JPS62195002A - Production of curable resin - Google Patents

Abstract

PURPOSE:To obtain the titled beautiful resin which causes no gelatinization in production process and has high transparency, by subjecting a partial esterified copolymer of an unsaturated acid anhydride and a vinyl compound to specific treatment and reacting the treated partially esterified copolymer with an unsaturated epoxy compound. CONSTITUTION:Firstly, an alpha, beta-unsaturated acid anhydride is copolymerized with a vinyl compound (preferably styrene) copolymerizable with it and the copolymer is esterified with >=3C monohydric alcohol such as propyl alcohol, etc., preferably at 40-100 deg.C. An unreacted acid anhydride group of the partially esterified polymer is esterified with an aliphatic monohydric alcohol such as methyl alcohol, etc., and a free carboxyl group of the polymer is reacted with an unsaturated epoxy compound such as glycidyl methacrylate, etc., preferably at 40-90 deg.C for 3-20hr to give the aimed resin.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a method for producing a curable resin, and more specifically, the present invention relates to a method for producing a curable resin, and more specifically, the main chain is composed of a polymer obtained by polymerizing vinyl heptamer, and the side chain contains carbon atoms. -Regarding a method for producing a curable resin in which carbon double bonds are corrected.

[Conventional technology]

Curable resins with carbon-carbon double bonds in their side chains have superior physical properties compared to curable resins such as unsaturated polyester resins, which have carbon-carbon double bonds and ester bonds in their main chains. Because of its excellent performance, its applications are expanding in various fields.

The above-mentioned curable resin having a carbon-carbon double bond in the side chain is generally produced by reacting a compound having a carbon-carbon double bond with the main chain.

For example, the acid anhydride group of a copolymer obtained by polymerizing an α,β-unsaturated acid anhydride and a vinyl compound that can be copolymerized with the same is combined with allyl alcohol, 2-hydroxyethyl methacrylate, etc.
After esterification with 1-,2-hydroxyedyl acrylate-1, unsaturated alkyl, free 1 tl
A resin having a carbon-carbon double bond in the side chain can be produced by reacting the carboxyl group of lt with an unsaturated epoxy compound such as allyl glycidyl ether, glycidyl methacrylate, or glycidyl acrylate.

[Problem that the invention seeks to solve]

However, in the above method, in the step of reacting a free carboxyl group with an unsaturated epoxy compound, when the reaction rate of the epoxy compound becomes high, gelation of the resin occurs and an unmoldable lump is formed. Furthermore, if the reaction rate of the unsaturated epoxy compound is suppressed in order to prevent gelation of the resin, the reaction rate of free carboxyl groups will not increase sufficiently, making it impossible to obtain a resin with good performance.

In view of the above circumstances, the present inventors conducted extensive research on a method that does not cause gelation even if the reaction rate of the unsaturated epoxy compound is increased, and as a result, they found that the acid anhydride group remaining in the main chain is the cause of gelation. I discovered that it is.

The present invention was made based on the above discovery, and it is possible to produce a curable resin having a vinyl polymer main chain and a carbon-carbon double bond in the side chain without gelation. The purpose of this research is to provide a method for producing curable resins.

[Means for solving problems]

The present invention has been made to achieve the above objects,
The gist is that the acid anhydride group of a copolymer consisting of α, β-unsaturated unsaturated anhydride and a copolymerizable vinyl compound is partially esterified with a saturated or unsaturated monohydric alcohol having 3 or more carbon atoms. In the method for producing a curable resin in which the free carboxyl groups of the polymer obtained by esterification are reacted with an unsaturated epoxy compound, before the free carboxyl groups of the partially esterified polymer are reacted with the unsaturated epoxy compound, the above-mentioned Partially esterified polymer with 1 or 2 carbon atoms
A method for producing a curable resin, which comprises esterifying the resin with an aliphatic monohydric alcohol.

[Specific structure and operation of the invention]

Hereinafter, the present invention will be explained in detail.

In the present invention, the α,β-
, As the β-acid anhydride, for example, maleic anhydride,
-laconic anhydride, 2-edylmaleic anhydride, anhydride 2
-, phenylmaleic acid.

Examples include 2-chloromaleic anhydride.

In addition, as for the vinyl compound to be copolymerized with α, β-unsaturated acid anhydride, any one can be used as long as it can be copolymerized with α, β-, β-acid anhydride, and two or more types can be used in combination. Good too. Typical examples of vinyl compounds include styrene, α-methylstyrene, acrylic esters, methacrylic esters, vinyl acetate, acrylonitrile, vinyl chloride, etc. Among these, styrene is particularly preferred.

The ratio of the above α, β-, β-acid anhydride and vinyl compound during copolymerization can be changed as appropriate depending on the desired performance of the resin.

