JPH0463897B2 - - Google Patents

Description

[Detailed description of the invention]

[Technical field of the invention] The present invention relates to a novel polymer and a method for producing the same,
More specifically, the present invention relates to a novel polymer that has excellent heat resistance, flame retardancy, solvent resistance, and mechanical strength, and a method for producing the same. [Technical background of the invention and its problems] Cyanoaryl ether polymers having various structures are disclosed in JP-A-47-14270 and JP-A-59-206433. Although these polymers have excellent mechanical properties and are useful as industrial materials, they cannot be said to have sufficient heat resistance. Therefore, there is a strong demand for the development of cyanoaryl ether polymers that have sufficiently excellent heat resistance as well as mechanical properties. [Object of the Invention] The object of the present invention is to provide a novel cyanoaryl ether polymer having excellent heat resistance, and also good mechanical strength, solvent resistance, and flame retardancy, and a method for producing the same. [Summary of the invention] The novel polymer of the present invention has the following formula: A crystalline polymer having a repeating unit shown in is the following formula: (In the formula, X represents a halogen atom.) A dihalogenobenzonitrile represented by the following formula: (In the formula, M represents a hydrogen atom or an alkali metal.) When M represents a hydrogen atom, an alkali metal salt is added to react the dihydroxynaphthalene or its alkali metal salt in the presence of a solvent. The reaction product is then treated with water or alcohol. The novel polymer of the present invention is based on a skeleton consisting of a plurality of repeating units of the formula () connected in a linear chain,
Both ends are hydrogen atoms,

【formula】

【formula】

【formula】

It is a polymer blocked with the formula: (wherein R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, an arylalkyl group, or a cyano group). The polymer of the present invention has a reduced viscosity (ηsp/c) of 0.3 dl/g or more at 60°C of the resin solution when the polymer is dissolved in parachlorophenol to a concentration of 0.2 g/dl. It is a crystalline polymer with a certain molecular weight. Reduced viscosity is 0.3
In the case of a polymer having a molecular weight of less than dl/g, the mechanical strength and heat resistance of the polymer will be poor, making it impractical. The crystalline polymer of the present invention is produced as follows. That is, a dihalogenobenzonitrile represented by the formula () and an alkali metal salt of dihydroxynaphthalene represented by the formula () are dissolved in a solvent described below and reacted under the conditions described below. In the compound of formula (), as halogen X,
Cl and F are preferred. In the compound of formula (), M may be any alkali metal, with Na and K being particularly preferred. This formula ()
The compound is a salt prepared by the neutralization reaction of dihydroxynaphthalene or dihydroxynaphthalene with an alkali metal salt such as potassium carbonate or potassium hydroxide. In addition, when the compound of formula () is dihydroxynaphthalene, an alkali metal salt such as potassium carbonate or potassium hydroxide is added together to carry out the reaction. The amount of the compound of formula () and the compound of formula () to be used is determined based on the relationship with the degree of polymerization of the desired polymer. Both may be used in approximately equimolar amounts, but there is no problem even if the amounts are not equimolar. In addition, when using dihydroxynaphthalene, the amount of alkali metal salt to be blended is not particularly limited, but in order for dihydroxynaphthalene to sufficiently form a salt, it is necessary to use an equimolar amount or slightly more than the amount of dihydroxynaphthalene used. Preference is given to using molar amounts. The reaction is carried out in a solvent. Solvents used include neutral polar solvents such as dimethyl sulfoxide, sulfolane, dimethylacetamide, N-
Methylpyrrolidone can be mentioned, and the amount used may be sufficient to dissolve each compound of formula () and formula (). Reaction temperature is 150-300℃, preferably 180-210℃
°C, reaction time is 0.5 to 5 hours, preferably 1 to 3 hours.
It's time. Moreover, the reaction may be carried out under normal pressure or under increased pressure. In addition, in this process, as a molecular weight regulator, the following formula: (In the formula, R represents any one of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, and a cyano group.) It is preferable to add a monovalent phenol represented by the following formula. In the compound of formula (), the aryl group is, for example,

【formula】

【formula】

[Formula] is preferred, and the aralkyl group is, for example,

[Formula] is preferred. The monovalent phenol represented by the formula () is
for example,

