JPH03285916A - Polyether copolymer and production thereof - Google Patents

Abstract

PURPOSE:To obtain the subject copolymer containing three specific kinds of recurring units at specific ratios and having excellent mechanical strength, moldability, etc., in high efficiency by reacting specific components such as dihalogenobenzonitrile in a neutral polar solvent in the presence of an alkali metal compound. CONSTITUTION:A compound of formula I (X is halogen; n is 1-2) is made to react with a dihalogenobenzonitrile of formula II, a compound of formula III (Y is group of formula IV, etc.) and 4,4'-biphenol in a neutral polar solvent in the presence of an alkali metal compound to obtain the objective copolymer having a melt viscosity of >=1,000 poise at 400 deg.C and containing (A) the recurring unit of formula V, (B) the recurring unit of formula II and (C) the recurring unit of formula III at molar ratios A/(A+B+C) of 0.65-0.85, (B+C)/(A+B+C) of 0.15-0.35, B/(A+B+C) of >=0.85 and C/(A+B+C) of >=0.05.

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a novel polyether copolymer and a method for producing the same, and more specifically, to a polyether copolymer useful as a material in the electric/electronic equipment field, mechanical field, etc. , and a manufacturing method that can efficiently obtain it through simple steps. [Prior art and problems to be solved by the invention 1i] In recent years, plastics with various structures have been developed as engineering resins, such as in the automobile field, electric/electronic field, precision machinery field, OA equipment field, optical communication equipment field, etc. It is used in a wide range of fields. However, its performance has not yet reached full satisfaction in all aspects, and furthermore, the required performance has become stricter, so the development of new materials is desired. On the other hand, a polyether copolymer, which is one of these engineering resins, has particularly excellent heat resistance, and various proposals have been made regarding this resin as well. For example, in Japanese Patent Application Laid-open No. 47-14270,
A method for producing an aromatic polyether copolymer has been proposed in which dinitrobenzonitrile, dihalogenobenzophenone, and dihydric phenol are reacted in the presence of an alkali metal compound. However, according to this method, only a low molecular weight copolymer with a melt viscosity of 200 voids or less at 400°C can be obtained, and the resulting copolymer does not necessarily have sufficient heat resistance or mechanical strength. hard. Furthermore, in JP-A No. 60-235835, by simultaneously reacting dihalogenobenzonitrile, 4,4'-dihalogenobenzophenone, and an alkali metal salt of divalent phenol, the following formula (a) is obtained. It consists of a repeating unit represented by: N and a repeating unit represented by the following formula (b);0 () (however, Ar in the above formula is a divalent aromatic group), A method has been proposed for producing a polyether copolymer having a composition ratio of repeating units represented by 0.5 or more. However, since this polyether copolymer is amorphous, it cannot maintain mechanical strength in a temperature range exceeding the glass transition temperature, and cannot be said to have sufficient heat resistance. The present invention has been made based on the above-mentioned vehicle situation. The object of the present invention is to have high mechanical strength by containing a specific proportion of unagigaeshi units with a specific chemical structure.