A copolymer of α, β-, β-acid anhydride and a vinyl compound can be produced by a conventionally known method. In order to facilitate the reaction, it is preferable to add an α, β-, β-acid anhydride to the vinyl compound and cause the reaction to occur.

Examples of the saturated or unsaturated monohydric alcohol having 3 or more carbon atoms to be reacted with the acid anhydride group of the copolymer of α, β-, β-acid anhydride and vinyl compound include propyl alcohol and butyl alcohol.

Hexyl alcohol, octyl alcohol, 2゜3-dichloro-1-propatol, 2,3-dibromo-1-propatol, allyl alcohol, 2-hydroxyethyl meccrylate, 2-hydroxyethyl acrylate,
Examples include benzyl alcohol.

The reaction between the acid anhydride group of the copolymer and the saturated or unsaturated monohydric alkonyl having 3 or more carbon atoms is performed by adding a saturated or unsaturated monohydric alcohol having 3 or more carbon atoms to the solution of the copolymer, and optionally a catalyst. is added, heated, and stirred. The solvent is not particularly limited as long as it dissolves the copolymer, and the concentration of the copolymer in the solution is such that the resin concentration of the final reaction solution is 10 to 10.
The content is appropriately selected to be about 90% by weight. The amount of the saturated or unsaturated monohydric alcohol having 3 or more carbon atoms to be reacted with the acid anhydride group of the copolymer -〇- can be appropriately selected depending on the performance of the resin, but in general, the amount of saturated or unsaturated monohydric alcohol having 3 or more carbon atoms is used. The amount of the saturated or unsaturated alcohol used is usually within the range of 0.1 to 1 mole per mole of acid anhydride group of the copolymer. As the catalyst used as necessary, a conventionally known esterification catalyst is used. Heating to room temperature 1
30°C, preferably within the range of 40 to 100°C, and the reaction time is determined by reaction starvation and the reactivity of the saturated or unsaturated monohydric alcohol having 3 or more carbon atoms, but is generally 1 to 20 hours. The esterified borine thus obtained is suitable for 8 of the acid anhydride groups of the copolymer.
An amount of less than 0% is partially esterified. This partially esterified polymer is then reacted with an aliphatic monohydric alcohol having 1 or 2 carbon atoms.

In a polymer in which 80% or more of the acid anhydride groups in the copolymer are esterified, gelation hardly occurs in the reaction with an unsaturated epoxy compound even if the reaction rate of the unsaturated epoxy compound increases. Therefore, there is no need to react an unreacted acid anhydride group with an aliphatic monohydric alcohol having 1 or 2 carbon atoms. However, when esterifying 80% or more of the acid anhydride groups in the copolymer, a large excess of saturated or unsaturated monohydric alcohol having 3 or more carbon atoms must be used, resulting in This results in an increase in cost and a decrease in the physical properties of the polymer due to the presence of alcohol in the reaction.

The unreacted acid anhydride group and the aliphatic monohydric alcohol having 1 or 2 carbon atoms include methyl alcohol, edyl alcohol, and the like. When a monohydric alcohol having a carbon number of more than 2 is used, its reactivity with acid anhydride groups is poor, so that the effect of esterifying unreacted acid anhydride groups is small.

The amount of aliphatic monohydric alcohol having 1 or 2 carbon atoms to be used is
Usually, the amount is preferably within the range of 0.1 to 1 mol per mol of acid anhydride group.

The reaction between the unreacted acid anhydride group and the aliphatic monohydric alcohol having 1 or 2 carbon atoms is carried out under the reaction conditions of the acid anhydride group of the copolymer and the saturated or unsaturated monohydric alcohol having 3 or more carbon atoms. It is done in the same way as Tobabo.

In the polymer thus obtained, 80% or more of the acid anhydride groups are esterified.

Furthermore, examples of unsaturated epoxy compounds that can be reacted with free carboxyl groups produced by the reaction of acid anhydride groups and alcohol include glycidyl methacrylate-1, glycidyl acrylate, and allyl glycidyl ether.

The amount of the unsaturated epoxy compound to be reacted with the carboxyl group produced by J and M in the reaction of the acid anhydride group and alcohol is determined by the amount of acid anhydride group 1 in the copolymer after the copolymerization reaction.
The amount may be 0.2 to 0.8 mol based on the mole, but it can be appropriately selected depending on the performance of the resin.

The reaction between a free carboxyl group and an unsaturated epoxy compound may be carried out under normal pressure, increased pressure, or reduced pressure. The reaction temperature is in the range of 20-120°C, preferably 4.0-90°C. Moreover, the reaction time is within the range of 1 to 30 hours, preferably 3 to 20 hours. At this time, in order to accelerate the reaction, quaternary ammonium salts, tertiary amines, zinc and lead carboxylates, organotin compounds such as di-n-butyltin carboxylate, p-toluenesulfonic acid, etc. are used as catalysts. may also be used.

