JPH03145452A - Fluorine-containing cyanate and production thereof - Google Patents

Abstract

NEW MATERIAL:A fluorine-containing cyanate expressed by formula I [n is 1 or 2; m is 0 to (6-n); X is halogen, 1-10C alkyl, fluoroalkyl, alkoxy or fluoroalkoxy]. EXAMPLE:1,4-Bis(2-cyanatohexafluoro-2-propyl)benzene. USE:Useful as a modifier, crosslinking agent, etc., for thermosetting or thermoplastic resins or further as a monomer, intermediate or prepolymer for producing polycyanuric acid esters. The resultant resins have physical properties such as a low dielectric constant, low moisture permeability and low refractive index and useful for applications such as electronic materials. PREPARATION:A fluorine-containing alcohol expressed by formula II is reacted with a cyanogen halide in the presence of an acid acceptor in a medium such as acetone at -40 to +40 deg.C to afford the compound expressed by formula I. Sodium hydroxide, etc., are used as the acid acceptor.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention provides a novel thermosetting resin useful as a monomer for thermosetting resins, or as a modifier, crosslinking agent, etc. for various thermosetting resins or thermoplastic resins. This article relates to base cyanate and its manufacturing method.

[Prior art and problems to be solved by the invention] Conventionally,
It is known that the corresponding aromatic cyanogen ester (cyanate) is produced by reacting an alcohol or a phenolic hydroxyl group with a cyanide halide, and a fluorine-containing cyanate can be obtained from a fluorine-containing alcohol or phenol. .

According to U.S. Pat. No. 4,745,215, dicyanate resin derived from bisphenol AF has a low dielectric constant, low hygroscopicity, and excellent compatibility with other resins, and is useful for various electronic materials. It is said that it is suitable for application as a resin for use in plastics.

In general, the introduction of fluorine atoms is effective in improving various properties such as reducing the rAt ratio, improving hygroscopicity, improving compatibility, and further improving flame retardancy. A large amount of monomer is desired.

From the viewpoint of heat resistance, aromatic compounds are acidophilic, but no compounds other than dicyanate derived from bisphenol AF are known, and in particular, aralkyl alcohol derivatives are unknown.

[Means for Solving the Problems] As a result of intensive studies aimed at achieving the above object, the present invention surprisingly found that bis(trifluoromethyl)carbinol, which has high acidity and extremely poor nucleophilic reactivity, The present invention was achieved by discovering the fact that cyanate is produced by reacting with cyanogen halide.

That is, the present invention provides - maximum (where n is 1 or 2, dust is an integer from O to (6-n),
X is a halogen atom or an alkyl group having 1 to 10 carbon atoms,
A novel fluorine-containing cyanate represented by a fluoroalkyl group, an alkoxy group, or a fluoroalkoxy group;
-n) integer, X is a halogen atom or carbon number 1 to 10
The general formula (formula Medium, n is 1 or 2, ■ is an integer from 0 to (6-n),
X is a halogen atom or an alkyl group having 1 to 10 carbon atoms,
The present invention provides a method for producing a novel fluorine-containing cyanate represented by ), which represents a fluoroalkyl group, an alkoxy group, or a fluoroalkoxy group.

The compound of general formula (n) that is a raw material of the present invention uses hexafluoroacetone as one of the raw materials.

They are obtained by reacting with benzene derivatives, and their production methods are described in detail, for example, in Japanese Patent Application No. 155717/1982 and Japanese Patent Application No. 162939/1999 filed by the same applicant.

Examples of the acid acceptor used in the reaction of the present invention include inorganic alkali compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate, and organic amines such as triethylamine and pyridine.

The cyanogen halides used are cyanogen chloride and cyanogen bromide, with cyanogen bromide being preferred from the viewpoint of yield and handling.The amount used is preferably equivalent to the alcoholic hydroxyl group contained in the raw material compound. Above, it is sufficient that it is 5 times equivalent or less, more preferably 1.5 times or more and 5 times equivalent or less. If the amount of cyanogen halide is less than the equivalent, expensive unreacted raw material (n) will remain. This is not preferable, and if the amount is more than 5 times equivalent, it is not preferable in terms of post-treatment of unreacted cyanogen halide.

As the reaction medium, it is preferable to use acetone, ether, tetrahydrofuran, toluene, xylene or halogenated hydrocarbon, and the reaction temperature is -40
℃~40℃, more preferably 10'C~1
If the zero reaction temperature, which is 0°C, is lower than 140°C, the reaction will hardly proceed, whereas if it is higher than 40°C, the cyanogen halide will easily volatilize, which is not preferable.

