JP3319061B2 - Method for producing cyanate compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a sealing of electronic parts, laminates, composite materials, methods for producing useful bis cyanate compound as a molding material for and adhesives.

[0002]

2. Description of the Related Art Conventionally, as a method for producing a cyanate compound, a method is known in which a corresponding hydroxy compound is reacted with a cyanogen halide in a solvent in the presence of a base in such a manner that the cyanogen halide is always present in excess of the base. (US Pat. No. 3,553,244). When the reaction is performed in this way,
Since the phenolate anion generated by the reaction of the hydroxy compound with a base such as a tertiary amine always encounters an excess of cyanogen halide, the phenolate anion reacts with the already generated cyanate ester to form an iminocarboxylic acid bis-carboxylate. It is described that the by-product of an ester can be suppressed. However, in the case of this method, on the contrary, since a tertiary amine is added to a large amount of cyanogen halide, a reaction of the tertiary amine and cyanogen halide tends to produce dialkyl cyanamide as a by-product, and the purity of the cyanate compound is not improved. There was a problem. In the case of the above method, it is necessary to drop the tertiary amine into the cyanogen halide or to add the cyanogen halide by co-injection dripping so as to always be in excess of the tertiary amine. It is a safety problem to charge a large amount of highly reactive cyanogen halide to the reaction vessel in advance, and if tertiary amine is dropped when excessively charged cyanogen halide having a low boiling point is excessively charged. There is a problem that salt is deposited near the dropping port and the dropping tube is blocked.

[0003]

The object of the present invention is to solve the above In view of the above problems, high safety, and to provide a production method and more process to easily pure bis cyanate compound.

[0004]

The present inventors have SUMMARY OF THE INVENTION As a result of continued extensive studies on production method of bis cyanate <br/> sulfonate compounds, high by controlling the method of adding the cyanogen halide and a tertiary amine It found that purity bis cyanate compound is obtained, and have completed the present invention.

That is, the present invention provides the following general formula [I] [Wherein, R and A each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and X represents a 1 to 20 carbon atom.
An alkylene group, i represents an integer of 0 or more and 3 or less], a tertiary amine is added to a bisphenol compound represented by the following formula, and a cyanogen halide is added dropwise. by併注dropwise amine, to provide a method for producing bis cyanate compound tertiary amine in a tertiary amine addition is characterized in that the reaction is carried out as a molar excess from cyanogen halide
Ru shall Der. Here, an alkyl having 1 to 6 carbon atoms
As the group, for example, methyl, t-butyl, cyclohexyl
And the like. Alkylene having 1 to 20 carbon atoms
Examples of the group include methylene, 2,2-propylene,
1,1-butylene, 1,1-cyclohexylene, dicyclo
Lopentylene and the like.

As the bisphenol compound to be used, any one can be used as long as it satisfies the general formula [I]. For example, bis (hydroxyphenyl) methane, bis (4-hydroxy-3,5-dimethylphenyl) Methane, bis (2-hydroxy-3-t-butyl-
5-methylphenyl) methane, bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-)
(Hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-t-butyl-6-methylphenyl) propane, 2,2-bis (4-hydroxy-3-
t-butylphenyl) propane, 1,1-bis (4-hydroxy-3-t-butyl-6-methylphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4 -Hydroxy-3-methylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-cyclohexyl-6-methyl) butane, bis (4-hydroxyphenyl) menthane, bis (4-hydroxy-3,5-dimethyl) ) Menthane, bis (4-hydroxy-3-t-butyl-6-methylphenyl) menthane, bis (4-hydroxyphenyl) dicyclopentane, bis (4-hydroxy-3,5-dimethylphenyl) dicyclopentane, Bis (4-hydroxy-3-t
-Butyl-6-methylphenyl) dicyclopentane and the like. For the purpose of obtaining a high-purity biscyanate, it is more preferable to use a bisphenol having an alkyl group at the ortho-position of the hydroxyl group, particularly an alkyl group having a large steric hindrance, since the generation of by-products is suppressed. When a bisphenol compound having a t-butyl group at the ortho-position is used, a highly pure biscyanate can be obtained.