A novel polyether copolymer that is useful as a new material, has excellent moldability, is crystalline, has excellent heat resistance, and has a high glass transition temperature. It is an object of the present invention to provide a manufacturing method that can efficiently obtain this polyether copolymer. [Means for Solving the Problems] The present inventors have discovered the following: (1) It has excellent properties such as excellent mechanical strength and formability, as well as crystallinity and excellent heat resistance. Precision machinery field, OA
As a result of intensive research to develop a new engineering resin that can be advantageously used in a wide range of fields such as equipment and optical communication equipment, we have discovered a new structural polyester that has a specific repeating unit in a specific composition ratio. After discovering that an ether copolymer is an excellent polymer that satisfies these requirements, and after conducting various studies on how to efficiently produce this polyether copolymer, we discovered a method for copolymerizing specific monomers. We have found that this is an excellent method for practical use that satisfies these requirements, and have completed the present invention based on these findings. That is, 1 the present invention is a repeating unit represented by the linear formula (1); and the repeating unit represented by the following formula (■): (m), and the composition ratio (molar ratio) of the repeating unit represented by the formula (I) [(I)/((I
) + (n) + (m) ) ] or 0.65 to 0.85
In addition, the composition ratio (mole ratio) of the total amount of the repeating unit represented by the formula (I[) and the repeating unit represented by the formula (Ilm)] [((II) + (m) )/( (
I) + (n) + (m) )] is 0.15 to 0
．． 35, and the composition ratio (molar ratio) of the repeating unit represented by the formula (rl) [(n)/((I)+(II)
+ (III) ) ] is 0.05 or more, and the composition ratio (molar ratio) of the repeating unit represented by the formula (m) [
(m)/((I)+(II)+(m))] is 0.05 or more, and the melt viscosity (zero shear viscosity) at a temperature of 400°C is 1.000 poise or more. In addition, as a method for efficiently producing the polyether copolymer of the present invention, the following general formula is used:

[1]: (However, in formula 1, X is a halogen atom, and n is 1 or 2.) A compound represented by the following general formula [2J: (However, in formula 1, X is a halogen atom) Dihalogenobenzonitrile represented by ) and the following general formula

[31; (However, in the formula, X is a halogen atom, and Y represents the same meaning as Y in the above formula (m)) and 4,4'-biphenol. The present invention also provides a method for producing a polyether copolymer, which is characterized in that the reaction is carried out in a neutral polar solvent in the presence of an alkali metal compound. The present invention will be explained in detail below. -Polyether copolymer- One of the important points in the polyether copolymer of the present invention is that the repeating unit represented by the formula (1) and the formula (
Consisting of a repeating unit represented by II) and a repeating unit represented by the formula (m), the composition ratio or molar ratio of the repeating unit represented by the formula (I); [(I)/(
(I)+(II)+(III))] is 0.65~
0.85 and the composition ratio of the total amount of the repeating unit represented by the formula (n) and the repeating unit represented by the formula (m) is a molar ratio; [((II)+(m) )/(
(I)+(II)+(m)) ] Theo, ts ~
Ii of 0.35! This is within the scope of I. The composition ratio of the repeating unit represented by the formula (I) is 0.6
5, and the formula (II) and the formula (m
) The composition ratio of the total amount of repeating units represented by is 0.35
If it exceeds this amount, the polyether copolymer will have insufficient crystallinity. On the other hand, the composition ratio of the repeating units represented by the formula (I) exceeds 0.85, and the composition ratio of the total amount of the repeating units represented by the formula (■) and the formula (III) is 0.15. If it is less than this, the melting point of the polyether copolymer will become too high, leading to a decrease in moldability. Further, the polyether copolymer of the present invention has the above composition ratio, and the composition ratio (molar ratio) of the repeating unit represented by the formula (n), [(II)/((r)+ (
n)+1m))] and the composition ratio (molar ratio) of the repeating unit represented by the formula (m): [(m)/((I)+(
If)+(m))] is also important to be 0.05 or more. If the number of repeating units represented by the formula (IIF) is less than 0.05, the fluidity of the polyether copolymer during melting may decrease, leading to a decrease in moldability. In addition, the repeating unit represented by the formula (m) is 0°05