An example of the above reaction can be expressed as a reaction formula as follows.

However, (a) vinyl compound: styrene (b) α,β-unsaturated acid anhydride: maleic anhydride (C
) ItOH, saturated or unsaturated monohydric alcohol having 3 or more carbon atoms (d) R'OH: aliphatic monohydric alcohol having 1 or 2 carbon atoms (e) unsaturated epoxy compound nigericidyl methacrylate (al (bl
(fl(cl
fQlCH2-CH-CH2-○-C-C-
CH2(e) [Example] Next, the present invention will be described with reference to Examples.

Example 1 Stirrer, temperature control 1. 1 reversible refras with reflux cold JJI vessel = 1, l-/re 1 nin: 2
E50 Q, Sudrene: After adding 187 G and 4 g of benzoyl peroxide, heat at 85°C under nitrogen atmosphere.
85% of a mixture of 170 g of maleic anhydride and toluene was added dropwise over 2 hours. Next, 4 g of benzoyl peroxide was further added, and the remaining mixture of maleic anhydride and toluene was added dropwise at 85° C. over 3 hours under a nitrogen atmosphere. After the dropwise addition was completed, the temperature was maintained at 110°C and the reaction was carried out for 2.5 hours. The liquid after this reaction is referred to as a resin solution (A).

This resin solution (A): 650q and allyl alcohol 12
．． 4q, triethylamine: 1.3Q and p-methoxyphenol: 0.2a were added, and under nitrogen atmosphere, 80
The reaction was carried out at ℃ for 15 hours. After the reaction was completed, the reaction rate of the acid anhydride group was approximately 50%. The liquid after this reaction is referred to as a resin solution (B).

This resin solution (B): 664g and methyl alcohol: 1
1.6Q was added, and the mixture was reacted at 80° C. for 6 hours under a nitrogen atmosphere. As a result, the reaction rate of acid anhydride groups was approximately 90%. Next, 45 g of allyl glycidyl ether was added and reacted at 80° C. for 15 hours to obtain a pale yellow, transparent, uniform resin solution (C). The viscosity of the resin solution (C) was about 30 voices at 20°C.

This resin solution (C): 100q and dicumyl peroxide: 1. After OQ was added and dissolved, decorative paper was impregnated with it and dried at 80°C for 10 minutes.

This dried impregnated paper was heated to 90°C at a temperature of 150°C and a pressure of 20°C.
/ cm for 1 hour, a cured decorative board with excellent hardness, chemical resistance, etc. was obtained.

Comparative Example 1 When 45 g of allyl glycidyl ether was added to 664 g of the resin solution (B) of Example 1 and reacted at 80°C for 15 hours, gelation occurred and a geladine-like mass was formed. Impregnating and hardening molding was not possible.

Example 2 In a 1J separable flask equipped with a stirrer, a thermometer, and a reflux condenser, acetone: 3200, styrene-maleic anhydride copolymer (Arco Chemica 1-1/
After preparing 300 CJ (manufactured by SHA 1000A) and making a homogeneous solution, 259 g of 2,3-dibromo-1-propatool and 5.3 g of L-liedylamine were added, and the mixture was reacted with 60'Cr for 9 hours under a nitrogen atmosphere. Saυ−ta. In this case, the reaction rate of the acid anhydride group was about 50%.

The solution obtained by this reaction is referred to as a resin solution (D>).

Methyl alcohol: 9 to this resin solution (D): 884 g
．． Add 50% sapota and react at 60°C for 9 hours. As a result, the reaction rate of acid anhydride groups was approximately 82%. Then p
-Methoxyphenol 2,7q and glycidyl methacrylate: 169g were added and reacted at 60°C for 18 hours.

This reaction solution was depressurized to about 75 mHU, and aletone: 15
After removing 0g by distillation, add sutyrene: 7/130,
Depressurize to about 25mHIJ and further aI? l- about 170
9 was removed by distillation.

The resin obtained in this way was a pale yellow transparent highly viscous solution, and the viscosity at 20° C. was about 160 poise. This solution was referred to as resin solution (E).

This resin solution (E): 1 cobal naphthenate per 10 C) g
~: 0.09g, antimony dioxide: 1,4q, t-butyl peroxybenzoate = 1. OQ, and 55% dimethyl phthalate solution of methyl ethyl ketone peroxide: 1. After adding Og and stirring well, the mixture was poured between two stainless steel flat plates covered with a polyester film. This was heated to 80°C for 2 hours, then to 150°C.
After curing for 1 hour at 120°C for 10 hours,
When after-curing was performed, a pale yellow transparent cured product was obtained.

