JPH03170509A - Production of reactive polymer - Google Patents

Abstract

PURPOSE:To produce a reactive high purity polymer useful for a coating material, adhesive, resin modifier, etc., by polymerizing an epoxidized alpha-methylstyrene deriv. in the presence of a specific catalyst. CONSTITUTION:An epoxidized alpha-methylstyrene deriv. (e.g. p-isopropenylphenyl glycidyl ether) is polymerized in the presence of a catalyst comprising acetic acid or deriv. thereof (e.g. acetic acid, trifluoroacetic acid, or monochloroacetic acid) and a divalent metal halide (e.g. ZnI2 or SnCl2) or in the presence of a catalyst comprising a sulfonate (e.g. a salt of methanesulfonic acid or trifluoromethanesulfonic acid). As being able to be purified by a conventional method such as rectification or recrystallization, the epoxidized alpha-methylstyrene deriv. has a high purity. Moreover, the formation of a halide derived from the catalyst in the polymn. is inhibited, thus giving a high purity polymer of the epoxidized alpha-methylstyrene deriv.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for producing a reactive polymer having an epoxy group. In particular, it relates to a method for producing a polymer of α-methylstyrene derivatives having an epoxy group, which is useful for various uses such as coating materials, adhesives, resins for FRP (fiber reinforced resin), and modifiers for resins. <Prior art> An α-methylstyrene derivative having an epoxy group is produced by first polymerizing an α-methylstyrene derivative having a phenolic hydroxyl group using a cationic catalyst, and then glycidyl etherifying this with shrimp chlorohydrin. It was manufactured in Organic Chemistry, 26 (12), 66 (1968)
describes a method for obtaining poly(vinylphenylglycidyl ether) by radical polymerization of vinylphenylglycidyl ether. However, α-methylstyrene derivatives having epoxy groups do not undergo radical polymerization, probably due to the presence of α-methyl substituents. JP-A-61-293209, JP-A-62-197
Publication No. 405 describes a method for selectively cationically polymerizing only isobrobenyl groups while leaving glycidyl groups in poly(isobropenylphenyl glycidyl ether), which is a type of α-methylstyrene derivative having epoxy groups. A method using hydrogen hydride or hydrogen iodide/iodine, or a halogen as a catalyst is disclosed. <Problems to be Solved by the Invention> In the method of glycidyl etherification of a polymer of α-methylstyrene derivative having a phenolic hydroxyl group with epichlorohydrin, in addition to the target product, various structures derived from shrimp chlorohydrin are Polymer with chlorine group, -OCR between molecules! Cl(OH)-CH! A bond consisting of O (
A polymer having a hydroxy ether bond (hereinafter referred to as a hydroxy ether bond), a polymer having an unreacted hydroxyl group, etc. are produced as by-products.

If these by-products are contained, there are problems when using the resin as an epoxy resin, such as a high amount of hydrolyzable chlorine, low heat resistance due to low crosslinking density, and low water resistance. Also, JP-A-61-293209, JP-A-62-
The method disclosed in Japanese Patent No. 197405 results in a polymer containing a hydrolyzable halogen. The present invention provides an advantageous method for producing an α-methylstyrene derivative having an epoxy group that has less of the force that causes these drawbacks and problems. Means for Solving the Problems> The present invention provides an epoxy group-containing α-methylstyrene derivative in the presence of a catalyst consisting of acetic acid or an acetic acid derivative and a halide of a divalent metal, or in the presence of a sulfone derivative as a catalyst. This is a method for producing reactive polymers that is polymerized in the presence of acids. Typical examples of the α-methylstyrene derivatives having an epoxy group of the present invention include nuclear-substituted or unsubstituted isobrobenylphenyl glycidyl ethers. In the general formula, this is CH3 -C tatami CHI R4 0 CH! CH C
Hx\. / (wherein Rl, Rz, Rs and R4 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).

