acrylamide (Ml
) and DADMAC (M2) are: r, =6.7 r2 =0.58,
It is noted that the reactivity of DADMAC is extremely low compared to acrylamide.

Due to the low polymerization activity of diallylamine derivative monomers, when performing a copolymerization reaction of diallylamine derivative monomers with acrylamide compounds, α, β-unsaturated carboxylic acids, etc., polymerization of acrylamide-based compounds, α, β-unsaturated carboxylic acids, etc. The reaction proceeds preferentially, resulting in a large amount of diallylamine derivative monomer remaining. On the other hand, if a polymerization initiator is added sequentially to reduce the remaining amount of diallylamine derivative monomer, only a low molecular weight polymer will be obtained, and in extreme cases, the undesirable situation of polymer chain splitting may occur. There is a danger of this happening.

<Means for Solving the Problems> The present inventors have completed the present invention as a result of intensive studies to solve these problems.

That is, the present invention is based on the general formula (1) (wherein R1 and R2 represent hydrogen or a methyl group, and R1,
R1 each independently represents hydrogen or an alkyl group having 1 to 6 carbon atoms. X represents an anion of an organic acid or an inorganic acid.

) A diallylamine derivative monomer (A) represented by
General formula (II) CH2=C(Rs) -CONH2(I
f) A method for producing a cationic copolymer by copolymerizing with an acrylamide compound (B) represented by (in the formula, Rs represents hydrogen or a methyl group), an aqueous solution containing (A) The present invention provides a method for producing a cationic copolymer, characterized in that (B) is continuously added during the polymerization reaction.

Furthermore, the present invention provides one or more compounds (C ), wherein (B) and (C) are continuously added to an aqueous solution containing (A) during the polymerization reaction. The present invention provides a method for manufacturing.

In the present invention, the diallylamine derivative heavy polymer (A) represented by the general formula (I) includes inorganic or organic acid salts of secondary amines exemplified by diallylamine and dimethallylamine, diallylmethylamine, diallylethylamine, Inorganic or organic acid salts of tertiary amines such as diallylbutylamine, diallyldimethylammonium chloride,
Specific examples include quaternary ammonium' salts such as diallyldimethylammonium bromide, diallyldiethylammonium chloride, diallyldibutylammonium chloride, and diallylmethylethylammonium chloride.

In addition, an acrylamide compound represented by the general formula (n) (
B) is acrylamide or methacrylamide.

In addition, unsaturated monocarboxylic acids of compound (C) include acrylic acid, methacrylic acid, etc., unsaturated dicarboxylic acids include maleic acid, fumaric acid, itaconic acid, etc., and salts thereof include these. Examples include alkali metal salts such as sodium salts and potassium salts, and ammonium salts.

In carrying out the method for producing a copolymer of the present invention, the proportion of compound (A) in all monomers used is preferably 1 to 1.
70 mol%, more preferably 2 to 50 mol%, the compound (
The proportion of B) is preferably 30 to 99 mol%, more preferably 50 to 98 mol%, and the proportion of compound (C) is preferably 0 to 20 mol%.

Furthermore, other monomers copolymerizable with the above-mentioned compounds can be introduced when carrying out the production method of the present invention.

These monomers include nonionic monomers such as (meth)acrylonitrile, methyl acrylate, hydroxyethyl (meth)acrylate, styrene, and vinyl acetate, dimethylaminoethyl (meth)acrylate, and dimethylaminopropyl (meth)acrylate. Examples include cationic monomers such as acrylamide or quaternized products thereof, and bifunctional monomers such as ethylene glycol di(meth)acrylate and methylene bis(meth)acrylamide.

As the polymerization initiator, commonly used initiators can be used. For example, persulfates such as ammonium persulfate and potassium persulfate, azo compounds such as 2,2°-diamidinyl-2°2°-azopropane dihydrochloride, azobisisobutyronitrile, di-t-butyl peroxide, cumene hydrochloride, etc. Examples include peroxides such as peroxide and hydrogen peroxide. Further, known redox initiators such as potassium persulfate and sodium bisulfite, or a combination of a tertiary amine can be used.