If it is less than that, the glass transition temperature of the polyether copolymer produced will not be sufficiently high. Furthermore, it is important that the polyether copolymer of the present invention not only have the above-mentioned composition, but also have a melt viscosity (zero shear viscosity) at 400° C. of 1,000 voices or more. This is because a low molecular weight polyether copolymer having a melt viscosity of less than 1.000 voids cannot maintain sufficient heat resistance and mechanical strength. 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 solvent resistance and It is a copolymer with excellent properties such as excellent mechanical strength and moldability, and is used in various electrical and electronic equipment fields such as the automobile field, precision machinery field, OA equipment field, optical communication equipment field, and various machinery. It can be suitably used as a new material in a wide range of fields. Note that specific examples and preferred examples of each unit (benzonitrile group, Y, etc.) in each of the above-mentioned repeating units will be explained in detail with reference to the heptamer compound used in the method of the present invention described later. 1. Method for producing a polyether copolymer - The polyether copolymer of the present invention is not particularly limited in its general production method and can be produced by various methods, but the polyether copolymer of the present invention can be produced by various methods. It can be produced particularly preferably and efficiently according to the method. That is, in the method of the present invention, the general formula [11
A compound represented by the above general formula [2], a compound represented by the above general formula [3], and 4,4'-biphenol (i.e., 4,4°-dihydroxy biphenyl) in a neutral polar solvent in the presence of an alkali metal compound to produce the polyether copolymer of the present invention. In the method of the present invention, X in each of the compounds represented by the general formulas [11, [2] and [3] represents a halogen atom. Specific examples of the halogen atom include:
Mention may be made of fluorine, chlorine, bromine and iodine atoms. Among these halogen atoms, fluorine atoms and chlorine atoms are preferred. In the method of the present invention, the general formula [2
Specific examples of diherogenobenzonitrile represented by 1 include the linear formula: difluorobenzonitrile, 2,4-dichlorobenzonitrile, and 2,4-difluorobenzonitrile, and particularly preferred are 2. 6-dichlorobenzonitrile. The 4,4-biphenol is 4,4°-dihydroxybiphenyl, and is represented by the following formula. (However, X in formula 1 is a halogen atom, and X may be the same type or different.) Various 2,6-cyhalogenobenzonitrile represented by Examples include various 2,4-diherogenobenzonitrile represented by the following formula: (wherein X has the same meaning as above). Among these, preferred is 2,6-dichlorobenzonitrile, 2.6-in the compound represented by the above general formula [1], n is 1 or 2, and X represents a halogen atom. X in the formula may be the same or different; preferred as X is F or 0 as described above. Among the compounds represented by the general formula [11], the compound in which n or 1 is 4,4°-dihalobenzophenone, that is, the following formula (wherein, X represents a halogen atom, and X is the same as each other) It is a compound represented by For example, 4,4°-dichlorobenzophenone, 4,4°-
Examples include difluorobenzophenone. general formula

Among the compounds represented by [11], examples of the compound where n is 2 include 1,4-bis(4-halobenzoyl)benzene, ie, the following formula %(4 fluorobenzoyl)benzene. Specific examples of the compound represented by the general formula [31] are:
There are various types depending on the type of Y, the type of X, and the combination, and examples for each type of Y are as follows. That is, as a compound represented by the general formula [3], a dihalogenodiphenylsulfone represented by the following formula (where X has the same meaning as above), a dihalogenodiphenylsulfone represented by the following formula (however, X has the same meaning as above) ), and its specific examples include various compounds depending on the type and combination of X, but among them, those that can be particularly preferably used include, for example, 1. 4, 4 represented by 4-bis (4-ri (however, X has the same meaning as above))
゛-bis(4-halobenzoyl)diphenyl ether,
4 expressed by the following formula (where X has the same meaning as above)
, 4'-bis(4-halobenzoyl)diphenylthioether, 4 represented by the following formula (Tatashi and X have the same meanings as above)
, 4-bis(4-halobenzoyl)biphenyl, 4 represented by the following formula (where X has the same meaning as above)
, 4'-bis(4-halobenzoyl)diphenylmethane, bis(4-halobenzoyl)naphthalene represented by the following formula (however, X has the same meaning as above), ) bis(4-halobenzoyl)dibenzofuran represented by (However, X has the same meaning as above.) 2
, 5-bis(4-halobenzoyl)pyridine, 1 represented by the following formula (where X has the same meaning as above)
, 4-bis(4-herophenylsulfonyl)benzene,
There are bis(4-herophenylsulfonyl)naphthalenes represented by 3 and the following formula (where X has the same meaning as above). Preferred examples of the dihalogenodiphenylsulfones include 4.4°-dichlorodiphenylsulfone and 4.4°-difluorodiphenylsulfone. Preferred examples of the 4,4'-bis(4-chlorobenzoyl) diphenyl ether include 4,4'-bis(4-chlorobenzoyl) diphenyl ether, 4,4'-bis(4-fluorobenzoyl), and 4,4'-bis(4-chlorobenzoyl) diphenyl ether. Examples include benzoyl) diphenyl ether. Preferred examples of the 4.4°-bis(4-helobenzoyl)diphenylthioether include 4.4′-bis(4-chlorobenzoyl)diphenylthioether, 4°4′-bis(4 -fluorobenzoyl)diphenylthioether and the like. Preferred examples of 4,4'-bis(4-herobenzoyl)biphenyl include 4.
4'-bis(4-chlorobenzoyl)biphenyl, 4.
