JPH03134002A - Production of epoxidized water-soluble polymeric compound - Google Patents

Abstract

PURPOSE:To obtain a water-soluble polymeric compound in which epoxy groups can be present stably and whose comonomer ratio can be extensively varied by radical-copolymerizing an epoxidized water-soluble unsaturated compound with a vinyl-sulfonate salt in a specified solvent. CONSTITUTION:A process for polymerizing a monomer composition comprising 5-90wt.% monomer mixture of an epoxidized unsaturated compound with another vinyl-polymerizable monomer in a weight ratio of 100/0-20/80 and 95-10wt.% vinylsulfonate salt in the presence of a radical generator in a nitrogen atmosphere, wherein a mixed solvent comprising a ketone solvent and water in a mixing ratio of 30/70-90/10 (by weight) is used as the solvent. As the ketone solvent, acetone is desirable. Examples of the epoxidized unsaturated compound include glycidyl (meth)acrylate, glycidyl itaconate and allyl glycidyl ether. Examples of the vinylsulfonate salt include allylsulfonate salt and methallylsulfonate salt.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing an epoxy group-containing water-soluble polymer compound.

[Prior Art] Epoxy group-containing polymer compounds utilize the reactivity of epoxy groups and are used in a wide range of applications including plastics, paints, inks, and adhesives.

In addition, sulfonic acid group-containing polymer compounds are also used in various fields as one of the polymers typified by naphthalene sulfonic acid formalin compounds. Therefore, if a polymer compound containing an epoxy group and a sulfonic acid group in any ratio can be obtained, it would be of great industrial value. However, due to the strong water solubility of vinyl sulfonates, the number of organic solvents that can be dissolved in them is limited.
Moreover, since the epoxy group-containing unsaturated compound is oil-soluble and has poor water solubility, it has been difficult to obtain a polymer compound by copolymerizing the two in an arbitrary ratio. Polymerization example of an epoxy group-containing unsaturated compound and a vinyl sulfonate salt! ,
, Japanese Patent Application Publication No. 59-5.3505! Publication '/c There is an example of modification of carbon Il & iL by depolymerization of carbon fiber to 11%, but this is the present invention)! It's different.

The present inventors have investigated various solvents to synthesize polymer compounds containing epoxy groups and sulfonic acid groups in arbitrary ratios, but one problem is that most of the epoxy groups are lost depending on the synthesis conditions. I also faced

[Problem to be solved by the invention]

The present invention provides a production method that allows copolymerization of an epoxy group-containing unsaturated compound and a vinyl sulfonate in a wide range of ratios, and that allows the epoxy group to remain stably in the resulting polymer compound. It is.

[Means to solve the problem]

That is, 1 the present invention is characterized in that the weight ratio of the epoxy group-containing unsaturated compound and the vinyl polymerizable monomer is 10010 to 20/8.
In the presence of a monomer composition consisting of 5 to 90!1% of a monomer mixture of 0.0% and 95 to 10% of a vinyl sulfonate and 95% to 10% of a vinyl sulfonate.

When polymerizing in a nitrogen gas atmosphere, the mixing ratio of ketone solvent and water as a solvent is 30/70 to 90/10.
This is a method for producing an epoxy group-containing water-soluble polymer compound, which is characterized by using a mixed solvent with a heavy working ratio.

In the present invention, epoxy group-containing unsaturated compounds include unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate, glycidyl methacrylate, glycidyl itaconate, and glycidyl crotonate, and unsaturated alcohols such as allyl glycidyl ether and methallyl glycidyl ether. Examples include glycidyl ethers.

Examples of monomers copolymerizable with the epoxy group-containing unsaturated compound include styrene and α-methylstyrene.

Aromatic vinyl compounds such as vinyltoluene and general formula CI
) acrylic acid or methacrylic acid (hereinafter 1
Both are collectively called (meth)acrylic acid), (meth)
Examples of acrylic esters include vinyl chloride, vinyl acetate, and acrylate.

CH,=CRICOOR2・・・・・・・・・・・・C
I) (here, R1 is a hydrogen atom or a methyl group, R2 is a hydrogen atom, a furkyl group having 1 to 22 carbon atoms, or (AO)
nR3, AO is an oxyethylene group or an oxybupylene group, n is 0 to 100, and R3 is a hydrogen atom or a furkyl group having 1 to 12 carbon atoms. ) Vinyl sulfonates include allylsulfonate, methallylsulfonic acid tJ1.2-(meth)acryloyloxyethylsulfo/acid, 3-(meth)acryloyloxypropylsulfonic acid 1, and the like.

