JPH062784B2 - Method for producing poly (p-isopropenylphenylglycidyl ether) - Google Patents

Description

Detailed Description of the Invention a. TECHNICAL FIELD The present invention relates to a method for producing poly-p-isopropenylphenylglycidyl ether. More specifically, p-
The present invention relates to a method for producing a vinyl polymerization type poly (p-isopropenylphenylglycidyl ether), which comprises polymerizing isopropenylphenylglycidyl ether using a specific catalyst.

B. 2. Description of the Related Art Conventionally, poly (p-isopropenylphenyl glycidyl ether) is conventionally synthesized by polymerizing p-isopropenylphenol using a cation catalyst or the like to synthesize poly (p-isopropenylphenol), and then poly (p-isopropenylphenol). It was manufactured by the method of glycidyl etherification.

However, in this method, as a by-product, polymers having chlorine groups of various structures derived from epichlorohydrin,
Between molecules Bond consisting of (hereinafter referred to as hydroxy ether bond)
And a polymer having an unreacted p-isopropenylphenol moiety are produced.

Synthetic Organic Chemistry, 26 (12), 66 (1968),
A method of radically polymerizing vinyl phenyl glycidyl ether to obtain poly (vinyl phenyl glycidyl ether) is described. However, p-isopropenylphenyl glycidyl ether does not undergo radical polymerization, probably due to the presence of the α-methyl substituent.

Further, in ionic polymerization, a glycidyl group is polymerized together with the isopropenyl group, and thus it is considered difficult to obtain a vinyl polymerization type poly (p-isopropenylphenylglycidyl ether) having an epoxy group by this method. It was

C. Problems to be Solved by the Invention In the method for obtaining poly (p-isopropenylphenylglycidyl ether) by glycidyl etherifying poly (p-isopropenylphenol) with epichlorohydrin,
In addition to the target compound, polymers having chlorine groups of various structures derived from epichlorohydrin, polymers having a hydroxy ether bond by intermolecular reaction, polymers having an unreacted p-isopropenylphenol moiety, etc. To live.

When poly (p-isopropenylphenyl glycidyl ether) containing these by-products is used as an epoxy resin, in particular, in applications involving electronic materials, corrosion due to hydrolyzable chlorine occurs, and such a resin cannot be used. Absent. Further, the presence of a polymer having a hydroxyether bond lowers the crosslink density when the poly (p-isopropenylphenyl glycidyl ether) is cured, and thus lowers the heat resistance of the resin. Further, the presence of a hydroxyl group has an adverse effect such as a decrease in water resistance.

The present invention relates to an advantageous method for producing poly (p-isopropenylphenylglycidyl ether) having fewer components causing these defects and problems.

D. MEANS FOR SOLVING THE PROBLEMS The present invention is characterized by polymerizing p-isopropenylphenylglycidyl ether by using hydrogen iodide or a combination system of hydrogen iodide and iodine as a catalyst. -Isopropenyl phenyl glycidyl ether).

p-isopropenylphenyl glycidyl ether is p
-Obtained by a method of reacting isopropenylphenol with epichlorohydrin.

For this method, for example, as disclosed in JP-A-58-189223, a generally known method for producing a glycidyl ether of a phenol from a monohydric or polyhydric phenol can be applied.

The p-isopropenylphenyl glycidyl ether obtained by these methods can be used as it is. However, when p-isopropenylphenyl glycidyl ether is used as an epoxy resin, it is desirable that there are few coexisting substances.

The content of the coexisting substance can be arbitrarily selected depending on its use.

The p-isopropenylphenylglycidyl ether obtained from p-isopropenylphenol and epichlorohydrin can be purified by well-known and conventional rectification or recrystallization.

By this purification, the oligomer component and the chlorine-containing derivative formed by the reaction of p-isopropenylphenol and epichlorohydrin can be removed to an arbitrary amount.

Especially when used as an epoxy resin for electronic materials, p
It is desirable that the purity of the isopropenylphenyl glycidyl ether is 98.7% by weight or more and the chlorine-containing derivative of p-isopropenylphenyl is 0.3% by weight or less.

The higher the purity of p-isopropenylphenyl glycidyl ether, the higher the heat resistance and water resistance when used as an epoxy resin, and the less the chlorine-containing derivative of p-isopropenylphenyl, the less the amount of hydrolyzable chlorine. .

The amount of hydrogen iodide used as a catalyst is preferably 0.01 to 10 mol% based on p-isopropenylphenylglycidyl ether. If it is less than 0.01 mol%, the polymerization reaction will be slow, and if it is more than 10 mol%, the effect will be relatively small.

It is also possible to add iodine as a co-catalyst to hydrogen iodide.

Addition of iodine has the effect of improving the polymerization rate and the degree of polymerization.

The amount of iodine may be 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 iodine 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 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.

F. EXAMPLES Hereinafter, the present invention will be described with reference to Examples, but the epoxy equivalent in the present invention is defined by gram equivalents per 1 mol of glycidyl ether groups.

Also, the chlorine content is obtained by dissolving poly (p-isopropenylphenyl glycidyl ether) in dioxane, adding an alcohol solution of potassium hydroxide, and removing chloride ions with a silver nitrate solution when the mixture is heated at reflux for 2 hours. It is determined by back titration and defined by the weight percentage of chlorine atoms in the compound.

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 ring-opening bond of the glycidyl group in the polymer was determined by absorption at 1110 cm ^-1 by infrared spectroscopy.