Examples include 4'-bis(4-fluorobenzoyl)biphenyl. Preferred examples of the 4.4°-bis(4-herobenzoyl)diphenylmethane include 4,4°-bis(4-chlorobenzoyl)diphenylmethane, 4,4′-bis(4-fluorobenzoyl), and 4,4′-bis(4-fluorobenzoyl)diphenylmethane. Examples include benzoyl) diphenylmethane. Preferred examples of the bis(4-herobenzoyl)naphthalene include, for example, 2,6-bis(4-herobenzoyl)naphthalene.
4-chlorobenzoyl)naphthalene, 2,7-bis(4
-chlorobenzoyl)naphthalene, 1,5-bis(4-
Examples include fluorobenzoyl) naphthalene. Preferred examples of the bis(4-herobenzoyl)dibenzofurans include, for example, 2
．． 7-bis(4-chlorobenzoyl)dibenzofuran,
Examples include 2,7-bis(4-fluorobenzoyl)dibenzofuran. Preferred examples of the bis(4-herobenzoyl)dibenzothiophenes include, for example, 2,7
-bis(4-chlorobenzoyl)dibenzothiophene,
Examples include 2,7-bis(4-fluorobenzoyl)dibenzothiphene. Preferred examples of the 2,6-bis(4-herobenzoyl)pyridine include, for example, 2,6-bis(4-herobenzoyl)pyridine.
Examples include bis(4-chlorobenzoyl)pyridine, 2,6-bis(4-fluorobenzoyl) and lysine. Preferred examples of the 1,4-bis(4-herophenylsulfonyl)benzene include, for example,
1.4-bis(4-chlorophenylsulfonyl)benzene, 1.4-bis(4-fluorophenylsulfonyl)
Examples include benzene. Preferred examples of the bis(4-herophenylsulfonyl)naphthalene include, for example, 2,6
-bis(4-chlorophenylsulfonyl)naphthalene,
2.7-bis(4-chlorophenylsulfonyl)naphthalene, l,5-bis(4-chlorophenylsulfonyl)
Examples include naphthalene. Note that the general formulas [11, [21 and

Each of the compounds represented by [3] may be used alone or in combination of two or more. The alkali metal compound is not particularly limited as long as it can convert the 4,4'-biphenol into an alkali metal salt, but alkali metal carbonates 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 carbonate 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. Examples of the neutral polar solvent include N,N-dimethylformamide, N,N-diethylformamide, N,N
-dimethylacetamide, N. N-diethylacetamide, N,N-diethylacetamide, N,N-dimethylbenzoic acid amide, N-methyl-
2-pyrrolidone, N-ethyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-isobutyl-2-pyrrolidone, N-n-propyl-2-pyrrolidone, N-n
-butyl-2-pyrrolidone, N-cyclohexyl-2-
pyrrolidone, N-methyl-3-methyl-2-pyrrolidone, N-ethyl-3-methyl-2-pyrrolidone, N-methyl-3,4,5-trimethyl-2-pyrrolidone, N-methyl-2-piperidone, N-ethyl-2-piperidone,
N-inpropyl-2-piperidone, N-methyl-6-
Methyl-2-piperidone, N-methyl-3-ethylpiperidone, dimethyl sulfoxide, diethyl sulfoxide, l-methyl-1-oxosulfolane, 1-ethyl-1
-oxosulfolane, l-phenyl-1-oxosulfolane, N,N-dimethylimidazolidinone, diphenylsulfone, and the like. The ratio of the dihalogenobenzonitrile represented by the general formula [2], the compound represented by the general formula [11], and the compound represented by the general formula [3] is usually the same as the above 4.
, relative to the amount of 4'-biphenol used. Those compounds (the dihalogenobenzonitrile and the general formula [1]
It is appropriate that the total amount of the compound represented by the formula [3] and the compound represented by the general formula [3] be selected in a molar ratio of 0.98 to 1.02. The usage ratio of the alkali metal compound is 4.4°-
The molar ratio to the amount of biphenol used (however, if 1 mole of the alkali metal compound used is 2 equivalents, generally the equivalent ratio) is 5. Usually, it is appropriate to select a value in the range of 1.03 to 1.25. It is. In addition, at that time, the usage ratio of each of the 100% compound is such that the ratio of the repeating units (I) to (m) in the resulting polyether copolymer falls within the range of the specific composition ratio (molar ratio). Set it so that it fits. The amount of the neutral polar solvent to be used is not particularly limited, but is usually selected in the range of 200 to 000 parts by weight per 100 parts by weight of the raw material and the alkali metal compound. In order to obtain the polyether copolymer of the present invention, a dihalogenobenzonitrile represented by the general formula [2], 4.
