JPS60235835A - Production of cyanoaryloxy copolymer - Google Patents

Abstract

PURPOSE:To obtain the titled high-MW copolymer excellent in heat resistance, mechanical strength, etc., by reacting a dihalogenobenzonitrile with a 4,4'-dihalogenobenzophenone and an alkali metal salt of a dihydric phenol in a solvent. CONSTITUTION:A dihalogenobenzonitrile of formula I (wherein X is halogen), e.g., 2,6-dichlorobenzonitrile, with a 4,4'-dihalogenobenzophenone of formula II(e.g., 4,4'-difluorobenzophenone) and an alkali metal salt of a dihydric phenol of formula III (wherein Ar is a group of formula IV, V or the like), e.g., sodium salt of 4,4'-biphenol, in a solvent (e.g., sulfolan). The obtained product is treated with water or an alcohol to obtain the purpose cyanoaryloxy copolymer having repeating units of formulas VI and VII.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to a method for producing a cyanaryloxy copolymer having a sufficiently large molecular weight.

[Technical background of the invention and its problems]

Various cyanaryloxy copolymers have been disclosed in JP-A-47-
No. 14270, they are prepared by reacting dinitrobenzonitrile with dinologenopenzophenone and dihydric phenol in the presence of an alkali metal salt. However, according to this method, there are problems in that the molecular weight of the obtained copolymer is not large enough and the heat resistance and mechanical strength are not necessarily sufficient.

[Purpose of the invention]

The present invention aims to solve the above-mentioned conventional problems and provide a method for producing a shea/aryloxy copolymer having a sufficiently high molecular weight, good heat resistance, and excellent mechanical afterglow. .

[Summary of the invention]

The method for producing the cyanaryloxy copolymer of the present invention includes:
Dihalogenopenzonitrile 4,4'-dihalogenobenzopheno/ is reacted with an alkali salt of a dihydric phenol in the presence of a solvent, and the resulting product is then treated with alcohol or water. Preferably, a -hydric phenol or mono)rogenobenzonitrile is used as a molecular weight regulator.

To specifically explain the present invention, dihalogenobenzonitrile represented by (wherein X represents a halogen atom) and 4,4'-dihalogenobenzonitrile represented by (wherein X has the same meaning as above) A halogenobenzophenone and an alkali metal salt of a dihydric phenol represented by the following formula: MO-Ar-OM - (m represents a divalent hydrocarbon group having 1 to 13 carbon atoms) are reacted in the presence of a solvent. , and then the resulting reaction product is treated with water or alcohol to form a seven-return unit represented by N (wherein Ar has the same meaning as above), resulting in the following formula: Ni〇-Ar-0( Kohi CO (represents an integer that satisfies the relationship of one repeating unit represented by Koto (V) (in the formula, Ar has the same meaning as above)), the terminal group is a prime atom, and the number of carbon atoms is 1 to 10 alkyl groups, aralkyl groups, or nitrile groups) or ru) is obtained.

In the above production method, an alkali metal salt of a dihalogenobenzonitrile represented by formula (1), a 4,4'-dihalogenobenzophenone represented by formula (10), and a dihydric phenol represented by formula (g) is used. are dissolved in the solvent described below and reacted under the conditions described below.

In the compounds of formulas (1) and (II), as halogen X.

F and OJ are preferred. In the compound of formula (g), M may be any alkali metal, but %Na is particularly preferred.

Further, Ar may be any of those listed above, but Ar is particularly preferred.

The compound of formula (II) is a dihydric phenol represented by HO-Ar-OH (Ar has the same meaning as above) and an alkali metal such as potassium carbonate, sodium carbonate, potassium hydroxide, potassium hydroxide, etc. It can be easily prepared by neutralization reaction with salts and alkali metal hydroxides.

In addition, in proceeding with the reaction of the present invention, the compound of formula (g) is not used from the beginning of one reaction, and for example, the above-mentioned dihydric phenol and the above-mentioned alkali metal salt or alkali metal hydroxide are added to the reaction system. You may also add them together. In this case, as one reaction progresses, a compound of formula (to) will be produced in the reaction system.

The amount of each compound to be used is determined based on the relationship between polymerization and failure of the desired polymer. Number of moles of the compound of formula (1) used Th
mt sThe number of moles of the compound of formula (It) used is m2, and the number of moles of the compound of formula (It) is
If the number of moles of the compound used is tms, then m3-=m
It is sufficient if the relationship 1 + m z is satisfied, but it is not inconvenient even if this relationship collapses.

The reaction is carried out in a solvent. Various organic solvents can be used as the solvent, such as dimethyl sulfoxide, sulfola, diphenyl sulfone, N-methylpyrrolidone, and dimethylacetamide, and the amount used can be expressed by formula (■), formula (■), The amount may be sufficient as long as it dissolves each compound of formula (to).

The reaction temperature is 150-300°C, preferably 180-28°C.
0°C, reaction time Vi 1.0 to 5.0 hours, preferably 2
It is 0 to 30 hours. Further, the reaction may be carried out under normal pressure or under slightly increased pressure.

In this process, it is preferable to add m phenol modules or monohalogenobenzonitrile as a molecular weight regulator. Examples of the monohydric phenol used include p-tert-butylphenol, cumylphenol, and p-phenylphenol, and examples of the monohalogenobenzonitrile include p-chlorobenzonitrile and p-fluorobenzonitrile. Moreover, the amount used 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 and 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 reaction product into gold water or alcohol.