Isopropenylphenyl glycidyl ethers represented by the general formula include, for example, 0-isobropenylphenyl glycidyl ether, m-isobropenylphenyl glycidyl ether, p-isopropenylphenyl glycidyl ether, 2,6-dimethyl-4- Isopropenylphenyl glycidyl ether, 2,6-dibromo-4-
Examples include isopropenylphenyl glycidyl ether, 2-phenyl-4-isopropenylphenyl glycidyl ether, and the like.

Among them, p-isopropenylphenyl glycidyl ether is the most readily available raw material. These isobrobenyl phenyl glycidyl ethers can be used alone or in combination of two or more. An α-methylstyrene derivative having an epoxy group can be obtained by a method of reacting an α-methylstyrene derivative having a phenolic hydroxyl group with shrimp chlorohydrin.

For this method, a commonly known method for producing glycidyl ether of phenol from monohydric or polyhydric phenol can be used, for example, as disclosed in JP-A-58-189223. The epoxy group-containing α-methylstyrene derivatives obtained by these methods can be used as they are.

However, when used as a raw material for an epoxy resin, it is desirable to have fewer by-products, so it may be further purified by well-known and conventional purification methods for glycidyl ethers, such as rectification or recrystallization.

Through this purification, a certain amount of oligomers and by-product chlorine-containing derivatives can be removed to any desired amount. Especially when used as an epoxy resin for electronic materials, the purity is 98.7% by weight.
The above is desirable, and the content of the chlorine-containing derivative is preferably 0.8% by weight or less. It goes without saying that the higher the purity, the higher the heat resistance and water resistance when used as an epoxy resin, and the lower the chlorine-containing derivative, the lower the amount of hydrolyzable chlorine, which is preferable. During the polymerization of the α-methylstyrene derivative having an epoxy group, other unsaturated monomers may be copolymerized. The unsaturated monomer has at least one cationically polymerizable monomer.
It is a compound with one carbon-carbon double bond, for example,
Styrenes such as α-methylstyrene, methoxystyrene, and vinyltoluene; Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, 2-chloroethyl vinyl ether, and 2-acetoxyethyl vinyl ether; phthadiene, isobrene,
Conjugated dienes such as cyclopentadiene; cyclic unsaturated compounds such as indene; and aliphatic olefins such as isobutylene. One type of catalyst used is a combination system of acetic acid or its derivatives and a divalent metal halide. Acetic acid or its derivatives are cation sources, specifically acetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, isobutyloxyethyl acetate (CHsCH(O
iBu)-0COCHs). Phosphoric acid can also be used as another cation source. As the divalent metal halide, zinc or tin halide is preferred.

Among them, zinc iodide (Znlg), zinc bromide (ZnBr
t) Zinc chloride (ZnClt), stannous chloride (SnCl
At least one type selected from g). The amount of acetic acid or its derivative used is 0.01 mol% to 20 mol% based on the total number of moles of monomers. If it is less than 0.01 mol %, the polymerization reaction will be slow, and if it is more than 20 mol %, it will not be effective, and side reactions will increase, which is not preferable. The amount of divalent metal halide used may be in excess or in excess of the amount of acetic acid or its derivatives, but it is preferable to use an amount that is equivalent to the molar amount of acetic acid or its derivatives, and at most 4 times as much. It is good to have a mole.

If the amount of divalent metal halide is larger than this, side reactions will increase, which is not desirable. Sulfonic acids are used as another catalyst. Specifically, it is at least one selected from methanesulfonic acid, trifluoromethanesulfonic acid, and toluenesulfonic acid. The amount of sulfonic acids used is 0.01 mol% to 20 mol% based on the total number of moles of monomers. 0.01 mol%
If the amount is less, the polymerization reaction will be slow, and if it is more than 20 mol %, there will be no effect, and side reactions will increase, which is not preferable.

During polymerization, solvents commonly used in cationic polymerization can be used. Examples include aromatic hydrocarbons, halogenated hydrocarbons, and nitrated hydrocarbons. Specifically, benzene, toluene, dichloromethane, 1,2-dichloroethane, nitroethane, etc. In particular, when a sulfonic acid is used as a catalyst, one with a dielectric constant of 7 to 40 is desirable. For example, halogenated hydrocarbons and nitrated hydrocarbons such as dichloromethane, 1,2-dichloroethane, and nitroethane.