The tertiary amine used includes trimethylamine, triethylamine, tripropylamine, tributylamine, dimethylaniline, diethylaniline, pyridine, quinoline and the like.

Examples of the reaction solvent include ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; aromatic solvents such as benzene, toluene and xylene; ether solvents such as diethyl ether, dimethyl cellosolve, diglyme, tetrahydrofuran and dioxane; Halogenated hydrocarbons such as methylene, chloroform, carbon tetrachloride, and chlorobenzene; alcohol solvents such as methanol, ethanol, isopropanol, methyl cellosolve, and propylene glycol monomethyl ether;
Aprotic polar solvents such as dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidone and dimethylsulfoxide; nitrile solvents such as acetonitrile and benzonitrile; nitromethane and nitrobenzene; Ester solvents such as nitro solvents, ethyl acetate and ethyl benzoate can be used. Among them, ketone solvents are preferable, and methyl isobutyl ketone is most preferably used since it can be washed and separated after the reaction.

In the reaction, a bisphenol compound is first dissolved in a solvent, and a predetermined amount of a tertiary amine is added or added dropwise.
A tertiary amine is dropped more rapidly than a cyanide halide by a method of dropping a predetermined amount of cyanogen halide or by co-dropping.
The tertiary amine is added during the addition of the tertiary amine so that the tertiary amine is in an excess molar amount relative to the cyanogen halide. As the cyanogen halide, cyanogen chloride or cyanogen bromide is used. When cyanogen chloride is used, the reaction temperature is -30 to 30.
The reaction is performed at a temperature of 15 ° C, more preferably -10 ° C to 15 ° C, and in the case of using cyanogen bromide, at a temperature of -30 ° C to 65 ° C. Usually, it is said that when a cyanogen halide is dropped after generating a phenolate first, a large amount of a phenolate present in the system reacts with a generated cyanate and an iminocarboxylic acid bisester is by-produced, which is not preferable.
When a bisphenol compound having the general formula [I], particularly a bisphenol compound having a substituent having a steric hindrance at the ortho-position of the hydroxyl group is used, the reaction between the phenolate and the generated cyanate is suppressed, so that high-purity bisphenol is used. A cyanate compound is obtained in high yield. The amount of the tertiary amine and the amount of the cyanogen halide are 0.1 to 5 times, preferably 2 to 4 times the molar amount of the bisphenol compound, and there is no problem even if the tertiary amine is charged in excess of the amount of the cyanogen halide. . According to this method, the production of dialkyl cyanamide by the reaction of the tertiary amine and the cyanogen halide is smaller than in the conventional method in which the cyanogen halide is always present in excess of the tertiary amine, and the same cyanogen halide and when compared with a tertiary amine charged amount, higher purity bis cyanate compound.

The post-treatment is carried out by removing the by-produced tertiary amine hydrohalide salt by washing with water or by filtration, followed by concentration, precipitation or crystallization. When washing with water, it is preferable to use a solvent that is immiscible with water in advance as a reaction solvent. When an excess molar amount of the tertiary amine is charged relative to the cyanogen halide, the reaction solution is finally basic, so that the tertiary amine can be washed with an aqueous acidic solution such as hydrochloric acid in order to efficiently wash the tertiary amine. . Concentration is preferably carried out under reduced pressure at a temperature not lower than the melting point of the product and not higher than 200 ° C. If the temperature is too high, the polymerization of cyanate starts, which is not preferable. For precipitation and crystallization, any solvent having low solubility of the product can be used.For example, water or alcoholic solvents such as methanol, ethanol, and isopropanol, benzene, toluene, xylene, hexane, petroleum ether and the like can be used. It is carried out by adding a hydrocarbon-based solvent to the product solution or vice versa, and in particular, in the case of crystallization, may be carried out by cooling or concentrating the solution to some extent without adding a poor solvent. .

[0011]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples.