Polymerization is usually carried out at 10 to 100°C, preferably 40 to 90°C, for 1 to 12 hours. Although polymerization can be carried out in the presence of oxygen, it is preferably carried out in an atmosphere of an inert gas such as nitrogen gas.

The polymerization reaction is carried out by continuously adding compound (B) or compound (B) and compound m (C) to an aqueous solution containing diallylamine derivative monomer (A), but even if the addition rate is constant, It may be non-uniform velocity. Further, the addition time is usually 10 minutes to 10 hours.

In producing the amphoteric copolymer, compound (B) and compound (C) may be added separately and continuously, or may be mixed and then added continuously.

Further, a portion of these may be added to the system from the beginning of the polymerization reaction, as long as the spirit of the present invention is not impaired.

Also, compounds (A), (B) or (A>, (B), (C
) and other monomers copolymerizable with compound (B), compound (C), etc. may be mixed and added continuously, or may be added separately and continuously, or may be added in part from the beginning of the polymerization reaction. may be added to the system.

The polymerization initiator may be added in advance to an aqueous solution containing the diallylamine derivative monomer, or may be added to the compound (B),
It may be added continuously at the same time as compound (C).

<Examples> Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the Examples.

In the examples, % represents weight % unless otherwise specified.

In addition, the unreacted monomers in Examples and Comparative Examples were quantified by gas chromatography analysis, double bond quantification by iodine method, and colloid equivalent measurement.

Example 1 3.8 g of 98% diallylmethylamine hydrochloride (0,02
5 mol) and 97.6 g of ion-exchanged water were charged into a reactor equipped with a stirrer, and the pH was adjusted to 7.0. Next, after replacing the air in the device sufficiently with nitrogen gas to make the oxygen incompatible,
0.1 g of ammonium persulfate was added at °C. Continuation,
While keeping the internal temperature at 70° C. under nitrogen, 32.0 g (0,225 mol) of a 50% aqueous acrylamide solution was dropped into the reaction system over 2 hours. Thereafter, the mixture was kept at 70° C. for 2 hours to complete the reaction. Quantitative determination of unreacted monomers revealed that the reaction rates of diallyldimethylamine hydrochloride and acrylamide were each 99% or more.

The product had a polymer content of 15%, P H = 3.9, and Brookfield viscosity (25°C) of 55 Ps.

Example 2 10.7 g of 50% diallylamine hydrochloride aqueous solution (0,
04 mol), 144.1 g of ion-exchanged water was charged into a reactor equipped with a stirrer, and P was added with a small amount of 28% caustic soda aqueous solution.
Adjusted to H=6.0. Next, the air in the apparatus was sufficiently replaced with nitrogen gas to eliminate oxygen, and then 0.28 g of ammonium persulfate was added at 70°C.

Subsequently, 51.2 g (0.36 mol) of 50% acrylamide was added dropwise into the reaction system over 3 hours while maintaining the internal temperature at 70°C. Thereafter, the reaction was completed by keeping the temperature at 70°C for 3 hours. Based on the quantitative determination of unreacted residual material, the reaction rates of diallylamine hydrochloride and acrylamide were each 99%.
% or more.

The product had a polymer content of 15%, P H = 3.5, and Brookfield viscosity (25°C) of 38 Ps.

Example 3 10.7 g of 50% diallylamine hydrochloride aqueous solution (0,
04 mol), 116.1 g of ion-exchanged water was charged into a reactor equipped with a stirrer, and P was added with a small amount of 28% caustic soda aqueous solution.
Adjusted to H=5.5. Next, the air in the apparatus was sufficiently replaced with nitrogen gas to eliminate oxygen incompatibility. Then, while maintaining the internal temperature at 70°C, add 28.0 g of 1% ammonium persulfate aqueous solution.
,, 51.2 g (0.36 mol) of 50% acrylamide
were simultaneously added dropwise into the reaction system over a period of 2 hours.

Thereafter, the reaction was completed by keeping the temperature at 70°C for 5 hours. From the quantitative determination of unreacted monomers, the reaction rates of diallylamine hydrochloride and acrylamide were 95% and 99%, respectively.

The product had a polymer content of 15%, P H = 3.9, and Brookfield viscosity (25°C) of 18 Ps.