Example 1 (1) Synthesis of crude p-isopropenylphenylglycidyl ether A thermometer, a separating tube, a dropping funnel, and a stirrer were attached 1
P-isopropenylphenol 1.0 in a liter flask.
Mol and epichlorohydrin 7.0 mol to make a homogeneous solution. Keeping the temperature at 80 ℃ and the pressure at 250mmHg, 48 in 6 hours
% NaOH aqueous solution was added continuously. During this time, epichlorohydrin and water were azeotropically liquefied to be liquefied and separated into an organic layer and an aqueous layer by a separation tube, the aqueous layer was removed outside the system, and the organic layer was circulated inside the system. After completion of the reaction, the temperature was kept for 1 hour to evaporate and remove unreacted epichlorohydrin, and the reaction product was dissolved in methyl isobutyl ketone.

Next, the by-produced salt was filtered off, and then methyl isobutyl ketone was evaporated and removed to obtain a solid crystal at room temperature. The epoxy equivalent was 201 and the chlorine content was 830 ppm.

In the analysis by GC-Mass (gas chromatograph-mass spectrometer, JEOL Ltd DX-300) and GPC (gel permeation chromatograph, JASCO TRIROTAR-SR ₂ ), p-isopropenylphenylglycidyl ether was obtained. 80.95% by weight, its oligomer 17% by weight,
The chlorine-containing derivative of p-isopropenylphenyl is 0.42.
% By weight.

(2) Purification of p-isopropenyl phenyl glycidyl ether 100 g of crude p-isopropenyl phenyl glycidyl ether obtained in (1) was separated by a rectification column having 10 theoretical plates and 120 ° C to 122 at 1.8 Torr. Fraction 67 up to ℃
g was obtained. This fraction became white crystals at room temperature. The epoxy equivalent was 190 and the chlorine content was 30 ppm. According to GC analysis, the purity of p-isopropenylphenyl glycidyl ether was 99.95% by weight, and the chlorine-containing derivative of p-isopropenylphenyl was 0.01% by weight.

(3) Synthesis of poly (p-isopropenylphenyl glycidyl ether) 19 g of p-isopropenyl phenyl glycidyl ether obtained in (2) was dissolved in 181 g of toluene dehydrated with Molecular Sieves 4A and cooled to -15 ° C. Then, 0.128 g of hydrogen iodide and 2.5 g of toluene were added, and the mixture was kept warm for 15 minutes. After adding 100 g of methanol to stop the reaction,
After washing with 100 g of a 10 wt% sodium thiosulfate aqueous solution, the solvent and the residual monomer were removed by distillation to obtain 6.0 g of a colorless resin. The epoxy equivalent was 197, the chlorine content was 20 ppm, and the number average molecular weight was 1,000.

This resin was soluble in tetrahydrofuran, and ring-opening bond of glycidyl group was not detected by infrared spectrum analysis. In addition, ¹ H and ¹³ C NMR analysis confirmed that only the isopropenyl group of the monomer had a polymerized structure.

Example 2 0.128 g hydrogen iodide in place of 0.128 g hydrogen iodide,
Polymerization was carried out in the same manner as in (3) of 1 except that 0.254 g of iodine was used. 18.7 g of colorless resin was obtained. The epoxy equivalent was 195, the chlorine content was 30 ppm, and the number average molecular weight was 4,600.

This resin was soluble in tetrahydrofuran and no ring-opening bond of the glycidyl group could be detected.

Comparative Example 1 Boron triboride ethyl ether complex in place of hydrogen iodide
Polymerization was conducted in the same manner as in (3) of Example 1 except that 0.14 g was used. 2.7 g of a pale yellow resin was obtained.

This resin was insoluble in tetrahydrofuran, and the ring-opening bond of the glycidyl group was detected.

Comparative Example 2 The same method as in Example 1- (3) was performed except that 0.15 g of trifluoromethanesulfonic acid was used instead of 0.128 g of hydrogen iodide.

1.5 g of colorless resin was obtained.

This resin was also insoluble in tetrahydrofuran, and the ring-opening bond of the glycidyl group was detected.

Comparative Example 3 When poly (p-isopropenylphenol) (number average molecular weight 1,000) obtained in (3) of Example 1 was glycidyl etherified in the same manner as in (1) of Example 1, a pale yellow color was obtained. A resin was obtained. The epoxy equivalent of this resin was 203 and the chlorine content was 860 ppm.

G. EFFECTS OF THE INVENTION In the present invention, a substance having two kinds of functional groups of an isopropenyl group and a glycidyl group in one molecule such as p-isopropenylphenylglycidyl ether is used as a catalyst for the polymerization of the glycidyl group by using hydrogen iodide as a catalyst. In this method, the polymerization is carried out only with an isopropenyl group.

Conventionally, such vinyl-polymerized poly (p-isopropenylphenylglycidyl ether) was obtained only by the reaction of poly (p-isopropenylphenol) with epichlorohydrin, and from this conventional method, epichlorohydrin was obtained. Even if the resulting chlorinated substance coexists, it is difficult to remove this coexisting substance.

However, in the present invention, p-isopropenylphenylglycidyl ether can be purified by a conventional technique such as rectification or recrystallization, so that poly (p-isopropenylphenylglycidyl ether) having any coexisting substance content can be obtained.

When the content of the coexisting substance is smaller, this polymer is preferably used as a raw material for electronic materials when it is an epoxy resin.

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

Claims (1)

[Claims] 1. A method for producing poly (p-isopropenylphenylglycidyl ether), which comprises polymerizing p-isopropenylphenylglycidyl ether using hydrogen iodide or a combination system of hydrogen iodide and iodine as a catalyst.