Examples of the cation moiety of the vinyl sulfonate include alkali metals, alkaline earth metals, ammonium, etc., and sodium and potassium are particularly preferred.

The weight ratio of the epoxy group-containing unsaturated compound and the vinyl polymerizable monomer is 10010 to 20/80, but if this ratio is smaller than 20/80'J, there will be fewer epoxy groups in the copolymer. This makes it unsuitable for applications that utilize 2 epoxy groups.

The weight ratio of this monomer mixture to the vinyl sulfonate is preferably 5/95 to 90/10. If the direct ratio of the two is less than 5/95, the amount of epoxy group-containing compounds will be too small, and if it exceeds 90/10, the amount of sulfonate will be too small, making it unsuitable for applications that utilize anion d.

As the ketone solvent used in the present invention, acetone and methyl ethyl ketone can be used, but acetone is preferable.

The mixing ratio of ketone solvent and water is 30/70 to 90/1
If the mixing ratio is less than 30/70, the epoxy group-containing unsaturated compound and the monomer capable of vinyl polymerization may not dissolve and become non-uniform, which is not preferable.
If it exceeds 0/10, vinyl sulfonate may precipitate and become non-uniform, which is not preferable.

Examples of the radical generator used in the present invention include organic peroxides such as benzoyl peroxide and t-butylperoxyoctoate, azo oil-soluble radical generators such as N,N'-azobiswingtyl nitrile, Water-soluble radical generators such as persulfates and hydrogen peroxide can be used.

The formula J of the present invention includes an unbonded epoxy group-containing compound (B) and other vinyl-polymerizable monomers.

Among (C) vinyl sulfonate, (D) radical generator, (E) mixed solvent of ketone solvent and water, (DJ
If is oil-soluble, dissolve (■) in a mixture of (Al or jt-(Bl or (81), then (C) and tlE
) is preferably added dropwise into the mixed solution. However, the invention is not limited thereto, and polymerization may be carried out after adding (4) to (E) in sequence to make the mixture uniform.

In the present invention, since a ketone solvent with a low boiling point is used, the ring-opening reaction of the epoxy group due to high temperatures can be avoided, but it is preferable to carry out the reaction below the boiling point from the viewpoint of easy temperature control.

〔Effect of the invention〕

According to the present invention, an epoxy group-containing unsaturated compound and a vinyl sulfone a salt can be copolymerized in a wide range of ratios, and a water-soluble molecular compound in which an epoxy group is stably present can be produced.

〔Example〕

The present invention will be explained in more detail by way of examples.

Example engineering.

A 1 ton four-hole flask was equipped with a stirrer, a temperature needle, a nitrogen gas blowing hole, a reflux condenser, and a dropping funnel, and 2501E of acetone and 250% of water were placed in it. F and 100Pt of sodium methallylsulfonate (hereinafter referred to as MASNm) were taken at a reflux temperature (64 to 66
The temperature was raised to C). A monomer solution prepared by dissolving 101 parts of KN,N'-7zobiswinti p-nitrile and 100 parts of glycine methacrylate (hereinafter referred to as GMA) was transferred to Urashita at the same temperature for 1 hour, and then heated at the same temperature for 2 hours. held. Next, acetone was distilled off under reduced pressure, and GMA
-MAS Na copolymer aqueous solution 431F was obtained.

The solid content of the resulting copolymer aqueous solution was 47%.

The residual rate of epoxy groups was 88%.

However, the solid content measurement was performed at 140C for 90 minutes and under reduced pressure for 5 minutes.
It was dried in a steamer and obtained. The residual rate of epoxy groups was calculated from the addition of hydrogen chloride in a dimethylformamide solution. In addition, the liquid was a translucent and viscous liquid.

Example 2 Acetone 200JE was added to the equipment used in Example 1.

300 p of water and 12 sodium 2-methacryloyloxybotylsulfonate (hereinafter referred to as SIIEMANa)
0F was dissolved, and the temperature was raised to reflux temperature (64 to 66 c) while blowing nitrogen gas at a rate of 50 d/min.

To this, benzoyl peroxide 6P%GMA60y,
A mixed solution of 20 ml of styrene (hereinafter referred to as St) was added dropwise over 1 hour, and the mixture was further maintained at the same temperature for 2 hours. The subsequent operations were performed in the same manner as in Example 1. As a result, G.M.
An aqueous copolymer solution 450F of A-8L-8EMANa was obtained. The solid content of the obtained aqueous copolymer solution was 44.4 yen, and the residual rate of epoxy groups was 90%. The appearance was that of a transparent viscous liquid.

