JPH03162417A - Polyether-based copolymer and production thereof - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a novel polyether copolymer and a method for producing the same, and more specifically, to a polyether copolymer with particularly excellent heat resistance and a method for producing the same. and a manufacturing method for obtaining it. [Prior art and problems to be solved by the invention] In recent years,
Resins with various structures have been developed as engineering plastics, such as in the automobile field, electric/electronic field, and precision machinery field. It is used in a wide range of fields such as OA equipment and optical communication equipment. However, its performance has not yet reached full satisfaction in all aspects, and the required performance has become more stringent, so the development of new materials is desired. On the other hand, polyether copolymers, which are one of these engineering plastics, are heat-resistant resins, and various proposals have been made regarding these polyether copolymers. For example, JP-A-47-14270 proposes a method for producing an aromatic polyether copolymer in which dinitrobenzonitrile, dihalogenobenzophenone, and dihydric phenol are reacted in the presence of an alkali metal compound. There is. However, according to this method, it is not possible to obtain a copolymer with a sufficiently high molecular weight, and the copolymer cannot necessarily be said to have sufficient heat resistance and mechanical strength. Furthermore, in Japanese Patent Application Laid-Open No. 60-235835,
By simultaneously reacting dihalogenobenzonitrile, 4,4'-dihalogenobenzophenone, and an alkali metal salt of dihydric phenol, a repeating unit represented by the following formula (a): and the following formula (b): (b ) (However, Ar in the above formula is a divalent aromatic group.), and the composition ratio of the repeating units represented by the formula (a) is 0.5 or more. A method for producing a copolymer has been proposed. However, since this polyether copolymer is of poor quality, it cannot maintain mechanical strength in the temperature range exceeding the glass transition temperature, and it is difficult to say that it has sufficient heat resistance. be. The present invention has been made to improve the above situation. An object of the present invention is to provide a polyether copolymer that has excellent heat resistance, particularly a sufficiently high glass transition temperature, and is useful as a new material, and a method for efficiently producing the same. [Means for solving "aB"] The configuration of the invention of claim 1 to achieve the above object is as follows:
(1) It consists of a repeating unit represented by the following formula (I); and a repeating unit represented by the following formula (■): (II), and the molar composition or ratio of the repeating unit represented by the formula (1) [(I )
/((I)+(n)11 is from 0.45 to 0.80, and the polyether copolymer has a melt viscosity of 1,000 voids or more at 400°C. The ether copolymer is produced by combining dihalogenobennitrile, 4,4-bis(4-halogenobenzoyl)biphenyl, and 4,4-biphenol in a neutral polar solvent in the presence of an alkali metal compound. The present invention will be described in detail below.

One of the important points in the polyether copolymer according to claim 1 is that the repeating unit represented by the formula (r) and the repeating unit represented by the formula (II) and the molar ratio of the repeating units represented by the formula (I) is 0.45 to 0. It is within the range of aO. When the polyether copolymer is composed of repeating units described above and the molar ratio is within the above range, the polyether copolymer has sufficient chemical resistance, mechanical strength, etc., and has a sufficiently high glass transition temperature. jwIt also has excellent heat resistance. When the molar composition ratio of the repeating unit represented by the formula (I) exceeds 0.80, the polyether copolymer becomes inferior in quality and has poor heat resistance and chemical resistance. On the other hand, if it is less than 0.45, the glass transition temperature of the polyether copolymer becomes low. Further, it is important for the polyether copolymer of the present invention that the melt viscosity at a temperature of 400° C. is t2,00 poise or more. This is because a low molecular weight polyether copolymer having a melt viscosity of less than 1,000 voids cannot achieve sufficient heat resistance and mechanical strength. In addition, in the present invention, for example, as shown in the examples, 3
Although a polyether copolymer having a melt viscosity of 0,000 poise can be obtained, it can still exhibit good moldability. The polyether copolymer of the present invention has, for example, a crystal melting point of about 330 to 400°C, has crystallinity, has a sufficiently high molecular weight, exhibits sufficient heat resistance, and has excellent resistance to solvents and mechanical properties. It has excellent mechanical strength and can be suitably used as a new material in the electrical/electronic equipment field, mechanical field, etc. -Production method of polyether copolymer 1 The polyether copolymer of the present invention is produced according to the method according to claim 2.
