JPS58109511A - Production of polymer containing glycidyl acrylate or glycidyl methacrylate - Google Patents

Abstract

PURPOSE:To obtain the polymer without causing gelation and side reactions, by dissolving a radical polymerization initiator in a monomer consisting predominantly of a glycidyl (meth)acrylate and adding this solution to a solvent maintained at a specified temperature or higher. CONSTITUTION:About 1-5wt% radical polymerization initiator (e.g., azobisisobutyronitrile, benzoyl peroxide) is added to a glycidyl (meth)acrylate or a mixture containing one or more of these monomers and at least one difficultly polymerizable vinyl monomer (e.g., ethyl acrylate, styrene). The purpose polymer containing glycidyl (meth)acrylate is obtained by polymerizing the above- produced solution by adding it to a solvent (e.g., ethanol, acetone) maintained at a temperature which is about 10-50 deg.C above the temperature at which the polymerization initiator has a half life of 10hr.

Description

[Detailed Description of the Invention] Abbreviated as [Detailed Description of the Invention]. ).

When performing solution polymerization in the single 11-polymerization of glycidyl (meth)acrylate or in the copolymerization with other polymerizable hynyl monomers, popcorn polymers are often formed after the middle stage of the reaction, or the entire reaction system becomes gelled. happen.

In order to improve this point, Japanese Patent Publication No. 48-8594 discloses a method in which t-butyl peroxyhybarate or diisopropyl peroxydi(9) carbonate is used as a polymerization initiator and the reaction is carried out at 20 to 55°C. However, even in this case, the entire reaction system may sometimes gel.

In the method described in JP-A-54-155295, an organic peroxide having a decomposition temperature of 60°C or lower is used as a polymerization initiator to obtain a half-life of 10 hours, and
'React at a high temperature of 0 to 50°C, and 2IP!' the organic peroxide! The above-mentioned drawbacks have been improved by dividing the initiator into one or more parts and adding them to the reaction system, but since a highly active initiator is used, handling is cumbersome, and the method itself is complicated, such as adding in parts. It was also found that copolymerization of glycidyl (meth)acrylate with a monomer having a functional group such as a hydroxyl group causes gelation, and that this method also has its limitations.

Regarding the copolymerization of glycidyl (meth)acrylate and a vinyl monomer having a blue water property of 1, JP-A-52-9
As described in the Examples of No. 2290', when this method was repeated, gelation still occurred when trying to reduce the polymerization rate.

In order to overcome these drawbacks of the prior art, the present inventors conducted extensive research and developed a method for producing glycidyl (meth)acrylate homopolymers or copolymers with other vinyl monomers by gelling or submerging them. A method for obtaining this without involving any reaction was discovered, leading to the present invention.

That is, the present invention provides glycidyl (meth)acrylate, or one or two of these and one or two of other polymerizable vinyl monomers.
A radical 1 initiator is added and dissolved in the mixture with more than one species,
A method for producing a polymer containing glycidyl (meth)acrylate, characterized in that this mixed solution is added to a solvent maintained at a temperature higher than the temperature at which the polymerization initiator obtains a half-life of 10 hours. be.

In the present invention, even if a compound having a functional group such as a hydroxyl group that can react with an epoxy group is used as another vinyl monomer or solvent, a polymer can be obtained without gelation or side reactions, and the copolymer can be used as a solvent. In the case of polymerization, a distinctive feature not seen in the prior art is that it can be applied at any composition ratio.

Polymerizable vinyl monomers that can be copolymerized include methyl acrylate and methyl methacrylate (acrylic acid and methacrylic acid derivatives are hereinafter referred to as (meth)acrylic acid derivatives), and alkyl (meth)acrylates such as ethyl (meth)acrylate. , hydroxyethyl (meth)acrylic l/-)-, hydroxypropyl (meth)acrylate, diethylene glycol mono(meth)
Examples include hydroxyl group-containing (meth)acrylates such as f-acrylate, styrene, (meth)acrylonitrile, and vinyl acetate.

Solvents used in the present invention include alcohols such as methanol, ethanol, and isopropanol; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ethers such as acetic acid esters, diethyl carbitol, and diethyl cellosolve; Examples include ether alcohols such as methyl cellosolve, ethyl cellosolve, and carpitol, and ester ethers such as cellosolve acetate and carpitol acetate, and a hydrocarbon solvent may be used in combination if necessary.