3゜Add 200% acetone, 3007 water and 20F potassium 3-methacrylic ρyl oxidibqpyrsulfonate (hereinafter referred to as SPMAK) to the fffi used in Example 1, and add azobisisobutyl to this. The same operation as on the back side 1 was carried out except that a mixed solution of 1ay of nitrile, 40y of methallyl glycidyl ether (hereinafter referred to as MAG), and 40y of methyl methacrylate (hereinafter referred to as MMA) was subjected to tR.

As a result, 430 jl of an aqueous copolymer solution of MAG-MMA-8PMAK was obtained. The solid content of the obtained aqueous copolymer solution was 1146.4%, and the residual rate of epoxy groups was 93%. The appearance was a transparent viscous liquid.

Example Also, 100j of methyl ethyl ketone was added to the equipment used in Example 1.
i, dissolve water 4007 and MASNa 140y7.
Add to this 7 zobisin butyp nitrile 5y.

GMA 30 F, ω-hydroxypolyoxyethylene (9 mol) methacrylate (hereinafter referred to as PEMA) 3
The same operation as in Example 1 was performed except that 0.0% of the mixed solution was added dropwise. That double arrogance, GMA-PEMA-MASNa
440 g of an aqueous copolymer solution was obtained. The solid content of the resulting aqueous copolymer solution was 45.3%, and the residual rate of epoxy groups was 83%.

The appearance was a transparent viscous liquid.

Example 5゜The equipment used in Example 1? 1tVc7 seton 400j+,
Water 100jf, MASNa20p, GMA40y1ω-
Take 140 y of methyl polyoxyethylene (100 mol) methacrylate (hereinafter referred to as MPHMA) and 10 y of ambisisobutyronitrile, and blow nitrogen gas at 50 mol/min.
Blowing was started at d, and 30 minutes later, the temperature was started to rise and the reaction was carried out at a reflux temperature of 62 to 63C for 3 hours. Next, 300 yen of water
After adding jr.

Acetone was distilled off under reduced pressure, and GMA-MPEMA-M
An aqueous copolymer solution 501y of A S Na was obtained. The solid content of the obtained aqueous copolymer solution was 39.9%, and the residual rate of epoxy groups was 89%. The appearance was a translucent viscous liquid.

Example 6゜In the equipment used in Example 1, A7Ton 505E and water 450
! ! , SEMANa190y, GMAloF and benzoyl peroxide 3F were taken, and the same operation as in Example 5 was performed. As a result, an aqueous copolymer solution 595y of GMA-8EMANa was obtained. The solid content of the obtained copolymer aqueous solution was 33.6%, and the residual rate of epoxy groups was 80%.
It was Chi. The appearance was a transparent viscous liquid.

Comparative example l.

The procedure was carried out in exactly the same manner as in Example 1 except that methanol was used instead of 77 tons. As a result, the reflux temperature was 66C, and the GMA-M obtained by trapping after removing methanol
A copolymerized aqueous solution 425y of A S Na was obtained. The solid content of the obtained copolymer was 47%, and the residual rate of epoxy groups was 12-5%.

The appearance was a clear viscous liquid.

Comparative Example 2 Water 5009i and SEMA were added to the equipment used in Example 1.
Nalooy was dissolved, the temperature was raised to 70C while blowing nitrogen gas at 5 degrees per minute, and CMAloop in which 5 NO of benzoyl peroxide was dissolved was added dropwise over 1 hour.
The reaction was then continued for 2 hours. The system was heterogeneous, with water-insoluble polymer deposited on the flask walls.

Comparative example 3゜ 400y of 7 setons was added to the equipment used in Example 1.

Take GMAloo and MASNalOOP, blow nitrogen gas at 50 m/min, raise the temperature to reflux temperature while stirring vigorously, and add 10y of azobisinbutylnitrile.
A mixed solution of 1007 and 77 tons was added dropwise over 1 hour, and then maintained under the same conditions for 2 hours. Then 500j of water
While adding iE& dropwise, acetone was distilled off under reduced pressure to replace acetone with water.

As a result, metal particles precipitated on the flask wall K, and only a water-insoluble polymer was obtained.

Claims (1)

[Claims] 1. 5 to 90% by weight of a monomer mixture in which the weight ratio of the epoxy group-containing unsaturated compound to other vinyl-polymerizable monomers is 100/0 to 20/80 and vinyl sulfonate 95
When polymerizing a monomer composition consisting of ~10% by weight in a nitrogen gas atmosphere in the presence of a radical generator, the mixing ratio of the ketone material and water as a solvent is 30/70 to 9.
A method for producing an epoxy group-containing water-soluble polymer compound, the method comprising using a mixed solvent having a weight ratio of 0/10.