JPH0463899B2 - - Google Patents

Description

[Detailed description of the invention]

[Technical Field of the Invention] The present invention relates to a new copolymer and a method for producing the same, and more particularly to a new copolymer and its production method that have better mechanical properties, especially elongation and impact strength, than conventional cyanoaryl ether polymers. Regarding the manufacturing method. [Technical background of the invention and its problems] Conventionally, as a cyanoaryl ether polymer, dihalogenobenzonitrile and hydroquinone or biphenol have been used as disclosed in JP-A-59-206433 (UCC patent). Cyanoaryl ether polymers obtained as starting materials are known. This polymer has excellent mechanical properties and heat resistance. However, such polymers are not necessarily satisfactory in terms of properties, such as mechanical properties, required of materials for electronic and electrical equipment and mechanical parts. Therefore, it is desired to develop a cyanoaryl ether polymer having better mechanical properties than ever before. [Object of the invention] The present invention answers the above-mentioned needs,
The object of the present invention is to provide a new crystalline copolymer that has better mechanical properties, especially elongation and impact strength, than conventional cyanoaryl ether polymers, and a method for producing the same. [Summary of the Invention] The novel crystalline copolymer of the present invention has the following formula: k repeating units, and the following formula: (In the formula, Ar is

【formula】

[Formula] or

[Formula]) has l repeating units represented by (however, each kl represents a number satisfying the relationship of 0.03≦l/k+l≦0.1), and the concentration using p-chlorophenol as a solvent.
Reduced viscosity [ηsp/
c] is 1.2 dl/g or more, and the manufacturing method thereof is as follows: (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.) Hydroquinone or its alkali metal salt; , Ar is

【formula】

[Formula] or

When M represents a hydrogen atom, a divalent phenol or its alkali metal salt represented by [formula] is added to the above formula () and formula () in the presence of a solvent. The reaction product is then treated with water or alcohol. In the case of the novel crystalline copolymer of the present invention, a repeating unit of the formula () or a connected body formed by appropriately connecting a plurality of repeating units in a linear chain, and a repeating unit of the formula ()
One repeating unit or a linkage formed by appropriately connecting a plurality of repeating units in a linear chain are connected to each other in a disordered or ordered linear chain. In this copolymer, the total numbers k and l of each repeating unit must satisfy the relationship 0.03≦l/k+l≦0.1. When l/k+l is less than 0.03, no improvement in elongation and impact strength is observed, and
When it exceeds 0.1, the obtained copolymer becomes amorphous, which is not preferable. Preferably, the relationship is 0.05≦l/k+l≦0.1. The copolymer of the present invention has a reduced viscosity (ηsp/c) of 1.2 dl/g at 60°C of the resin solution when the copolymer is dissolved in parachlorophenol to a concentration of 0.2 g/dl. It is a copolymer having a molecular weight as above. Reduced viscosity is 1.2dl/g
If the degree of polymerization is less than this, the copolymer will have poor mechanical strength and heat resistance, and will be impractical. The copolymer of the present invention is produced as follows. That is, dihalogenone benzonitrile represented by the following formula (), an alkali metal salt of hydroquinone represented by the formula (), and an alkali metal salt of a divalent phenol represented by the formula () are blended in the ratios described below, and It is dissolved in a solvent and reacted under the conditions described below. In the compound of formula (), F and Cl are particularly preferable as the halogen X, and specific examples thereof include 2,6-dichlorobenzonitrile,
Examples include 2,4-dichlorobenzonitrile, 2,6-difluorobenzonitrile, and 2,4-difluorobenzonitrile. In each of the compounds of formula () and formula (), M may be any alkali metal, with Na and K being particularly preferred. Formula () and the compound of formula () are salts prepared when M is a hydrogen atom, or by neutralization reaction of a compound that is a hydrogen atom and an alkali metal salt. Alkali metal salts used in neutralization reactions include:
Examples include potassium carbonate and potassium hydroxide. In addition, when the compound of formula () and () is a hydrogen atom, an alkali metal salt as described above is added together and reacted.In that case, the amount of addition of the alkali metal salt is determined by the formula () or It is preferable to use an equimolar amount or a slightly larger amount than the compound of formula ().The amount of each compound is j′ mole of the compound of formula (), and k′ mole of the compound of formula (). ,
Assuming that the amount of the compound of formula () is l' mole, it is sufficient that the relationship j'=k'+l' is approximately satisfied. Next, the above k' and l' need to satisfy the relationship 0.03≦l'/k'+l'≦0.1, corresponding to the above relationship 0.03≦l/k+l≦0.1. The reaction is then carried out in a solvent. Examples of the solvent used include neutral polar solvents such as dimethyl sulfoxide, sulfolane, diphenyl sulfone, dimethylacetamide, and N-methylpyrrolidone, and the amounts used are as follows: formula (), formula (), formula () It is sufficient that the amount is sufficient to dissolve each compound. Reaction temperature is 100-350℃, preferably 150-280℃
°C, reaction time is 0.1 to 8 hours, preferably 1 to 6 hours.
It's time. Further, the reaction may be carried out under normal pressure or slightly increased pressure. In addition, if necessary, as a molecular weight regulator in this process, the following formula: (In the formula, R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, an arylalkyl group, or a cyano group.) It is preferable to add a monovalent phenol represented by the following formula. The monovalent phenol represented by the formula () is:
for example,