Example 1 A reactor equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser was charged with 1,1-bis (4-hydroxy-
3-t-butyl-6-methylphenyl) butane (Sumitomo Chemical Co., Ltd., trade name Sumilyzer BBM-S) 20
After 0.0 g (0.5228 mol) and 800 g of methyl isobutyl ketone were charged and dissolved at room temperature, 148.1 g (1.464 mol) of triethylamine was added. After cooling the solution to 0 ° C, 89.99 g of cyanogen chloride (1.4
64 mol) was added dropwise at 0 to 6 ° C over 2 hours, and the mixture was kept at the same temperature for 1 hour. After washing three times with 300 g of water,
After concentrating the solvent by 650 g under reduced pressure, 400 g of methanol was added dropwise, cooled to 5 ° C., and stirred for 3 hours.
The obtained slurry was filtered, washed with 200 g of methanol, and dried under reduced pressure to obtain 208 g of white crystals having a melting point of 123 ° C (yield 92%). The purity of the dicyanate compound by LC is 9
8.0%. Note that the content of diethyl cyanamide in the methyl isobutyl ketone solution after washing with water was 1.90%.

Example 2 In Example 1, 158.7 g (1.56 g) of triethylamine was used.
8 mol), 83.55 g (1.359 m) of cyanogen chloride
ol), and the procedure was carried out under exactly the same conditions except that a 10% aqueous hydrochloric acid solution was used in the first water washing to obtain 205 g of white crystals (yield: 91%). The purity of the dicyanate compound by LC is 9
7.0%. In addition, the diethyl cyanamide content of the methyl isobutyl ketone solution after water washing was 0.70%.

Example 3 In Example 1, 148.1 g (1.46 g) of triethylamine was used.
4 mol) and 96.40 g (1.568 m) of cyanogen chloride.
ol) White crystal 2
08 g was obtained (92% yield). The purity of the dicyanate compound by LC was 97.0%. The methyl isobutyl ketone solution after washing with water had a diethyl cyanamide content of 2.1.
9%.

Example 4 In a reactor equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser, 1,1-bis (4-hydroxy-
3-t-butyl-6-methylphenyl) butane (Sumitomo Chemical Co., Ltd., trade name Sumilyzer BBM-S) 20
0.0 g (0.5228 mol) and 800 g of methyl isobutyl ketone were charged, dissolved at room temperature, cooled to 0 ° C., and triethylamine 148.1 g (1.464 mol)
l) over 30 minutes to give 89.99 g (1.4) of cyanogen chloride.
64 mol) over 2 hours at 0 to 6 ° C, and the mixture was further kept at the same temperature for 1 hour. After washing three times with 300 g of water, the solvent was concentrated under reduced pressure by 6,450 g, and 400 g of methanol was added dropwise, cooled to 5 ° C., and stirred for 3 hours. The obtained slurry was filtered, washed with 200 g of methanol, and dried under reduced pressure to obtain 208 g of white crystals (yield 92).
%). The purity of the dicyanate compound by LC was 97.0%. Incidentally, the content of diethyl cyanamide in the methyl isobutyl ketone solution after washing with water was 2.00%.

Example 5 A reactor equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser was charged with 1,1-bis (4-hydroxy-
20-0.0 g of 3-methylphenyl) cyclohexane
(0.6747 mol), methyl isobutyl ketone 80
After dissolving at room temperature, triethylamine 19 was added.
1.2 g (1.889 mol) were added. Solution at 0 ° C
After cooling to 107.8 g of cyanogen chloride (1.754 mo)
l) was added dropwise at 0 to 6 ° C over 2 hours, and 1
Incubated for hours. After washing with 300 g of a 10% aqueous hydrochloric acid solution and twice with 300 g of water, 648 g of the solvent was concentrated by vacuum concentration, 400 g of methanol was added dropwise, and the mixture was cooled to 5 ° C. and stirred for 3 hours. The obtained slurry was filtered, washed with 200 g of methanol, and dried under reduced pressure to obtain 175 g of white crystals having a melting point of 94 ° C. (yield: 75%). LC
The purity of the dicyanate was 96.9%.

