JPS6126626A - Preparation of copolymer of aldehydoaniline and alpha, beta monoethylenic unsaturated monomer containing no carboxyl group - Google Patents

Abstract

PURPOSE:To obtain a polymer having improved water resistance without danger of using a peroxide, by copolymerizing an aldehydoaniline with a monoethylenic unsaturated monomer. CONSTITUTION:(A) A saturated carboxylic acid such as formic acid, oxalic acid, etc. is blended with (B) an aldehydoaniline such as butylaldehydozniline, acetalde hydoaniline, etc., and (C) an alpha, beta monoethylenic unsaturated monomer such as methyl methacrylate, etc. containing no carboxyl group in a weight ratio of >=3pts.wt. component A and 3-20pts.wt. component B based on 100pts.wt. component C and polymerized by block polymerization, solution polymerization, etc. at normal temperature, to give the aimed polymer. The reaction rate can be controlled by changing an amount of the component A used, and, since there is no danger, the monomers can be impregnated into paper, wood, cloth, etc. and polymerized.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention is directed to the polymerization of aldehyde aniline and α,β monoethylenically unsaturated monomer having no carboxyl group without using a peroxide polymerization initiator. Regarding how to.

[Prior art] α,β monoethylenically unsaturated monomers such as vinyl esters, (meth)acrylic acid esters, (meth)acrylic acid, ethylene, styrene, vinyl chloride, etc. are combined with saturated monomers, which are extremely common. Specifically, it is well known that polymerization can be easily carried out using peroxides such as persulfuric acid, benzoyl peroxide, or a peroxide polymerization initiator using a combination of a peroxide and a reducing agent.

However, depending on the amount of peroxide used and the amount of polymerization inhibitor in the monomer, polymerization using such peroxide polymerization initiators can cause unexpectedly violent polymerization reactions, such as bumping. The disadvantage is that it creates a dangerous situation.

Furthermore, recently, polymerization has been increasingly carried out by impregnating a monomer into a porous substance on-site.

In such cases, peroxide must be transported to the site or stored, but peroxide has the disadvantage of being difficult to use due to the risk of spontaneous combustion.

Furthermore, when a common m salt is used, the sulfate groups remain at the ends of the polymer as fragments, which may be a problem depending on the application.

The present inventor has made efforts to develop polymerization initiators other than this type in order to solve the drawbacks of peroxide polymerization initiators. As a result of studying many types of compounds, they found that when aldehyde aniline is used, a polymerization reaction may occur even without using a peroxide polymerization initiator.

In many cases, the polymerization reaction did not occur, but as a result of further investigation into the cases in which the polymerization reaction did occur, we found that the presence of saturated carboxylic acid in the reaction system with α and β monoethylenically unsaturated monomers is important. I figured something out.

However, since the polymers obtained in this way inevitably contain carboxyl groups, while they have good affinity for polar substrates, they also have limitations in properties such as water resistance and alkali resistance. I don't like being beaten.

[Summary of the Invention] Considering the drawbacks of peroxide polymerization initiators, the present inventor conducted research to create a polymer that does not use peroxide polymerization initiators and does not contain carboxyl groups. By the presence of α and β without carboxyl groups,
The present invention was completed by discovering that a monoethylenically unsaturated monomer can be polymerized using the saturated monomer rhdehyde aniline to produce a polymer containing no carboxyl group.

That is, the present invention combines aldehyde aniline and an α,β monoethylenically unsaturated monomer having no carboxyl group,
Aldehyde aniline, which is copolymerized in the presence of a saturated monomer, a saturated carboxylic acid, and in the absence of a peroxide polymerization initiator - α, β, which does not have a carboxyl group,
This is a method for producing a β-monoethylene saturated monomer copolymer.

The characteristics of the present invention are the use of aldehyde aniline,
The saturated carboxylic acid should be present in the reaction system, and the peroxide polymerization initiator should not be used.

Peroxide polymerization initiators have a negative effect on the polymerization reaction of the present invention.

[Example] The aldehyde aniline used in the present invention is a reaction product of aldehyde and aniline, such as butyraldehyde aniline, acetaldehyde aniline, crotonaldehyde aniline, heptaldehyde aniline, etc.d Carboxyl used in the present invention α,β monoethylenically unsaturated monomers having no groups are combined with saturated monomers, (meth)acrylates such as methyl methacrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, vinyl acetate, etc. Vinyl esters such as vinyl esters of saturated carboxylic acids, ethylene, styrene, vinyl chloride, etc.

Saturated carboxylic acids that can be used in the present invention include formic acid, oxalic acid, acetic acid, and butyric acid.

Aldehyde aniline and α, β without carboxyl group
When the monoethylenically unsaturated monomer is mixed with the saturated monomer and the carboxylic acid, a polymerization reaction is initiated at room temperature, and a polymer containing no carboxyl group is obtained.