Produced by reacting dihalogenobenzonitrinole, 4.4゜-bis(4-halogenobenzo"inole)bi7enyl, and 4.4゛-biphenol in a neutral polar solvent in the presence of an alkali metal compound. Specific examples of the above dihalogenobenzonitrile include 2,6-dihalogenobenzonitrile represented by the following formula; (wherein, X is a halogen atom); 2, dihalogenobenzonitrile represented by -difluorobenzonitrile, 2.←
Dichlorobenzonitrile, 2,4-difluorobenzonitrile, and particularly preferred is 2,6-dichlorobenzonitrile. Next, as for 4,4'-bis(←halogenobenzoyl)biphenyl, there is no restriction on the substituted halogen, but chlorine and fluorine are preferred. That is, 4,4'-bis(4-halogenobenzoyl)biphenyl preferred in the present invention is represented by the following formula. In addition, in the present invention, another polymerization step 4.4
゛-Biphenol is represented by the following formula. The alkali metal compound may be any compound that can convert the 4,r-biphenol into an alkali metal salt, and is not particularly limited, but alkali metal diacids and alkali metal hydrogen carbonates are preferred. Examples of the alkali metal carbonates include lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate,
Examples include cesium carbonate. Among these, preferred are sodium carbonate and potassium carbonate. Examples of the alkali metal hydrogen carbonates include lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate,
Examples include rubidium hydrogen carbonate and cesium hydrogen carbonate. Among these, preferred are sodium hydrogen carbonate and potassium hydrogen carbonate. In the method of the present invention, among the various alkali metal compounds mentioned above, sodium carbonate and potassium carbonate can be particularly preferably used. As the neutral polar solvent,
For example, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide.
N,N-jethylacetamide, N,N-dipropylacetamide, N,N-dimethylbenzoic acid amide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone,
N-isopropyl-2-pyrrolidone, N-inbutyl-2-pyrrolidone, N-n-propyl-2-pyrrolidone, N-n-butyl-2-pyrrolidone, N-cyclohexy-2-pyrrolidone, N-methyl-3-methyl- 2-pyrrolidone, N-ethyl-3-methyl-2-pyrrolidone,
N-methyl-3.4.5-}limethyl-2-pyrrolidone, N-methyl-2-piperidone, N-ethyl-2-
piperidone, N-improvir-2-piperidone, N-
Methyl-6-methyl-2-piperidone, N-methyl-3
-Ethylpiperidone, dimethyl sulfoxide, diethyl sulfoxide, 1-methyl-1-oxosulfolane, 1
-ethyl-1-oxosulfolane, 1-phenyl-1-
Examples of the dihalogenobenzonitrile include oxosulfolane, N,N-dimethylimidazolidinone, and diphenylsulfone. The molar ratio of the dihalogenobenzonitrile to the total amount is from 45 to 0.80, and the ratio of the alkali metal compound used is usually 1. 01-2.5
0 equivalent, better ratio is 1.02 to 1.20 equivalent. There is no particular restriction on the amount of the neutral polar solvent used, but usually the dihalogenobenzonitrile and the 4.
The amount is selected in the range of 200 to 2,000 parts by weight per 100 parts by weight of the 4°-biphenol and the alkali metal compound. In the method of the present invention, there is no particular restriction on the order of polymerization, but generally dihalogenobenzonitrile and
, 4゜-bis(4-halogenobenzoyl)biphenyl and 4,4゛-biphenol are simultaneously charged and reacted, or dihalogenobenzotolyl and 4,4゜-biphenol are reacted and then the reaction obtained. 4 living things
, 4°-bis(4-halogenobenzoyl)biphenyl. In the method of the present invention, the molar ratio of the total amount of bis(←halogenobenzoyl)biphenyl and dihalogenobenzonitrile to the amount of 4,1-biphenol used is 0.99 to 1.02, preferably 1.00. ~
Set it to 1.01. The reaction temperature is usually 150 to 380°C, preferably 180°C.
The temperature is in the range of ~330°C. ．． If the reaction temperature is less than 150°C, the reaction rate is too slow to be practical, and if it exceeds 380°C, side reactions may occur. Further, the reaction time for this series of reactions is usually 0.1 to 10 hours, preferably 1 hour to 5 hours. After completion of the reaction, a polyether copolymer is obtained by separating and purifying the polyether copolymer from the resulting neutral polar solvent solution containing the polyether copolymer according to a known method. Can be done. In this way, the polyether copolymer according to claim 1 can be efficiently produced through simple steps. [Examples] Next, the present invention will be explained in more detail based on Examples. (Example 1) Internal volume 300 equipped with a Dean-Starck trap filled with toluene, a stirring device and an argon gas blowing tube
mJl reactor, 2,6-dichlorobenzonitrile 3
．． 440 g (0.02 mol), biphenol 7.3
66 g (0.04 mol), potassium carbonate 6.634
g (0.048 mol) and 80 mM of N-methylpyrrolidone were added, and the temperature was raised from room temperature to 195°C over 1 hour while blowing argon gas. After raising the temperature, a small amount of toluene was added to remove viable water by azeotropy. Next, after carrying out a reaction at a temperature of 195°C for 40 minutes,
A solution of 7.968 g (0.020 mol) of 4,4°-bis(4-fluorobenzoyl)biphenyl in 120 mjL of N-methylpyrrolidone was added, and the reaction was further carried out for 1 hour and 30 minutes. After the reaction, the raw material was pulverized using a blender (manufactured by Warning Co., Ltd.), washed with water and methanol in that order, and then dried to obtain 16.5 g of white powdery raw material. When we conducted IR measurements on this biomaterial, we found that 2.22
The absorption by the nitrile group at the 0 cm-' position is 1,65
The absorption by the carbonyl group at the 0 cm-1 position is 1,2
Absorption due to ether bond was confirmed at the position of 40 cm-1. From these results and the results of elemental analysis, this product was confirmed to be a polyether copolymer consisting of repeating units with the following structure. The yield of this polyether copolymer was 100% based on the above yield. However, (I) / ((I) + (II))
=0.5 When the properties of this polyether copolymer were measured, the melt viscosity (zero shear viscosity) at a temperature of 400°C was 32,000 poise, and the glass transition temperature was 1.