Comparative Example 1 A reactor equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser was charged with 1,1-bis (4-hydroxy-
3-t-butyl-6-methylphenyl) butane (Sumitomo Chemical Co., Ltd., trade name Sumilyzer BBM-S) 20
0.0 g (0.5228 mol) and 800 g of methyl isobutyl ketone were charged, dissolved at room temperature, cooled to 0 ° C., and 96.40 g (1.568 mol) of cyanogen chloride was added. Thereafter, 148.1 g of triethylamine (1.
464 mol) was added dropwise at 0 to 6 ° C. over 2 hours, and the mixture was kept at the same temperature for 1 hour. After washing three times with 300 g of water, 650 g of the solvent was concentrated by vacuum concentration, 400 g of methanol was added dropwise, and the mixture was cooled to 5 ° C. and stirred for 3 hours. The obtained slurry was filtered, washed with 200 g of methanol, and dried under reduced pressure to obtain 188 g of white crystals (yield: 83).
%). The purity of the dicyanate compound by LC was 91.0%. The content of diethyl cyanamide in the methyl isobutyl ketone solution after washing with water was 3.50%.

Comparative Example 2 A reactor equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser was charged with 1,1-bis (4-hydroxy-
3-t-butyl-6-methylphenyl) butane (Sumitomo Chemical Co., Ltd., trade name Sumilyzer BBM-S) 20
0.0 g (0.5228 mol) and 800 g of methyl isobutyl ketone were charged, dissolved at room temperature, cooled to 0 ° C., and triethylamine 148.1 g (1.464 mol)
l) and 96.40 g (1.568 mol) of cyanogen chloride
Was co-injected and dropped at 0 to 6 ° C. over 2 hours, and further kept at the same temperature for 1 hour. After washing three times with 300 g of water, 653 g of the solvent was concentrated by vacuum concentration, and then methanol 40%.
0 g was added dropwise, and the mixture was cooled to 5 ° C. and stirred for 3 hours. The obtained slurry was filtered, washed with 200 g of methanol, and dried under reduced pressure to obtain 192.2 g of white crystals (yield: 85%).
The purity of the dicyanate compound by LC was 92.0%. Note that the content of diethyl cyanamide in the methyl isobutyl ketone solution after washing with water was 3.05%.

[0019]

As is clear from the examples, by using the production method of the present invention, a dicyanate compound having a high yield and a high purity can be obtained. Compared with the method in which the reaction is carried out in such a manner that the cyanogen halide is always present in excess of the tertiary amine as shown in the comparative example, the purity and yield of the dicyanate compound are compared when the cyanide halide and the tertiary amine are compared at the same charge. The rate is high, and the by-product of dialkyl cyanamide is small. In addition, since a large amount of highly dangerous cyanogen halide does not stay in the reaction vessel, the safety is higher and the process is more excellent because there is no trouble such as dropping tube clogging at the time of dropping of tertiary amine.

Continued on the front page (72) Inventor Shuichi Kanakawa 6 Kitahara, Tsukuba-shi, Ibaraki Sumitomo Chemical Co., Ltd. (56) References JP-A-47-10227 (JP, A) JP-A-51-108039 (JP, A) Special table 1986-500120 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C07C 261/02

Claims (3)

(57) [Claims] 1. A compound represented by the following general formula [I]: [Wherein, R and A each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and X represents a 1 to 20 carbon atom.
The alkylene group, i represents an integer of 0 or more and 3 or less. In the presence of a solvent, a tertiary amine is added to the bisphenol compound represented by the formula, and then a cyanogen halide is added dropwise. Alternatively, a cyanogen halide and a tertiary amine are co-added and added. method for producing bis cyanate compound tertiary amine is characterized by performing the reaction as a molar excess from halogenated cyan. 2. A general formula A process according to claim 1 bis cyanate compound according R bisphenol compounds represented by [I] is characterized in that it is a t- butyl group. 3. A general formula A process according to claim 1 bis cyanate compound according bisphenol compound represented by [I] is characterized in that it is represented by the following formula. Embedded image (In the formula, t-Bu represents a t-butyl group.)