JPH062787B2 - Method for producing reactive polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial field of application) The present invention relates to a reactive polymer having an epoxy group, such as a coating material, an adhesive, a resin for FRP (fiber reinforced resin), and a modifier for resin. The present invention relates to a method for producing a copolymer of isopropenylphenyl glycidyl ethers useful in various applications and an unsaturated monomer copolymerizable therewith.

(Prior Art) Conventionally, a method for obtaining a copolymer of isopropenylphenyl glycidyl ether and another unsaturated monomer such as methyl methacrylate, styrene and acrylonitrile is described in, for example, JP-A-54-90234. As described above, only radical copolymerization methods are known.

In the method of obtaining a copolymer by ionic polymerization, since the epoxy group is also polymerized together with the isopropenyl group of isopropenylphenyl glycidyl ether, it is difficult to obtain a vinyl polymerization type copolymer of isopropenylphenyl glycidyl ether by this method. Was being considered.

(Problems to be solved by the invention) In the method of obtaining a copolymer by radical polymerization, isopropenylphenyl glycidyl ether itself is because of the presence of α-methyl group, or because it does not perform radical polymerization by itself,
There is a problem that it is difficult to obtain a copolymer having many isopropenylphenylglycidyl ether moieties.

The present invention, by cationic copolymerization using a specific catalyst,
It is intended to provide a method for obtaining a vinyl-type copolymer having a wide range of composition ratios of isopropenylphenyl glycidyl ether and other unsaturated monomer without polymerizing the epoxy group of this monomer.

(Means for Solving Problems) The present invention provides a compound represented by the general formula (1) (In the formula, R ₁ , R ₂ , R ₃ and R ₄ are each a group selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms and a phenyl group.) Isopropenylphenylglycidyl Reactivity characterized by copolymerizing at least one ether and at least one unsaturated monomer copolymerizable therewith with hydrogen iodide or a combination system of hydrogen and halogen as a catalyst. It is a method for producing a polymer.

Isopropenyl phenyl glycidyl ethers are obtained by the method of reacting isopropenyl phenols and epichlorohydrin.

As this method, for example, as disclosed in JP-A-58-189228, a generally known method for producing a glycidyl ether of a phenol from a monohydric or polyhydric phenol can be applied.

The isopropenyl phenyl glycidyl ethers used in the present invention include three types of isopropenyl phenyl glycidyl ethers, ortho, meta, and para.
2,6-dimethyl-4-isopropenylphenyl glycidyl ether, 2,6-dibromo-4-isopropenylphenyl glycidyl ether, 2-phenyl-4-isopropenylphenyl glycidyl ether and the like can be mentioned.

The other unsaturated monomer copolymerizable with isopropenylphenyl glycidyl ethers is a compound having at least one carbon-carbon double bond which is cationically polymerizable, and examples thereof include α-methylstyrene, methoxystyrene and vinyltoluene. Styrenes; methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, 2-
Chloroethyl vinyl ether, 2-acetoxyethyl vinyl ether, vinyl ethers; conjugated dienes such as butadiene, isoprene and cyclopentadiene; cyclic unsaturated compounds such as indene; and aliphatic olefins such as isobutylene.

The amount of hydrogen iodide used as a catalyst is preferably 0.01 to 10 mol% based on the total number of moles of the monomer. 0.
If it is less than 01 mol%, the polymerization reaction is slow, and if it is more than 10 mol%, the effect is not obtained.

It is also possible to add halogen as a cocatalyst to hydrogen iodide.

The addition of halogen has the effect of improving the polymerization rate and the degree of polymerization.

Types of halogen include iodine, bromine, iodine bromide and iodine chloride, with iodine being most preferred.

The amount of halogen may be either excessive or insufficient with respect to the amount of hydrogen iodide, but it is preferable to use an amount that is equimolar to hydrogen iodide, and a large amount is preferably up to 4 times the molar amount of hydrogen iodide.

As a result, when the amount of halogen is large, side reactions increase, which is not preferable.

At the time of polymerization, a solvent used in ordinary cationic polymerization can be used.

Examples thereof include aromatic hydrocarbons, halogenated hydrocarbons, nitrated hydrocarbons and the like.

Specifically, benzene, toluene, dichloromethane,
1,2-dichloroethane, nitroethane and the like.

The polymerization temperature is preferably -50 ° C to 30 ° C, -25 ° C to 0
C is even more preferred.

When the temperature exceeds 30 ° C., the polymerization yield is low, which is not preferable.

