JPH062785B2 - Process for producing poly (isopropenylphenylglycidyl ether) s - Google Patents

Description

Detailed Description of the Invention a. TECHNICAL FIELD The present invention relates to a method for producing poly (isopropenylphenylglycidyl ether) s useful as a coating material, an adhesive, a resin for FRP (fiber reinforced resin), a modifier of resin, and the like. More specifically, the present invention relates to a method for producing vinyl polymerization type poly (isopropenylphenylglycidyl ethers), which comprises polymerizing isopropenylphenylglycidyl ethers using a specific catalyst.

B. Conventional technology Conventionally, poly (isopropenyl phenyl glycidyl ether) s are first synthesized by polymerizing isopropenyl phenols by using a cation catalyst or the like to synthesize poly (isopropenyl phenols), which are then glycidyl etherified with epichlorohydrin. Was manufactured by the method.

However, in this method, as a by-product, a complex having a chlorine group of various structures derived from epichlorohydrin,
Between molecules Bond consisting of (hereinafter referred to as hydroxy ether bond)
And a polymer having an unreacted 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, isopropenyl phenyl glycidyl ethers do not undergo radical polymerization, probably due to the presence of the α-methyl substituent.

Further, in the conventional 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 (isopropenylphenylglycidyl ether) having an epoxy group by this method. Was there.

C. Problems to be Solved by the Invention In a method for obtaining poly (isopropenylphenylglycidyl ether) s by converting glycidyl ethers of poly (isopropenylphenols) with epichlorohydrin to obtain poly (isopropenylphenylglycidyl ethers), chlorine having various structures derived from epichlorohydrin can be obtained. A polymer having a group, a polymer having a hydroxy ether bond by an intermolecular reaction, a polymer having an unreacted isopropenylphenol moiety and the like are by-produced.

When poly (isopropenyl phenyl glycidyl ether) containing these by-products is used as an epoxy resin, the corrosion of hydrolyzable chlorine occurs in applications involving electronic materials, and such resins cannot be used. .
Further, the presence of a polymer having a hydroxyether bond lowers the crosslink density when the poly (isopropenylphenyl glycidyl ether) s are cured, which causes the heat resistance of the resin to lower. 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 (isopropenylphenyl glycidyl ether) s having fewer components that cause these drawbacks and problems.

D. Means for Solving the Problems The present invention provides a general formula (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.) Poly (characterized in that a monomer comprising isopropenyl phenyl glycidyl ethers (excluding p-isopropenyl phenyl glycidyl ether alone) is polymerized by using hydrogen iodide or a combination system of hydrogen iodide and halogen as a catalyst. Isopropenyl phenyl glycidyl ethers). When p-isopropenylphenyl glycidyl ether is used alone as a monomer, a patent application has already been filed (Japanese Patent Application No. 60-117190).

Examples of the isopropenylphenylglycidyl ethers represented by the above general formula used in the present invention include o-isopropenylphenylglycidyl ether, m
-Isopropenyl phenyl glycidyl ether, p-isopropenyl phenyl glycidyl ether, 2,6-dimethyl-4-isopropenyl phenyl glycidyl ether, 2,6-dibromo-4-isopropenyl phenyl glycidyl ether, 2-phenyl-4-iso Examples include propenyl phenyl glycidyl ether.

These isopropenylphenyl glycidyl ethers can be used alone or in combination of two or more.

Isopropenylphenyl glycidyl ethers are obtained by a method of reacting isopropenylphenols with epichlorohydrinto.

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 obtained by these methods can be used as they are. However, when isopropenyl phenyl glycidyl ethers are used as a raw material for the 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.

Isopropenylphenyl glycidyl ethers obtained from isopropenylphenols and epichlorohydrin can be purified by well-known and conventional rectification or recrystallization.

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

Particularly when used as an epoxy resin for electronic materials, the purity of isopropenylphenyl glycidyl ethers is 9
It is preferably 8.7% by weight or more and the chlorine-containing derivative of isopropenylphenyl is 0.8% by weight or less.

The higher the purity of isopropenylphenyl glycidyl ethers, the higher the heat resistance and water resistance when used as an epoxy resin, and the smaller the chlorine-containing derivative of isopropenylphenyl, the less hydrolyzable chlorine is preferred.

The amount of hydrogen iodide used as a catalyst is 0.01 with respect to the total number of moles of isopropenylphenyl glycidyl ethers.
Mol% to 10 mol% is preferred. 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 halogen as a cocatalyst to hydrogen iodide.

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

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 approximately 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.

The types of halogen include iodine, bromine, iodine chloride,
Examples thereof include iodine bromide, and iodine is most 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 80 ° C, -25 ° C to 0
C is even more preferred.

When the temperature exceeds 80 ° 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 such as printed circuit boards, and resin modifiers.

F. 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 means a glycidyl ether group 1
Defined in gram equivalents per mol.