The polymerization initiator may be any one known as a radical polymerization initiator, such as azobisisobutyronitrile, benzoyl peroxide, lauroyl peroxide, tert-butyl peroxyvivalate, methyl ethyl ketone. Peroxide, dicumyl peroxide - dicumyl peroxide, tertiary
Examples include butyl hydroperoxide.

The amount of the initiator added needs to be changed depending on the reaction temperature, the desired molecular weight of the polymer, etc., but the preferable amount is 1 to 5 weight i based on the total amount of monomers.

The reaction temperature is closely related to the polymerization initiator used, and the temperature at which the polymerization initiator obtains a half-life of 10 hours (hereinafter referred to as T
(abbreviated as 1/2℃), T1
It is an essential requirement of the present invention that the mixture of monomer and initiator be added to a solvent maintained at a temperature of /2° C. or above. Conversely, there are methods in which an initiator or an initiator diluted with a solvent is added to a monomer or a mixture of monomer and solvent maintained at a temperature above T-℃, or in which all components are reacted from the beginning. , side reactions such as kelization and ring opening of epoxy groups occur, and the desired polymer cannot be obtained.The preferred reaction temperature is ('l"l, /2 +10) 'C~('
l'l/2 +50) 'C.

According to the method of the present invention, no gelation or side reactions occur during the reaction, and a polymer with a polymerization rate of 95% or more can be easily obtained.

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

Example 1 Ill equipped with a stirring bar, thermometer, nitrogen inlet tube, dropping funnel, and reflux condenser! Ethyl cellosolve 66 in a four-loaf flask
0? was charged and the system was purged with nitrogen. Thereafter, the temperature was raised to 90°C, and to this was added 12Of glycidyl methacrylate.

Hydroxyethyl methacrylate 1201, azobisisobutyronitrile 7.2 F (weight of monomer 8 96
) were mixed and dissolved in advance and added dropwise over 1 hour.

After dropping, the solution was kept at the same temperature for 2 hours to obtain a copolymer solution of glycidyl methacrylate and hydroxyethyl methacrylate. The epoxy equivalent of the obtained 1 mixture was 966, which was almost in agreement with the theoretical value of 956. Moreover, the number average molecular weight of the copolymer was 7,000, and the polymerization rate was 9,596.

Comparative Example 1 In Example 1, glycidyl methacrylate and hydroxyethyl methacrylate were charged in advance in a flask, heated to 90°C, and asobisisobutyronitrile 7.2% was added to the flask. If you use the method of dropping 1 drop of dissolved Cellosolve in ethyl cellosolve 560y, side reactions will occur. , some of the epoxy groups in the resulting polymer were ring-opened. Furthermore, when the reaction was carried out at 60°C using this method, the entire reaction system was gelatinized.

Example 2 Methyl cellosolve 4201 was charged into the same apparatus as in Example 1, and the yarn was replaced with nitrogen. After that, the temperature was raised to 100°C, and to this, glycidyl methacrylate 162f, hydroxyethyl methacrylate 181, and benzoyl peroxide 8.2P were added. (8% by weight of the monomer) was mixed and dissolved in advance and added dropwise over a period of 2 hours, and after the dropwise addition it was kept warm at the same temperature Ik for 2 hours. The epoxy equivalent of the obtained polymerization solution was 640, which was almost the same as the theoretical value of 580. Moreover, the number average molecular weight of the copolymer was 5000, and the polymerization rate was 97%.

Comparative Example 2 When the reaction was carried out in the same manner as in Example 2 except that the reaction temperature was 50°C, a side reaction occurred and some of the epoxy groups of the produced polymer were ring-opened.

Claims (1)

[Claims] l) Adding and dissolving a radical polymerization initiator to glycidyl acrylate or glycidyl methacrylate, or a mixture of one or two of these and one or more other polymerizable vinyl monomers, Glyci, characterized in that this mixed solution is added to a solvent maintained at a temperature higher than the temperature at which the polymerization initiator obtains a half-life of 10 hours,
A method for producing a polymer containing dilacrylate or glycidylmethacrylate. 2) Other polymerizable vinyl monomers include acrylic acid alkyl esters, methacrylic acid gamma alkyl esters, hydroxyl group-containing acrylates, hydroxyl group-containing methacrylates, styrene, acrylonitrile (1), methacrylonitrile, and vinyl acetate. The manufacturing method described in paragraph 1. 8) Claim 1, characterized in that the solvent is mainly composed of a compound having one or more than 2a functional groups selected from hydroxyl group, ketone group, ether group, and ester group.
2. The manufacturing method according to item 2 or item 2.