JPH062788B2 - Glycidyl ether group-containing reactive polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to isopropenylphenylglycidyl ethers useful as coating materials, adhesives, FRP (fiber reinforced resin) resins, resin modifiers, and the like. The present invention relates to a glycidyl ether group-containing reactive polymer composed of a copolymer with an alkyl vinyl ether.

(Prior Art) Poly (isopropenylphenyl glycidyl ether)
Is known as a heat resistant epoxy resin. Current,
Commercially available heat-resistant epoxy resins include glycidyl ether of phenol novolac, and glycidyl ether of o-cresol novolac.
Poly (isopropenylphenyl glycidyl ether)
Has a higher glass transition temperature than these epoxy resins and is expected to be applied to a wide range of applications.

In addition, isopropenyl phenyl glycidyl ether,
Since it is a vinyl polymerization type monomer, unlike a novolak type glycidyl ether, it is possible to obtain a compound having a new property by copolymerizing with another monomer. For example, as described in Examples of JP-A-54-90234,
Copolymerization of isopropenyl phenyl glycidyl ether with monomers such as methyl methacrylate, styrene and acrylonitrile is known.

(Problems to be Solved by the Invention) Isopropenyl phenyl glycidyl ethers and alkyl vinyl ethers do not copolymerize with a radical initiator, and with an ion catalyst, an epoxy group together with an isopropenyl group of isopropenyl phenyl glycidyl ethers. Since it also polymerizes, a copolymer of vinyl polymerization type isopropenyl phenyl glycidyl ethers and alkyl vinyl ethers has not been obtained.

An object of the present invention is to provide a copolymer of isopropenylphenyl glycidyl ethers and alkyl vinyl ethers, which is useful as a coating material, an adhesive, a resin for FRP, a modifier of resin, and the like.

(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, and R ₅ is 1 to 1 carbon atoms. 8 alkyl group or its halogen-substituted or acyloxy-substituted product, and the ratio of x / y is (1 to 99) / (99 to 1). ] And a number average molecular weight of 500 to 50,000 is a reactive polymer compound comprising a group polymer of isopropenylphenyl glycidyl ethers and alkyl vinyl ethers.

Specific examples of the substituents R _{1 to} R ₄ in the general formula (1) include a hydrogen atom, a chlorine atom, a bromine atom, a methyl group, and t.
-Butyl group, phenyl group and the like.

Specific examples of the substituent R ₅ include methyl group, ethyl group, isobutyl group, n-butyl group, 2-ethylhexyl group, 2-chloroethyl group, 2-acetoxyethyl group, 2
A benzoyloxyethyl group and the like.

The number average molecular weight of the compound of the present invention varies depending on the type of monomer used. The optimum number average molecular weight varies depending on the use, but the number average molecular weight is preferably 500 to 50,000. If the number average molecular weight is 500 or less, the viscosity is too low, and if it is 50,000 or more, the viscosity is too high, which is not preferable because it is difficult to handle.

The compound of the present invention has, for example, the general formula (2): (In the formula, R ₁ , R ₂ , R ₃ and R ₄ are the same as those in the general formula (1).) And an isopropenylphenylglycidyl ether represented by the general formula (3) CH ₂ ═CH- By copolymerizing an alkyl vinyl ether represented by OR ₅ (wherein R ₅ is the same as that in the general formula (1)) using hydrogen iodide or a combination system of this and halogen as a catalyst. can get.

Specific examples of the isopropenylphenyl glycidyl ethers represented by the general formula (2) include three types of isopropenylphenyl glycidyl ethers, ortho, meta, and para, 2,6-dimethyl-4-isopropenylphenyl glycidyl ether, 2,6-dibromo-4-isopropenylphenylglycidyl ether, 2-phenyl-4-isopropenylphenylglycidyl ether and the like.

Specific examples of the alkyl vinyl ethers represented by the general formula (3) include methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, n-butyl vinyl ether, 2-ethylhexyl vinyl ether, 2
-Chloroethyl vinyl ether, 2-acetoxyethyl vinyl ether, 2-benzoyloxyethyl vinyl ether and the like.

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. If the amount of halogen is larger than this, 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 about -50 ° C to 30 ° C and is -25 ° C to 0 ° C.
Is preferred.

If the temperature exceeds 30 ° C, the polymerization yield will be low, which is not preferable. Further, even if the temperature is lowered below −50 ° C., the effect is not obtained, which is industrially disadvantageous and not preferable.

The glycidyl group-containing polymer of the present invention can be hardened 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-formamide 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 such as 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 Corp., molecular weight measuring device 117 type). In addition, for the structural analysis of polymers, deuterium-substituted chloroform was used as the solvent.
_{It was performed by C-NMR} spectroscopy (FT-NMR, R-90H manufactured by Hitachi Ltd.).

Examples 1 to 8 Methylene chloride 233.8 obtained by dehydrating vinyl ether and isopropenylphenyl glycidyl ethers shown in Table 1
It was dissolved in g and cooled to -10 ° C, and the corresponding initiator described in Table 1 was added and reacted for 1 hour. 100 g of methanol
Was added to stop the reaction, and 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.
All the obtained resins were soluble in tetrahydrofuran. In addition, the 13 _C-NMR chart of the resin of Example 1 was
Shown in the figure. In the figure, the peaks of the glycidyl group are 68.
At 0,49.2,44.6 (ppm), the peak of the ethoxy group is 63.5,15.
Observed at 0 (ppm).

The composition of the copolymer is 1600 cm in the infrared absorption spectrum.
It was calculated by quantifying the absorption of the aromatic ring of ^-1 . This value is in good agreement with the value calculated from the epoxy equivalent of the copolymer.

(Effect of the Invention) The glycidyl ether-based reactive polymer of the present invention is a copolymer of isopropenylphenyl glycidyl ethers and alkyl vinyl ethers having a wide range of compositions and has an epoxy group in the molecule, The epoxy resin can be used in a wide range of applications, for example, as a film forming material and as a resin modifier.

For example, for those with a large amount of isopropenylphenylglycidyl ethers, the epoxy resin that uses this as a raw material maintains heat resistance, and due to the presence of the alkyl vinyl ethers, the effect of absorbing internal stress during curing is It can be expected as a resin that does not easily crack. Also, for those with a large amount of alkyl vinyl ethers, it becomes a rubber-like substance, and as a rubber with reactive groups,
For example, application as a flexibility-imparting agent can be expected by adding it to a conventional epoxy resin composition.

[Brief description of drawings]

FIG. 1 is a 13 _C-NMR chart of the copolymer of p-isopropenylphenylglycidyl ether and ethyl vinyl ether obtained in Example 1.

Continued Front Page (72) Noriaki Saito Inventor Noriaki Saito 5-1 Sokai-cho, Niihama City, 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, and R ₅ is 1 to 1 carbon atom. 8 alkyl group or its halogen-substituted product or acyloxy-substituted product, and the ratio of x / y is 1 to 99/99 to 1. ] The glycidyl ether group-containing reactive polymer having a number average molecular weight of 500 to 50,000.