Comparative Example 2 Resin solution (D) of Example 2: 884q and p-me[-xifinol:Q, 7Q, glycidyl methacrylate:
When 169o was added and reacted at 60°C for 18 hours,
Gelation started, and hardening and molding as in Example 2 could not be performed.

Comparative Example 3 A resin solution (C') corresponding to the resin solution (C) was prepared in exactly the same manner as in Example 1 except that butyl alcohol: 10.6Q was added to the resin solution (B): 664o.
Gelation occurred during the reaction with glycidyl ether.

Example 3 Resin solution (A) of Example 1: 650 g, 2-hydroxyethyl methacrylate: 27.8 g, triethylamine: 1.30 and p-methoxyphenol: 0.2
0 was added thereto, and the mixture was reacted at 60° C. for 5 hours under a nitrogen atmosphere. After the reaction is completed, the reaction rate of the acid anhydride group is approximately 40%.
Met. This reaction-completed liquid is referred to as a resin solution (F).

Methyl alcohol: 4 to this resin solution (F): 679q
．． 6() was added and the reaction was allowed to proceed for 3 hours at 60°C under a nitrogen atmosphere, and the reaction rate of the acid anhydride group was 80%.Next, 32.6q of allyl glycidyl ether was added and the reaction was carried out at 80°C. After 4 hours of reaction, a pale yellow, transparent, uniform resin solution (G) was obtained.The viscosity of the resin solution (G) was about 25 voids at 20°C.

Add dicumyl peroxide to this resin solution (G) + 100<h: 1. After adding and dissolving oo, decorative paper was impregnated with it and dried at 80° C. for 10 minutes.

This dried impregnated paper was heated at a temperature of 150°C and a pressure of 20K.
By pressing at g/air for 1 hour, a cured decorative board with excellent hardness, chemical resistance, etc. was obtained.

Comparative Example 4 When allyl glycidyl ether +32.60 was added to the resin solution (F): 679q of Example 3 and reacted at 80°C for 4 hours, gelation was observed, and impregnation was performed as in Example 3. Hardening molding was not possible.

Example 4 A 1J separable flask equipped with a stirrer, a thermometer, and a reflux condenser was charged with 300 g of acetone (320<y) and styrene-maleic anhydride copolymer (manufactured by Arco Chemica 1, 5) IA 100QA). After making a homogeneous solution, n-butyl alcohol: 66Q
, triethylamine: 5.3q was added, under nitrogen atmosphere,
The reaction was carried out at 60°C for 9 hours. In this case, the reaction rate of the acid anhydride group was about 45%. The solution obtained by this reaction is referred to as a resin solution (11).

This resin solution (H): 691g and ethyl alcohol = 2
7 g was added, and the reaction was stirred at 60°C for 5 hours. That connection,
The reaction rate of the acid anhydride group was approximately 81%. Next, 0.7 q of p-methoxyphenol and 169 <2 glycidyl methacrylate were added, and the reaction was allowed to proceed at 60°C for 10 hours.

This reaction solution was depressurized to about 75 mmHH, and acetone:1
After removing 50q by distillation, 568C1 was added, the pressure was reduced to about 25mmHCl, and about 17ml of azetone was added.
00 was removed by distillation.

The resin thus obtained was a pale yellow, transparent, highly viscous solution with a viscosity of about 100 poise at 20°C. This solution will be referred to as resin solution (1).

This resin solution <1): 100g of cobalt nanothenate +
Q, 10Xt-butylperoxybenzo-1~:1.
0 g, and 55% of medylethyl ketone peroxide
After adding dimedyl phthalate solution = 1 and Oc+ and stirring well, it was poured between two stainless steel decks covered with a polyester film. Heat this to 80℃ 2
After curing for 1 hour and then holding at 150°C for 1 hour,
After curing for 10 hours at 120℃,
A pale yellow transparent cured product was obtained.

Comparative Example 5 When p-methoxyphenol: 0.7Q and glycidyl methacrylate: 169CI were added to the resin solution ()-1): 691o of Example 4 and reacted at 60°C for 10 hours, gelation started and implementation was carried out. It was not possible to perform hardening molding as in Example 4.

〔effect〕

As described above, the method for producing a curable resin according to the present invention is an excellent method that does not cause any gelation during the production process and can produce a highly transparent and beautiful curable resin.

Claims (1)

[Claims] Obtained by partially esterifying the acid anhydride group of a copolymer consisting of an α,β-unsaturated acid anhydride and a vinyl compound copolymerizable therewith with a saturated or unsaturated monohydric alcohol having 3 or more carbon atoms. In the method for producing a curable resin in which free carboxyl groups of a polymer are reacted with an unsaturated epoxy compound, before reacting free carboxyl groups of the partially esterified polymer with the unsaturated epoxy compound, the partially esterified polymer is A method for producing a curable resin, which comprises esterifying with an aliphatic monohydric alcohol having 1 or 2 carbon atoms.