Further, even if the temperature is lowered below -50 ° C, its effect is small and it is industrially disadvantageous, which is not preferable.

The polymer obtained by the method of the present invention can be cured by adding a curing agent like the conventional epoxy resin, and can be used for the same purpose.

As the curing agent, known ones can be used, for example, amine type such as amine and polyamide; acid type such as acid anhydride; aldehyde condensate type such as phenol-, urea- or melamine-formaldehyde resin; boron trifluoride. Examples thereof include Lewis acid type such as complex.

Applications include paints, coating materials such as semiconductor encapsulation materials, adhesives, FRP resins for printed circuit boards, and resin modifiers.

(Examples) Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited thereto. The epoxy equivalent in the present invention is defined as gram equivalent per mol of glycidyl ether group.

The number average molecular weight was measured by a vapor pressure osmotic pressure method (Corona Corporation, molecular weight measuring device 117 type). The presence of the bond formed by ring-opening of the glycidyl group in the copolymer (hereinafter referred to as ring-opening bond) is due to the solubility of 0.2 g of the polymer in 10 ml of tetrahydrofuran and the infrared spectrum of 1110 cm ^-1.
Determined by absorption at. The composition ratio of the constitutional units of the copolymer was calculated from the value of epoxy equivalent.

Examples 1 to 8 In a 500 ml four-necked flask, the two kinds of monomers shown in Table 1 were dissolved in 233.8 g of methylene chloride dehydrated by Molecular Sigs 4A, cooled to -10 ° C, and added to Table 1. The catalyst shown in 1 was added and the temperature was kept for 1 hour. Methanol 5
After the reaction was stopped by adding 0 g, the mixture was washed with 100 g of a 10 wt% sodium thiosulfate aqueous solution and further washed with 100 g of pure water, and then the solvent and residual monomers were removed by distillation.
A polymer was obtained.

All of these polymers were soluble in tetrahydrofuran, and neither glycidyl group nor ring-opening bond was detected by infrared spectrum analysis. In addition, ¹³ C-NMR confirmed that a vinyl polymerization type copolymer was formed.

Comparative Examples 1 and 2 In the same manner as in Examples 1 to 8, polymerization was performed using the monomers and catalysts shown in Table 1. The obtained polymer was insoluble in tetrahydrofuran, and the ring-opening bond of the glycidyl group was detected by infrared spectrum analysis.

Comparative Example 8 The monomers and catalysts shown in Table 1 were placed in a 6 ml ampoule for polymerization, replaced with high-purity N ₂ , then sealed and kept at 80 ° C. for 4 hours. Then, after dissolving in toluene and washing with pure water, the toluene and the residual monomer are removed by distillation,
A polymer was obtained.

This polymer was soluble in tetrahydrofuran, and ring-opening bond of glycidyl group was not detected by infrared spectrum analysis.

(Effects of the Invention) The present invention uses two types of cationically polymerizable functional groups in one molecule such as isopropenylphenyl glycidyl ethers by using a specific catalyst of hydrogen iodide or a combination system of hydrogen iodide and halogen. It is a method of obtaining a vinyl polymerization type copolymer by cationically polymerizing a monomer having a group only with an isopropenyl group.

As shown in Comparative Examples 1 and 2, when a cation catalyst other than the present invention is used, only an insoluble polymer in which both the isopropenyl group and the glycidyl group are ring-opened can be obtained.

Also, with isopropenyl phenyl glycidyl ether,
When copolymers of other unsaturated monomers are produced by radical polymerization, for example, as shown in Comparative Examples 3 to 5, it is difficult to obtain polymers having a high proportion of isopropenylphenylglycidyl ether moieties. In particular, when vinyl ethers having low radical polymerizability are used as the comonomer, the yield is low and it cannot be said to be a good method. In contrast, the method of the present invention gives a polymer in which the glycidyl group remains unreacted. This polymer has a wide range of applications as a special epoxy resin.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Noriaki Saito 5-1 Sokai-cho, Niihama-shi, Ehime Sumitomo Chemical Co., Ltd.

Claims (1)

[Claims] 1. A general formula (1) (In the formula, R ₁ , R ₂ , R ₃ and R ₄ are each a group selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms and a phenyl group.) Isopropenylphenylglycidyl Reactivity characterized by copolymerizing at least one ether with at least one other unsaturated monomer copolymerizable therewith using hydrogen iodide or a combination system of this and halogen as a catalyst. Method for producing polymer.