【formula】

【formula】

【formula】

[Formula] can be given. Further, the amount of the molecular weight regulator to be added is determined based on the relationship with the molecular weight of the target polymer. Next, the reaction product obtained through the above process is treated with water or alcohol to eliminate the alkali metal present at the end of the reaction product and replace it with H and OH. As the alcohol, methanol and ethanol are preferred. Further, as a treatment method, it is sufficient to simply throw the above reaction product into water or alcohol. [Examples of the invention] Example 1 In a 300 ml separable flask equipped with a rectification device, a stirring device, and an argon gas blowing tube, 2,
6-dichlorobenzonitrile 8.6g (0.05mol)
and 7.928g of 2,7-dihydroxynaphthalene
(0.0495 mol), potassium carbonate 8.3g (0.06 mol),
Add 100 ml of sulfolane and 50 ml of toluene and heat at 160°C for 1.5 hours while blowing argon gas.
The reaction was carried out at 200°C for 2 hours. After the reaction is complete,
The polymer was precipitated in methanol and ground in a Warning blender. Then add 1 part of the crushed material to water.
and methanol 1 and dried to obtain a crystalline polymer. The yield of the polymer was 12.8 g, a yield of 99%. In addition, 0.2 using p-chlorophenol as a solvent
The reduced viscosity [ηsp/c] (measured in the following examples as well) at 60°C of a solution with a concentration of g/dl is 1.00.
It was dl/g. A film was made by press molding using this polymer, and as a result of infrared absorption spectrum (IR) analysis using this film, it was found that 3030 cm ^-1
and the C-H bond of the benzene ring at the position of 830 cm ^-1 ,
C-C bond of benzene ring at position 1590cm ^-1 , 1240
Absorption due to the presence of an aromatic ether bond at the cm ^-1 position and a nitrile at the 2220 cm ^-1 position was observed. For thermal properties, glass transition temperature (Tg)
is 220℃, melting point is 350℃, thermal decomposition onset temperature (Td)
The temperature was 520℃ (in air). Regarding the mechanical properties of this polymer film,

【table】

[Table] It was. Next, the solvent resistance of this polymer was examined, and it was found to be insoluble in the following solvents: acetone, methanol, toluene, methylene chloride, and chloroform. Furthermore, a lighter's flame was applied to this polymer film.
After 10 seconds of exposure, when the flame was removed, the flame quickly extinguished, and no melt dripping was observed, indicating good flame retardancy. Example 4 In a separable flask similar to Example 1, 2,
6-dichlorobenzonitrile 17.201g (0.1mol)
and 15.859g of 2,7-dihydroxynaphthalene
(0.099 mol), potassium carbonate 16.58g (0.12 mol),
100 ml of sulfolane was added, and the mixture was reacted at 220°C for 2.5 hours while blowing argon gas. After the reaction was completed, the same treatment as in Example 1 was carried out to obtain 25.7 g of polymer.
(yield 100%). The reduced viscosity [ηsp/c] of this polymer was 1.28 dl/g. The IR analysis results are the same as in Example 1, Tg is 220℃, Td is 520℃
It was hot. Moreover, the solvent resistance and flame retardance were the same as in Example 1. [Effects of the Invention] As is clear from the above explanation, the crystalline polymer of the present invention has excellent heat resistance, mechanical strength, flame retardance, and solvent resistance, and is suitable for electrical and electronic equipment. ,
It is useful as a material for various mechanical parts.

Claims (1)

[Claims] Primary formula: A crystalline polymer having a repeating unit represented by: and having a reduced viscosity of 0.8 dl/g or more at 60° C. in a solution of parachlorophenol at a concentration of 0.2 g/dl. Quadratic formula: (In the formula, X represents a halogen atom.) A dihalogenobenzonitrile represented by the following formula: (In the formula, M represents a hydrogen atom or an alkali metal.) When M represents a hydrogen atom, dihydroxynaphthalene or an alkali metal salt thereof is added with the alkali metal salt in the presence of a solvent. reaction, and then treating the resulting reaction product with water or alcohol, according to the following formula: A method for producing a crystalline polymer having a repeating unit represented by the following formula and having a reduced viscosity of 0.8 dl/g or more at 60°C in a solution having a concentration of 0.2 g/dl using parachlorophenol as a solvent. Cubic formula: (In the formula, R represents any one of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, an arylalkyl group, and a cyano group.) Claims in which a monovalent phenol represented by the following is used as a molecular weight regulator. 2. A method for producing a crystalline polymer according to item 2.