The reaction time is 3 hours or more, preferably 6 hours or more to allow the reaction to proceed sufficiently.

The compounds obtained in the present invention include 1,4-bis(2-
Examples include cyanatohexafluoro-2-propyl)benzene and its derivatives, 1,3-bis(2-cyanatohexafluoro-2-propyl)benzene and its derivatives.

The compound of the present invention is useful as a monomer, intermediate, or prepolymer in the production of polycyanuric acid ester, and the resulting resin has physical properties such as low dielectric constant, low moisture permeability, and low refractive index. Suitable for applications such as electronic materials.

[Examples] Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples.

Example 1 1.205 g of 4-bis(2-hydroxyhexafluoro-2propyl)benzene and 159 g of bromocyanine were mixed into 1.
3 Il was dissolved in methylene chloride, and while sufficiently stirring and cooling, 126.3 g of triethylamine was added dropwise over 6 hours while maintaining the reaction temperature at 5 to 10°C.

After completion of dropping and aging for 12 hours, the reaction solution was washed and removed with a mixed solution of 800 ml of methanol and 800 mA of water, and methylene chloride was removed.
A pale yellow viscous substance was obtained.

Dissolve this in 500 ml of acetone and add 160 ml of
1 of water was added dropwise while stirring to precipitate the desired product in the form of a white powder.

After collecting the precipitated solid matter by suction filtration,
The solid matter was poured into 0 ml of water, washed with water, and separated again by suction filtration.
01 layer 11g, time 12 hours), target objects 1 and 4
96.2 g of crystals of -bis(2-cyanatohexafluoro-2-propyl)benzene were obtained. (Yield, 41
．． 8%) Melting point = 115-116℃ 'Hn@r (CDC13, TMS) δ:
7. Q pHl Garden In (KBr) v (cm(
) 730(S), 750(S), 820(S)95
0(S), 990(S), 1000(S), 1130(
S), 1170(S).

1200(S), 1210.1220(S), 1250
(S), 1300(S).

1420 (W), 2550 (m) Example 2 205 g of 1.4-bis(2-hydroxyhexafluoro-2-propyl)benzene and 92.3 g of chlorocyan were dissolved in 1.31 methylene chloride and stirred thoroughly. While cooling, 126.3 g of triethylamine was added dropwise over 6 hours while maintaining the reaction temperature at 5 to 10°C.

After the dropwise addition was completed, the mixture was aged for 12 hours, and then the reaction solution was washed and removed with a mixed solution of 800 ml of methanol and 800 ml of water, and methylene chloride was removed to obtain a pale yellow viscous substance. Ta.

Dissolve this in 500 m It of acetone and add 160 m It.
ml of water was added dropwise while stirring to precipitate the desired product in the form of a white powder. After removing the precipitated solid by suction filtration, it was further poured into 600 ml of water, washed with water, and separated by suction filtration again. (Drying conditions: Temperature: 30°C, pressure: 10+++m, 11g, 1 hour, 12
time), crystals of the target product 1,4-bis(2-cyanatohexafluoro-2-propyl)benzene 16.
Obtained 0g. (Yield: 7.0%) [Effect of the invention] The novel fluorine-containing cyanate of the present invention can be obtained by mixing the alcohol of the corresponding compound with cyanogen halide,
In particular, it is obtained by reacting with bromic cyanide, and is extremely useful as a monomer for thermosetting resins, or as a modifier, crosslinking agent, etc. for thermosetting or thermoplastic resins.

Claims (2)

[Claims] (1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (In the formula, n is 1 or 2, m is an integer from 0 to (6-n),
X is a halogen atom or an alkyl group having 1 to 10 carbon atoms,
Indicates a fluoroalkyl group, an alkoxy group, and a fluoroalkoxy group. ) A novel fluorine-containing cyanate. (2) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (II) (In the formula, n is 1 or 2, m is an integer from 0 to (6-n),
X is a halogen atom or an alkyl group having 1 to 10 carbon atoms,
Indicates a fluoroalkyl group, an alkoxy group, and a fluoroalkoxy group. ) A general formula characterized by reacting a fluorine-containing alcohol and a cyanogen halide in the presence of an acidifying agent ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ( I ) (In the formula, n is 1 or 2, m is an integer from 0 to (6-n),
X is a halogen atom or an alkyl group having 1 to 10 carbon atoms,
Indicates a fluoroalkyl group, an alkoxy group, and a fluoroalkoxy group. ) A method for producing a novel fluorine-containing cyanate.