In addition, chlorine content means that the poly (isopropenylphenyl glycidyl ether) s are dissolved in dioxane, the alcohol solution of potassium hydroxide is added, and the chloride ion desorbed when heated for 2 hours under reflux is reversed with silver nitrate solution. It is determined by titration and is defined as 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.

The composition ratio of the copolymer obtained by combining at least two kinds of o-isopropenylphenyl glycidyl ethers, m-isopropenylphenyl glycidyl ethers and p-isopropenylphenyl glycidyl ethers is ¹³ C-NMR, It was calculated from the peak area ratio of the aromatic ring carbon substituted with the glycidyl ether group. (P body,
The peaks of the m-form and the o-form are 154.3 ppm and 151.6, respectively.
ppm and 155.2 ppm. ) Reference 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
134 g (containing 2.5% oligomer) and 7.0 mol of epichlorohydrin are added to make a uniform solution. While keeping the temperature at 74 ° C. and the pressure at 250 mmHg, 48% NaOH aqueous solution was continuously added in 6 hours. 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. This product had an epoxy equivalent of 201 and a chlorine content of 830 ppm.

In 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 14.7% by weight, and a chlorine-containing derivative of p-itepropenylphenyl of 0.9.
It was 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. Epoxy equivalent of this product is 190, chlorine content is 30pp
It was m. According to GC analysis, the purity of p-isopropenylphenylglycidyl ether was 99.95% by weight, p
-The content of chlorine-containing derivative of isopropenylphenyl is
It was 0.01% by weight.

Reference Example 2 (1) Synthesis of crude m-isopropenylphenyl glycidyl ether p-isopropenylphenyl glycidyl ether 134
A viscous liquid was obtained by synthesizing in the same manner as in (1) of Reference Example 1, except that 134 g of m-isopropenylphenyl glycidyl ether (containing 53% of oligomer) was used instead of g. The epoxy equivalent of this product was 20 g, and the chlorine content was 850 ppm.

The composition was 42.3% by weight of m-isopropenylphenyl glycidyl ether, 56% by weight of its oligomer, and 0.53% by weight of a chlorine-containing derivative of m-isopropenylphenyl.

(2) Purification of m-isopropenyl phenyl glycidyl ether 100 g of crude m-isopropenyl phenyl glycidyl ether obtained in (1) was purified in the same manner as in (2) of Reference Example 1. The purified product had an epoxy equivalent of 190 and a chlorine content of 60 ppm. According to GC analysis, the purity of m-isopropenylphenyl glycidyl ether was 99.3% by weight, and the content of chlorine-containing derivative of m-isopropenylphenyl was 0.03% by weight.

Reference Example 3 (1) Synthesis of crude o-isopropenylphenylglycidyl ether p-isopropenylphenylglycidyl ether 134
A viscous liquid was obtained by synthesizing in the same manner as in (1) of Reference Example 1, except that 134 g of o-isopropenylphenylglycidyl ether (containing 63% of oligomer) was used instead of g. This product had an epoxy equivalent of 221 and a chlorine content of 790 ppm.

The composition was 29.4% by weight of o-isopropenylphenyl glycidyl ether, 69.8% by weight of its oligomer, and 0.51% by weight of a chlorine-containing derivative of m-isopropenylphenyl.

(2) Purification of o-isopropenyl phenyl glycidyl ether 100 g of crude o-isopropenyl phenyl glycidyl ether obtained in (1) was purified in the same manner as in (2) of Reference Example 1. The purified product has an epoxy equivalent of 191 and a chlorine content of 9
It was 0 ppm. According to GC analysis, the purity of o-isopropenylphenyl glycidyl ether was 99.1% by weight, and the content of chlorine-containing derivative of o-isopropenylphenyl was 0.05% by weight.

Example 1 Synthesis of poly (m-isopropenylphenylglycidyl ether) 19 g of m-isopropenylphenylglycidyl ether obtained in Reference Example 2 was dissolved in 181 g of toluene dehydrated with Molecular Sieves 4A and cooled to -20 ° C. Then, 0.128 g of hydrogen iodide and 2.5 g of toluene were added and the mixture was kept warm for 1 hour. After adding 100 g of methanol to stop the reaction and washing with 100 g of a 10 wt% sodium thiosulfate aqueous solution, the solvent and residual monomers were removed by distillation,
2.1 g of a pale yellow resin was obtained. The epoxy equivalent was 198, the chlorine content was 60 ppm, and the number average molecular weight was 1,200.

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 Example 1 except that 0.254 g of iodine was used.

6.7 g of a pale yellow resin was obtained. The epoxy equivalent was 197, the chlorine content was 70 ppm, and the number average molecular weight was 3,500.

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

Example 3 0.128 g hydrogen iodide instead of 0.128 g hydrogen iodide
Polymerization was carried out in the same manner as in Example 1 except that 0.163 g of iodine chloride was used. 6.7 g of a pale yellow resin was obtained. The epoxy equivalent was 198, the chlorine content was 60 ppm, and the number average molecular weight was 2,900.