The polymerization temperature is preferably -100°C to 30°C, and -80°C to
0°C is more preferred.

When the temperature exceeds 30°C, the polymerization yield decreases. Further, even if the temperature is lowered to below -100°C, the effect is small, which is industrially disadvantageous, and is not preferred.

The polymer obtained by the method of the present invention can be cured by adding a curing agent in the same way as conventional epoxy resins, and can be used for the same purposes. As the curing agent, known ones can be used, such as amine types such as amines and polyamides; acid types such as acid anhydrides; polyphenol types such as phenol novolafuku, polyvinylphenol, and polyisopropenylphenol; Examples include Lewis acid types such as boron complexes.

Applications include paints, semiconductor encapsulants, adhesives, FRP resins for printed circuit boards, and resin modifiers. Effects of the Invention> The present invention provides a method for producing a substance having two types of functional groups, an unsaturated double bond group and an epoxy group, in one molecule, such as an α-methylstyrene derivative having an epoxy group, using a specific catalyst. This method suppresses the reaction of epoxy groups and allows polymerization to occur only with unsaturated double bond groups.

Generally, such a vinyl polymerization type polymer of an α-methylstyrene derivative having an epoxy group is produced by reacting a polymer of an α-methylstyrene derivative having a phenolic hydroxyl group with shrimp chlorohydrin. It was difficult to remove coexisting chlorinated substances caused by shrimp chlorohydrin. However, in the present invention, since the α-methylstyrene derivative having an epoxy group can be purified by conventional techniques such as rectification and recrystallization, it is possible to obtain an α-methylstyrene derivative having an epoxy group with a low content of impurities. During polymerization, the formation of halides derived from the catalyst can also be suppressed, and a polymer of α-methylstyrene derivatives having epoxy groups with higher purity can be obtained.

EXAMPLES> The present invention will be described below with reference to Examples, but the present invention is not limited thereto.

In the present invention, the epoxy equivalent means glycidyl ether group 1
Defined in duram equivalents per mole. In addition, the chlorine content refers to the chlorine ions released when a polymer of α-methylstyrene derivative having an epoxy group is dissolved in dioxane, an alcoholic solution of potassium hydroxide is added, and the mixture is heated under reflux for 2 hours. It is determined by back titration in a solution and defined as the weight percentage of chlorine atoms in the compound. The number average molecular weight Mn and weight average molecular weight IMW of the polymer are gel. Permeation. It was determined using a chromatograph (manufactured by Shimadzu Corporation, LC-6A) and MFa using standard boristyrene.

H-NMR spectra were obtained using JEOL F manufactured by JEOL Ltd.
Measured with X-90Q.

The amount of residual iodine was measured by elemental analysis. Reference example + ll Collection of crude p-isopropenyl phenyl glycidyl ether 1 flask equipped with a thermometer, separation tube, dropping funnel, and stirrer}4 flasks were charged with p-isopropenyl phenol (12
．． 134 g (containing 5% oligomer) and 7.0 mol of shrimp chlorohydrin were added to make a homogeneous solution. Maintaining the temperature at 74℃ and the pressure at 2501 Hg, the temperature was 48℃ in 6 hours.
% NaOH aqueous solution was added continuously. During this time, epichlorohydrin and water were azeotropically liquefied and separated into an organic layer and an aqueous layer using a separation tube.The aqueous layer was removed from the system and the IR layer was circulated into the system. After completion of the reaction, the mixture was kept warm for 1 hour, unreacted shrimp chlorohydrin was removed by evaporation, and the reaction product was dissolved in methyl isobutyl ketone.

Next, by-product salts were filtered off, and methyl isobutyl ketone was removed by evaporation to obtain solid crystals at room temperature.

The epoxy equivalent of this product is 201 and the chlorine content is 830.
It was ppm. GC-Mass (gas chromatograph-mass spectrometer, JEOL DX-800) and gel-bar chromatography (JASCO Corporation TRIROTAR-S)
R! ) p-isobrobenylphenyl glycidyl ether 80. 95% by weight of the oligomer, 14.7% by weight of the oligomer, and 0.42% by weight of the chlorine-containing derivative of p-isopropenylphenyl.