Example 4 23.8 g (0,106 mol) of 71.4% diallyldimethylammonium chloride aqueous solution, 71 mol of ion-exchanged water
．． 0 g was charged into a reactor equipped with a stirrer, and the air in the apparatus was sufficiently replaced with nitrogen gas to eliminate oxygen incompatibility.

After adding 1.88 g of potassium persulfate at an internal temperature of 70°C, add 50% acrylamide 60% while maintaining an internal temperature of 70°C.
g (0,423 mol) was added dropwise into the reaction system over 2 hours and 30 minutes. Thereafter, the reaction was completed by keeping the temperature at 70°C for 3 hours. From the quantitative determination of unreacted monomers, the reaction rates of diallyldimethylammonium chloride and acrylamide were each 99% or more.

The product had a polymer content of 30%, P H = 2.3, and Brookfield viscosity (25°C) of 39 Ps.

Example 5 50% diallylamine salt-salt aqueous solution 9.6 g (0.03
6 mol) and 146.5 g of ion-exchanged water were charged into a reactor equipped with a stirrer, and then the air in the apparatus was sufficiently replaced with nitrogen gas to eliminate oxygen incompatibility. Then, after adding 0.39 g of potassium persulfate at an internal temperature of 70°C, while maintaining the internal temperature at 70°C,
50% acrylamide 47.2g (0,332mol)
And 80% 1ri! J le 1i12. 9 g (0,032
-f-ru) (The mixture D was added dropwise into the reaction system over 2 hours. The reaction was then kept at 70°C for 5 hours to complete the reaction. From the quantitative determination of unreacted monomers, diallylamine hydrochloride, acrylamide, The reaction rates of acrylic acid and acrylic acid were each 99% or more.

The product had a polymer content of 15%, a pH of 2.9, and a Brookfield viscosity (at 25° C.) of 100 Ps.

Example 6 The amount of 50% diallylamine hydrochloride aqueous solution was 2°14g
(0,008 mol), the amount of 50% acrylamide is 55
．． A cationic polymer was produced in the same manner as in Example 2 except that the amount was 7 g (0,392 mol). Quantitative determination of unreacted monomers revealed that the reaction rates of diallylamine hydrochloride and acrylamide were each 99% or more.

The product had a polymer content of 30%, a pH of 2.70, and a Brookfield viscosity (25° C.) of 10 PS.

Example 7 The amount of 50% diallylamine hydrochloride aqueous solution was 64°2g
(0.24 mol), the amount of 50% acrylamide was 22.
A cationic polymer was produced in the same manner as in Example 2 except that the amount was 8 g (0.16 mol).

Quantitative determination of unreacted monomers revealed that the reaction rates of diallylamine hydrochloride and acrylamide were each 99% or more.

The product had a polymer content of 30%, a pH of 2.67, and a Brookfield viscosity (at 25° C.) of IPs.

Example 8 The amount of 50% diallylamine hydrochloride aqueous solution was 5°35g
(0.02 mol), 0% acrylamide 42.
6 g (0.30 mol), the amount of 80% acrylic acid 7.
An amphoteric polymer was produced in the same manner as in Example 5 except that the amount was 2 g (0.08 mol).

From the quantitative determination of unreacted monomers, the reaction rates of diallylamine hydrochloride, acrylamide, and acrylic acid were each 99%.
That was it.

The product had a polymer content of 15%, a pH of 2.8, and a Brookfield viscosity (at 25° C.) of 41 Ps.

Example 9 The amount of 98% sialylmethylamine hydrochloride was 18°2g
A cationic polymer was produced in the same manner as in Example 1, except that the amount of the 50% acrylamide aqueous solution was changed to 39.8 g (0,280 mol). Quantitative determination of unreacted monomers revealed that the reaction rates of diallylmethylamine hydrochloride and acrylamide were each 99% or more.

The product had a polymer content of 15%, a pH of 3.5, and a Brookfield viscosity (at 25° C.) of 28 PS.