The polymer obtained by using the Ha method for cyanaryloxy polymer of the present invention is composed of one repeating unit of the formula (product) or a plurality of repeating units suitably connected in a linear chain. A linkage body and a linkage body formed by appropriately connecting one repeating unit of formula (V) or a plurality of repeating units in a linear chain are connected to each other in a disordered or ordered linear chain, The terminal end of the entire group represents an alkyl group, an aralkyl group, or a nitrile group having 1 to 10 carbon atoms. Of these, O
f-]3 OH3 OH3 In this polymer, if each repeating unit (good), (V) is less than 0, the molecular weight of the obtained polymer will decrease by 0.9
If it exceeds 8, the fluidity during molding will decrease.

The copolymer obtained by K in this way is
- dissolved in methylpyrrolidone to a concentration of 0.2 fl
/dl, the reduced viscosity v (ηsp/a) of this resin solution at 30°C is 0.4 di/g or more! There is a copolymer with l. This ηsp/c
When the degree of polymerization is less than 0.4 dl/g, the copolymer has a low molecular weight and therefore has low heat resistance and low mechanical strength.

[Embodiments of the invention]

Example 1 A 30 oml sevarapuru flask equipped with an argon gas blowing tube, a rectification device, and a stirring device contains 2,6-cyclopenzonitrile 7,74, pi' (0,04
5 mol) 4.4'-cyfur size lopenzophenone 1.0
91y (o, o o s mol), 4,4'-biphenol 93.9 (0,05 mol), potassium carbonate 7,0
59 (0.05 mol) and sulfolane were charged and stirred while blowing argon gas, and the reaction was carried out at 230°C for 30 minutes and then at 250°C for 2 hours and 30 minutes. After the reaction was completed, the product was pulverized in methanol using a Warlink blender, washed with 1/1 part of hot water and 1/1 part of M methanol, air-dried, and vacuum-dried at 120°C for 8 hours. As a result, 14.6p of copolymer
(yield: 100 cm).

The reduced viscosity at 30°C of a 0.2 ji/al mW N-methylpyrrolidone solution of this polymer [ηlIp/c
), when infrared absorption spectrum (IR) analysis of this copolymer was performed, it was found that 3030 cm and 830 cm-
'Absorption due to C-H bond of benzene ring, 1590 (7
)-1 due to the C-0 bond of the benzene ring, 2220
Absorption by aromatic nitriles at , absorption by aromatic ketones at 1650 cm-'1, and absorption by aromatic ketones at 1240 cm-'
Absorption by aromatic ether was observed. In addition, as a result of thermal analysis of this polymer, the glass transition temperature (Tg)
is 186°C, and the thermal decomposition onset temperature (Td) Vi, s6
z°C (in air, the same applies hereafter).

Furthermore, when the solubility in common solvents was examined using a film obtained by press-molding this copolymer, it was found to be insoluble in acetone, methylene chloride, chloroform, carbon tetrachloride, and ethanol. Further, when the flame of a lighter was applied to this film for 10 seconds and the flame was moved away, the flame immediately went out, and no molten dripping was observed.

Example 2 In a separable flask as in Example 1, 5.564/(0.04 mol) of 2°6-cyfluorohenzonitrile and 2,1829 4,4'-difluorobenzophenone were added.
(0.01 mol), 4,4'-biphenol 9.31
! (0,05 mol), potassium carbonate 89849 (0,0
65 Mok), 7100 d of N-mefk pyrrolide, and 4011 tl of toluene were charged, and the reaction was carried out at 150° C. for 2 hours to remove produced water and toluene by azeotropic distillation. After that, the temperature of the reaction system was raised to 190°C and
After the reaction was completed, 15.9 g of a copolymer was obtained in the same manner as in Example 1 (yield: 98%). The reduced viscosity of this copolymer was 0.8. Further, the IR analysis results were the same as in Example 1. As a result of thermal analysis, the T of this polymer
g was 203°C, and Td was 512°C. Furthermore, the solvent resistance and flame retardance were the same as in Example 1.

Example 3 Example 2 except that 0.15 p (0,001 mol) of p-tert-butylphenol was added as a molecular weight regulator.
Copolymer 15.09 was obtained in the same manner as = 0.8, Tg
= 198°C, Td = 529°C. (2) The test results for evaporation analysis, solvent resistance, and flame retardancy were all the same as in Example 1.

Example 4 As a dihydric phenol, 10.914 g of 4,4'-thiobisphenol was used instead of 4,4'-biphenol (
0.05 mol) 1 - The tl used was the same as in Example 1, and the copolymer 16.2. Obtain p fc (yield 100% Oni Tg
= 142°C, Td = 496°C. (2) The test results for evaporation analysis, solvent resistance, and flame retardancy were all the same as in Example 1.

Example 5 Example #1 using t,2,2-his(4-hydroxyphenyl)propane 1x, 4.9 (o, os mol) instead of 4,4'-biphenol as the dihydric phenol 16.7 fl of a copolymer was obtained in the same manner as in 1 (
Yield: 100 cm). Reduced viscosity [η@p/c) 0.42
468℃. The Ih analysis, solvent resistance, and 4 flammability test results were all the same as in Example 1.

〔Effect of the invention〕

As is clear from the above explanation, the copolymer obtained according to the method for producing a cyanaryloxy copolymer of the present invention has a sufficient molecular weight, has good git thermal properties, and has good mechanical strength. In addition to this, it has excellent bath agent resistance and flammability, so it can be used as a material for various electrical and electronic devices and mechanical parts that require heat resistance, solvent resistance, and nonflammability. Useful.

Claims (1)

[Claims] 1. Dihalogenobenzonitrile 4.4'-Dihalogenobenzoneenone and an alkali salt of a dihydric phenol are reacted in the presence of a solvent, and then the obtained product is reacted with an alcohol or A method for producing a cyanaryloxy copolymer, which is treated with water. 2. The method for producing a cyanaryloxy copolymer according to claim 1, in which m phenols or monohalogenobenzonitrile are used as the molecular weight regulator.