96℃, melting point 389℃, thermal decomposition start temperature '560℃
(5% weight loss in air). An attempt was made to measure the viscosity of the solution, but it was impossible to measure as it did not dissolve in any organic solvent. In addition, when a press film of this copolymer was prepared at 400°C and exposed to a lighter's flame to test its flame retardance, the flame quickly extinguished and there was no melting and dripping. In addition, a test piece was injected or shaped from this polyether copolymer and its mechanical strength was measured in accordance with ASTM D-638, and the following results were obtained. Tensile strength: 1100 kg/cm2 Tensile modulus: 35,000 kg/cm2
Elongation: 90% (Example 2) In a separable flask with an internal volume of 300+nfL equipped with an argon gas blowing tube, a Wl stirring device, and a distillation device, 4
, 4′-bis(4-fluorobenzoyl)biphenyl 9
．． 562 g (0.024 mol). 2.6-dichlorobenzonitrile 2.064 g (0.012 mol). 4.4'-biphenol 7.366 g (0
．． 04 mol), anhydrous potassium carbonate 6.081 g (0
．． 044 mol) and 80 g of diphenylsulfone were added.
The reaction was performed at 190°C for 45 minutes, at 250°C for 20 minutes, and at 330°C for 1 hour. After the reaction, the raw materials were ground in a blender in acetone, and the pulverized product was washed with acetone, water, and acetone in this order to obtain 16.4 g of a white powdery polyether copolymer.
(yield 99%). Measurement of the properties of this copolymer revealed that the melt viscosity (zero shear viscosity) at a temperature of 400°C was 26,000 poise, the glass transition temperature was 191°C, the melting point was 378°C, and the thermal decomposition onset temperature was 561°C.
(5% weight loss in air). Elemental analysis was conducted in the same manner as in Example 1, and it was confirmed that this copolymer was a polyether copolymer consisting of repeating units represented by (I) and (II) in Example 1. Ta. The proportions of repeating units were as follows. (I) / ((I) + (TI))
=0.3 (Example 3) In Example 1, the amount of 2,6-dichlorobenzonitrile used was 3,784 g (0.022 mol), 4.4
A polyether copolymer was produced in the same manner as in Example 1 except that the proportion of '-bis(4-fluorobenzoyl)biphenyl used was changed to 7,172 g (0.018 mol). The resulting polyether copolymer had a melt viscosity of 19,000 voids and a glass transition temperature of 198 at 400°C.
℃, the melting point was 385℃, and the thermal decomposition temperature was 555℃. The proportions of repeating units were as follows. (I) / ((I) + (II)) = 0.5
5 (Example 4) In Example 1, the amount of 2,6-dichlorobenzonitrile used was 4,816 g (0.028 mol) and 4,6-dichlorobenzonitrile.
A polyether copolymer was produced in the same manner as in Example 1 except that the proportion of 4°-bis(4-fluorobenzoyl)biphenyl used was changed to 4,781 g (0.012 mol). The resulting polyether copolymer had a melt viscosity of 13,000 poise and a glass transition temperature of 201 at 400°C.
'l:! The melting point was 395°C, and the thermal decomposition temperature was 552°C. The proportions of repeating units were as follows.
(r) / { (I) + (II) ) =0.7
[Effects of the Invention] According to the present invention, a practical polyether copolymer having excellent mechanical strength, chemical resistance, solvent resistance, etc. and particularly excellent heat resistance, and the efficient production thereof. We can provide methods for doing so. Therefore, the present invention is important as it provides engineering plastics that are useful as materials in various fields such as electricity, electronics, machinery, and chemistry.

Claims (2)

[Claims] (1) The following formula (I); ▲There are mathematical formulas, chemical formulas, tables, etc.▼ The repeating unit represented by (I) and the following formula (II); ▲Mathematical formula,
There are chemical formulas, tables, etc. ▼ Consisting of repeating units represented by (II), the molar composition ratio of repeating units represented by formula (I) [(I)/{(
I)+(II)}] is from 0.45 to 0.80, and has a melt viscosity at 400°C of 1,000 poise or more. (2) Dihalogenobenzonitrile and 4,4-bis(4
-Halogenobenzoyl)biphenyl and 4,4-biphenol are reacted in a neutral polar solvent in the presence of an alkali metal compound, the method for producing a polyether copolymer according to claim 1. .