Example 10 71.4% diallyldimethylammonium chloride aqueous solution 35.9 g (0.16 mol), ion-exchanged water 21
3.3 g was charged into a reactor equipped with a stirrer, and then the air in the apparatus was sufficiently replaced with nitrogen gas to eliminate oxygen incompatibility. Next, at an internal temperature of 70°C, 0.39 g of potassium persulfate was added, and then 31% of 50% acrylamide was added while maintaining the internal temperature at 70°C.
2g (0°22mol) and acrylonitrile 1.06g
(0°02 mol) was added dropwise into the reaction system over 2 hours. Thereafter, the reaction was completed by keeping the temperature at 70°C for 5 hours. From the quantitative determination of unreacted monomers, the reaction rates of diallyldimethylammonium chloride, acrylamide, and acrylonitrile were each 99% or more.

The product had a polymer content of 15%, a pH of 3.2, and a Brookfield viscosity (at 25° C.) of 30 Ps.

Example 11 21.4 g (0°08 mol) of 50% diallylamine hydrochloride and 43.3 g of ion-exchanged water were charged into a reactor equipped with a stirrer, and then the air in the device was sufficiently replaced with nitrogen gas to make it oxygen-free. . Then, at an internal temperature of 70°C, add 0.3% potassium persulfate.
After adding 9g, while keeping the internal temperature at 70℃, 50%
Acrylamide 39.8g (0.28 mol) and 80%
Acrylic acid 1°, 8 g (0.02 mol) and styrene 2
．． 1 g (0.02 mol) of the mixed solution was dropped into the reaction system over 4 hours. Thereafter, the reaction was completed by keeping the temperature at 70°C for 5 hours. From the quantitative determination of unreacted monomers, the reaction rates of diallylamine hydrochloride, acrylamide, acrylic acid, and styrene were each 99% or more.

The product had a polymer content of 30%, a pH of 3.0, and a Brookfield viscosity (at 25° C.) of 3 Ps.

Comparative Example 50% diallylamine hydrochloride aqueous solution 10.7 g (0,
04 mol) 144.1 g of ion-exchanged water was charged into a reactor equipped with a stirrer, and P H was added with a small amount of 28% caustic soda aqueous solution.
= 6.0. Add 50% acrylamide 5
After charging 1.2 g (0.36 mol), the air in the apparatus was sufficiently replaced with nitrogen gas to make it oxygen-incompatible. Next, the internal temperature was set to 70°C, and after adding 0.28 g of ammonium persulfate, the mixture was kept at 70°C for 6 hours. From the quantitative determination of unreacted monomers, the reaction rates of diallylamine hydrochloride and acrylamide were 63.0% and 95.1%, respectively.

The Brookfield viscosity of the product (at 25°C) is 23PS
, PH=3.3.

<Effects of the Invention> As can be seen from the comparison between Examples and Comparative Examples, diallylamine derivative monomers, which were difficult to react with conventional production methods, almost become reactive with the production method of the present invention.

Margin below

Claims (2)

[Claims] (1) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R_1 and R_2 represent hydrogen or methyl groups, and R
_3 and R_4 each independently represent hydrogen or an alkyl group having 1 to 6 carbon atoms. X represents an anion of an organic acid or an inorganic acid. ) Diallylamine derivative monomer (
A) and the general formula (II) CH_2=C(R_5)-CONH_2(II) (in the formula,
R_5 represents hydrogen or a methyl group. ) In the method of producing a cationic copolymer by copolymerizing with an acrylamide compound (B) represented by (B), (B) is continuously added to an aqueous solution containing (A) during the polymerization reaction. A method for producing a characteristic cationic copolymer. (2) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R_1 and R_2 represent hydrogen or methyl groups, and R
_3 and R_4 each independently represent hydrogen or an alkyl group having 1 to 6 carbon atoms. X represents an anion of an organic acid or an inorganic acid. ) Diallylamine derivative monomer (
A) and the general formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) (In the formula, R_5 represents hydrogen or a methyl group), an acrylamide compound (B), and α, In a method for producing an amphoteric copolymer by copolymerizing one or more compounds (C) selected from the group consisting of β-unsaturated monocarboxylic acids, α, β-unsaturated dicarboxylic acids, and salts thereof. , (B) and (C) in an aqueous solution containing (A).
1. A method for producing an amphoteric copolymer, which comprises continuously adding the following during a polymerization reaction.