【formula】

【formula】

[Embodiments of the invention]

Example 1 In a separable flask with an internal volume of 500 ml equipped with a rectification device, a stirring device, and an argon gas blowing tube,
2,6-dichlorobenzonitrile 17.201g (0.1
mole), 2,7-dihydroxynaphthalene 1.586
(0.01 mol), hydroquinone 9.811g (0.09 mol),
Potassium carbonate 16.585g (0.12mol), Sulfolane
200 ml and toluene 100 ml were added, stirred while blowing argon gas, heated to 160°C for 1.5 hours, and further heated to 200°C for 5 hours to react. After the completion of the polymerization reaction, the product was poured into water to precipitate and collect the copolymer, which was pulverized using a Warning blender, washed three times with hot water 3.5 times, and finally dried under reduced pressure at 140°C overnight. I went there. The yield of the obtained copolymer was 21.3 g (yield 100%). In order to examine the degree of polymerization of the obtained copolymer, p-
At a concentration of 0.2g/dl using chlorophenol as a solvent
The reduced viscosity [ηsp/c] at 60°C was measured, and the value of k/k+l was also measured, and these results are shown in the table. Next, by injection molding using this copolymer,
A molded article was prepared, and the mechanical properties of the copolymer were investigated using this molded article. That is, using Autograph IS-5000 manufactured by Shimadzu Corporation as a tensile tester, the tensile speed was 1 mm/
The following characteristics were measured at min, and the results are shown in the table. Yield strength (measured in accordance with ASTM D 638) Breaking strength (measured in accordance with ASTM D 638) Elastic modulus (measured in accordance with ASTM D 638) Elongation (measured in accordance with ASTM D 638) Izot impact strength (ASTM D 256
(using a notched test piece), and the results are shown in the table. Regarding thermal properties, glass transition temperature, melting point,
The thermal decomposition onset temperature was measured and the results are shown in the table. Example 2 In Example 1, 10.461 g of hydroquinone
(0.095 mol), 2,7-dihydroxynaphthalene
A copolymer was produced in the same manner as in Example 1, except that 0.801 g (0.005 mol) was used, and measurements were carried out in the same manner. The yield of the obtained copolymer was 21.2 g (yield 100%). Example 3 Example 1 except that 1.602 g (0.01 mol) of 1,6-dihydroxynaphthalene was used instead of 2,7-dihydroxynaphthalene.
A copolymer was prepared in the same manner as above and measurements were carried out in the same manner.
The yield of the obtained copolymer was 21.4g (yield 100%)
It was hot. Example 4 A copolymer was produced in the same manner as in Example 1, except that 0.551 g (0.005 mol) of resorcinol was used in place of 2,7-dihydroxynaphthalene, and measurements were carried out in the same manner. The yield of the obtained copolymer was 20.9 g (yield 100%). Comparative Example In Example 1, 11.01g of hydroquinone was added without using 2,7-dihydroxynaphthalene.
A polymer was produced in the same manner as in Example 1, except that (0.1 mol) was used, and measurements were carried out in the same manner. The yield of the obtained polymer was 20.9 g (yield 100%). The above results are summarized in the table.

〔Effect of the invention〕

As is clear from the above examples of the invention, the copolymer of the present invention has superior mechanical properties, especially elongation and impact strength, than conventional cyanoaryl ether polymers, and is suitable for use in electronic and electrical equipment and mechanical parts. It is useful when applied to materials such as

Claims (1)

[Claims] Linear formula: k repeating units, and the following formula: (In the formula, Ar represents [Formula] [Formula] or [Formula]) There are l repeating units shown by ) and the concentration using P-chlorophenol as a solvent
Reduced viscosity [ηsp/
c] is 1.2 dl/g or more. 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.) Hydroquinone or its alkali metal salt represented by the following formula: MO-Ar-OM ... () (In the formula, M represents a hydrogen atom or an alkali metal) , Ar represents [Formula] [Formula] or [Formula]) In the case where M in the above formula () and formula () represents a hydrogen atom, an alkali metal salt is added and a solvent is added. characterized by reacting in the presence of and then treating the resulting reaction product with water or alcohol, with the following formula: k repeating units, and (In the formula, Ar represents [Formula] [Formula] or [Formula]) It has l repeating units shown by (However, k and l each satisfy the relationship 0.03≦l/k+l≦0.1 (expressing a number) and the concentration using P-chlorophenol as a solvent
Reduced viscosity [ηsp/
c] is 1.2 dl/g or more. 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) 2. A method for producing a crystalline copolymer according to item 2.