(2) Purification of p-isopropenylphenyl glycidyl ether 100 g of crude p-isopropenylphenyl glycidyl ether obtained in (1) was separated in a rectification column with 10 theoretical plates and heated at 1.8 Torr to 120°C. 67g of fractions up to 122°C were obtained.

This fraction became white crystals at room temperature.

The epoxy equivalent of this product is 1901, and the chlorine content is 30p.
It was pm.

According to GC-Mass analysis, the purity of p-isopropenylphenyl glycidyl ether is 99.95 wt%, p
The content of the chlorine-containing derivative of isobropenylphenyl was 0.01% by weight.

Examples 1 and 2 Comparative Examples 1 and 2 The p-isobrobenylphenyl glycidyl ether obtained in Reference Example {2) was used as a raw material and dissolved in purified dichloromethane. The catalysts shown in Table 1 were prepared as dichloromethane solutions.

Into a test tube equipped with dry N, bottom and three-way stopcock, raw materials, catalyst solution and dichloromethane were added to the concentrations shown in Table 1, and polymerization was carried out at -78°C. After the polymerization was completed, the reaction was stopped with a cold ammonia methanol solution, and after washing with a 10% aqueous sodium thiosulfate solution and pure water, the solvent was recovered by vacuum distillation to obtain a polymer.

The obtained polymer was soluble in chloroform.

Furthermore, 'H-NMR confirmed that only isopropenyl groups were polymerized. The yield, average molecular weight, molecular weight distribution, and residual iodine content of the obtained polymer were measured and calculated. The results are shown in Table 1.

Comparative Example 3 Except for using the metal halide shown in Table 1 as the catalyst,
Polymerization was carried out in the same manner as in the example. The obtained polymer is
It was completely intolerant of chloroform. Examples 3 to 8 The p-isopropenylphenyl glycidyl ether obtained in Reference Example {2) was used as a raw material and dissolved in purified dichloromethane. The catalysts shown in Table 2 were prepared as dichloromethane solutions.

The raw materials, catalyst solution, and dichloromethane were placed in a test tube equipped with a three-way stopcock under a dry tube to give the concentrations shown in Table 2, and polymerization was carried out at -78°C. After the polymerization was completed, the reaction was stopped with a cold ammonia methanol solution, and after washing with a 10% aqueous sodium thiosulfate solution and pure water, the solvent was recovered by vacuum distillation to obtain a polymer.

The obtained polymer was soluble in chloroform. Further, 'H-NMR confirmed that only isobrobenyl groups were polymerized.

The yield, average molecular weight, molecular weight distribution, and residual iodine content of the obtained polymer were measured and calculated.

The results are shown in Table 2.

Claims (7)

[Claims] (1) A method for producing a reactive polymer, which comprises polymerizing an α-methylstyrene derivative having an epoxy group in the presence of a catalyst consisting of acetic acid or its derivative and a halide of a divalent metal. (2) A method for producing a reactive polymer, which comprises polymerizing an α-methylstyrene derivative having an epoxy group in the presence of a sulfonic acid as a catalyst. (3) The production method according to claim (1) or (2), wherein the α-methylstyrene derivative having an epoxy group is a nuclear-substituted or unsubstituted isopropenylphenyl glycidyl ether. (4) The method of claim (3), wherein the nuclear-substituted or unsubstituted isopropenylphenyl glycidyl ether is p-isopropenylphenyl glycidyl ether. (5) The method of claim (1), wherein acetic acid or a derivative thereof is at least one selected from acetic acid, trifluoroacetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, and isobutyloxyethyl acetate. (6) The method of claim (1), wherein the divalent metal halide is at least one selected from zinc iodide, zinc bromide, zinc chloride, and stannous chloride. (7) The method of claim (2), wherein the sulfonic acid is at least one selected from methanesulfonic acid, trifluoromethanesulfonic acid, and toluenesulfonic acid.