Aldehyde aniline and α, β without carboxyl group
The blending ratio of the monoethylenically unsaturated monomer and the saturated monomer/carboxylic acid is 3 parts by weight of aldehyde aniline per 10 parts by weight of the α,β monoethylenically unsaturated monomer that does not have a carboxyl group. As mentioned above, the amount of the saturated carboxylic acid is preferably 5 parts by weight or more, and the amount of the saturated carboxylic acid is 3 to 20 parts by weight.

In this polymerization reaction, the aldehyde aniline is excited by the carboxyl group in the saturated carboxylic acid to generate radicals, and the saturated monoethylenically unsaturated monomer and the α,β monoethylenically unsaturated monomer, which does not have a carboxyl group, are It is believed that the compound copolymerizes with the hydride aniline. This is because if the saturated carboxylic acid is removed from this reaction system, the polymerization reaction will not start. However, there are still some aspects of the theoretical elucidation of the initiation of polymerization reactions that are not necessarily clear.

The polymerization method in the present invention includes block polymerization, solution polymerization,
Well-known methods such as suspension polymerization and emulsion polymerization are used.

Although room temperature is sufficient for the polymerization temperature, the reaction will be faster if the polymerization temperature is raised to a higher temperature.

In emulsion polymerization, anionic, nonionic, cationic, or amphoteric surfactants, polymerizable emulsifiers, or polymeric protective colloids are used as emulsifiers.

A feature of the present invention is that it does not use a peroxide polymerization initiator, so there is no danger, and it is suitable for applications in which paper, wood, cloth, etc. are impregnated and polymerized.

Furthermore, since the obtained polymer does not contain carboxyl groups, it has excellent water resistance and alkali resistance.

Furthermore, the reaction rate can be controlled by changing the amount of aldehyde aniline used.

Next, the present invention will be explained with reference to Examples and Comparative Examples.

Example 1 Methyl methacrylate 859 was added to a beaker with a capacity of 500 d.
and 10 g of butyraldehyde aniline were added and mixed, then 10 g of acetic acid was added and mixed, and the mixture was left at room temperature.

After 3 hours, it became slightly viscous, after 8 hours it became pale yellow and starch syrup-like, and after 1 week it became a transparent brown solid.

The infrared absorption spectrum of this product is shown in FIG.

Example 2 300 d of methanol was placed in a polymerization reaction flask with a capacity of 2 g equipped with a stirrer, a reflux condenser, a thermometer, etc., and then 80 g of butyl acrylate, 20 g of styrene, 100 g of acetaldehyde aniline, and 30 g of oxalic acid were added, and the mixture was heated to room temperature. Stirring was performed with After 4 hours, the content became viscous, and after 7 hours, the degree of clogging was about 3000 centipoise.

Example 3 Butyl acrylate 809, ethyl acrylate 209 and acetaldehyde aniline 5 g in a 500 m beaker
Then, 1 og of vinegar was added, mixed, and left at room temperature.

After 4 hours, it became slightly viscous, after 10 hours it took on a yellow syrup-like appearance, and after 1 week it became a brown transparent solid.

Example 4 Into the same polymerization reaction flask as used in Example 2, 200 g of ion-exchanged water was added, and 10 g of oxyethylene nonylphenol ether (nonionic surfactant) was added thereto.
was added and dissolved.

Next, 50 g of methyl methacrylate and 120 g of vinegar were added, and while stirring at room temperature, butyraldehyde aniline i was added.
oog was added dropwise over 3 hours.

The resulting content is a yellowish white emulsion.
The viscosity was approximately 150 centivoise.

Comparative Example 1 100 g of butyl acrylate and 10 g of acetic acid were placed in a beaker with a capacity of 500 m and placed under the same polymerization conditions as in Example 1, but the polymerization reaction did not proceed.

Comparative example 2 Butyraldehyde aniline 1 in a beaker with a capacity of 500 d
00g and 10g of acetic acid were put therein and placed under the same polymerization conditions as in Example 1, but the polymerization reaction did not proceed.

Comparative Example 3 Butyl acrylate 1009 and butyraldehyde aniline 10 g were placed in a beaker with a capacity of 500 d and placed under the same conditions as in Example 1, but the polymerization reaction did not proceed.

[Brief explanation of the drawing]

FIG. 1 is an infrared absorption spectrum of the copolymer obtained in Example 1.

Claims (1)

[Claims] 1 Aldehyde aniline and α without carboxyl group
, β monoethylenically unsaturated monomer, in the presence of a saturated carboxylic acid and in the absence of a peroxide polymerization initiator. A method for producing a β-monoethylenically unsaturated monomer copolymer.