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

Example 4 Synthesis of poly (o-isopropenylphenylglycidyl ether) 19 g of m-isopropenylphenylglycidyl ether
Instead of 19 g of o-isopropenylphenyl glycidyl ether obtained in Reference Example 8 was used, polymerization was carried out in the same manner as in Example 1 to obtain 3.2 g of a pale yellow resin. Epoxy equivalent of this product is 199, chlorine content is 90pp
m and the number average molecular weight were 1,800.

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

Example 5 0.128 g of hydrogen iodide in place of 0.128 g of hydrogen iodide,
Polymerization was carried out in the same manner as in Example 4 except that 0.254 g of iodine was used to obtain 7.3 g of a pale yellow resin. The epoxy equivalent of this product was 199, the chlorine content was 90 ppm, and the number average molecular weight was 4,300.

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
In the same manner as in Example 1 except that 14 g was used, m-
Polymerization of isopropenyl phenyl glycidyl ether was carried out. 1.9 g of a yellow resin are obtained.

Comparative Example 2 Polymerization of m-isopropenylphenylglycidyl ether was carried out in the same manner as in Example 1 except that 0.164 g of trichloroacetic acid was used instead of hydrogen iodide. 2.3 g of a pale yellow resin was obtained.

Comparative Example 3 Boron triboride ethyl ether complex in place of hydrogen iodide
By the same method as in Example 4 except that 14 g was used, o-
Polymerization of isopropenyl phenyl glycidyl ether was carried out. 3.3 g of a yellow resin was obtained.

All the resins of Comparative Examples 1 to 3 were insoluble in tetrahydrofuran, and the ring-opening bond of the glycidyl group was detected.

Comparative Example 4 Poly (m-isopropenylphenol) (number average molecular weight 900) was glycidyl etherified in the same manner as in Example 1 to obtain a pale yellow resin. The epoxy equivalent of this resin was 217, and the chlorine content was 1020 ppm.

Examples 6 to 13 As shown in Table 1, toluene 1 obtained by dehydrating the two types of monomers obtained in Reference Examples 1 to 3 with Molecular Sieves 4A was used.
It was dissolved in 62 g and cooled to −15 ° C., and an initiator solution prepared by dissolving the catalyst shown in Table 1 in 2.5 g of toluene was added and kept warm for 60 minutes. After adding 100 g of methanol to stop the reaction, 100 g of 10 wt% sodium thiosulfate aqueous solution
After washing with 100 g of pure water, the solvent and residual monomers were removed by distillation to obtain a resin.

All of these resins were soluble in tetrahydrofuran, and no ring-opening bond of glycidyl group was detected by infrared spectrum analysis. In addition, ¹ H and ¹³ C-NM
From the R analysis, it was confirmed that only the isopropenyl group of the monomer had a polymerized structure.

Comparative Examples 5 to 6 As shown in Table 1, polymerization was carried out using boron triboride ethyl ether complex or trichloroacetic acid as a catalyst.
Both the obtained resins were insoluble in tetrahydrofuran, and the ring-opening bond of the glycidyl group was detected.

G. EFFECTS OF THE INVENTION The present invention uses a substance having two kinds of functional groups of isopropenyl group and glycidyl group in one molecule, such as isopropenylphenylglycidyl ethers, using hydrogen iodide or halogen and a glycidyl group as a catalyst. Is a method of suppressing the polymerization of the above and performing the polymerization only with the isopropenyl group.

In the past, such vinyl-polymerized isopropenylphenylglycidyl ethers were obtained only by the reaction of poly (isopropenylphenol) s with epichlorohydrin, and from this conventional method, chlorides due to epichlorohydrin were obtained. Even if they coexist
It was difficult to remove this coexisting substance.

However, in the present invention, since the isopropenyl phenyl glycidyl ethers can be purified by a conventional technique such as rectification or recrystallization, poly (isopropenyl phenyl glycidyl ether) s 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) Inventor Noriaki Saito 5-1 Sokai-cho, Niihama-shi, Ehime Sumitomo Chemical Co., Ltd.

Claims (3)

[Claims] 1. A general formula (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.) Monomers consisting of isopropenyl phenyl glycidyl ethers (excluding p-isopropenyl glycidyl ether alone) are polymerized using hydrogen iodide or a combination system of hydrogen and halogen as a catalyst. Propenyl phenyl glycidyl ether) manufacturing method. 2. The method according to claim 1, wherein the monomer is o-isopropenylphenyl glycidyl ether or m-isopropenyl glycidyl ether. 3. The method according to claim 1, wherein the monomer is a mixture of at least two selected from o-isopropenylphenyl glycidyl ether, m-isopropenyl glycidyl ether and p-isopropenyl phenyl ether. Production method.