After reacting 4'-biphenol with the compound represented by the general formula [31], the reaction product and the compound represented by the general formula [13 (4°4°-dihepenzophenone and h/ or 1°4-bis(4-herobenzoyl)benzene) is preferably employed. For example, in the neutral polar solvent, dihalogenobenzonitrile represented by the general formula [21] and the general formula [3
], the 4゜4゛-biphenol, and the alkali metal compound are simultaneously added and reacted, and then the compound represented by the general formula [1] (4 , 4' dihalobenzophenone and/or 1.
4-bis(4-herobenzoyl)benzene) is added to carry out the reaction. The reaction temperature is usually 150 to 380°C, preferably 18
A series of reactions are carried out at temperatures ranging from 0 to 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. The duration of this series of reactions is usually 0.1 to 10 hours, preferably 1 to 5 hours. After the reaction is completed, the polyether copolymer is separated and purified from the resulting neutral polar solvent solution containing the polyether copolymer according to a known method. Obtainable. In this way, the polyether copolymer of the present invention can be efficiently produced in a simple process. [Examples] Next, examples of the present invention will be shown and the present invention will be explained in more detail. However, the present invention is not limited to these examples, and various modifications and changes can be made without departing from the gist of the present invention. Application is possible. (Implementation Ml) 12.9 g of 2,6-cyclopenzonitrile (0,
0.075 mol), 4.4'-dichlorodiphenylsulfone 21.5 g (0.075 mol), 4゜4'-biphenol 92.1 g (0.50 mol), potassium carbonate 8.
2.9 g (0,6 (1 mol) and N-methyl-2-
840 mJL of pyrrolidone was added, and the temperature was raised from room temperature to 195°C over 40 minutes while blowing argon gas. After raising the temperature, a small amount of toluene was added and the water produced was removed by azeotropic distillation. Next, after carrying out a reaction at 195°C for 30 minutes,
4.4'-difluorobenzophenone 76.4g (0,
15 mol) to 1160 mJ of N-methyl-2-pyrrolidone
A solution containing 1 was added and the reaction was continued for an additional 90 minutes. After the reaction was completed, the mixture was cooled to near room temperature, pulverized by adding water, washed with water and methanol, and then dried. According to the analysis results described below, the obtained solid content was a polyether copolymer, and the yield was 173.7 g (yield g
8%). The results of the IR measurement of the solid content are shown in FIG. From the IR results and the elemental analysis results, the obtained solid content was recognized to be a polyether copolymer consisting of repeating units having the following structure. (Ia) M υ (IIIa) (Ia) : (IIa): (■a)=0.7
: 0.15 : 0.15 When the properties of this polyether copolymer were measured, the glass transition temperature was 190.
°C, melting point: 354 °C, thermal decomposition start temperature: 551 °C (in air, 5% reduction), melt viscosity at 400 °C: 26,000 voids. A tensile test was performed on a test piece obtained by injection molding this polyether copolymer at 400°C according to ASTM D-633.
It was carried out in accordance with the . Tensile strength 980kg/cm"Tensile modulus
31,000kg/cII” growth
40% Also, when this test piece was used to examine its solubility in various solvents, it was found to be insoluble in acetone, chloroform, carbon tetrachloride, methylene chloride, ethanol, toluene, and xylene, and no stress cracks occurred. Ta. Furthermore, when the flame of a lighter was brought close to this test piece for 10 seconds and immediately removed, the flame of the test piece went out immediately and no melt dripping occurred. (Examples 2 to 7) In Example 1, 2,6-dichlorobenzonitrile, 4.4°-dichlorodiphenylsulfone, and 4.
The same procedure as in Example 1 was carried out except that the ratio of 4'-difluorobenzophenone used was changed to that shown in Table 1. Table 1 shows the melt viscosity at 400° C. and thermal properties of the polyether copolymer obtained. According to the results in Table 1, it is understood that as the dichlorobenzonitrile unit increases, the thermal decomposition onset temperature increases, and as the diphenylsulfone unit increases, the glass transition temperature increases. (Example 8) Internal volume 300 m equipped with a Dean-Starck trap filled with toluene, a stirring device, and an argon gas blowing pipe
137 liters of 2,6-cyclopenzonitrile in a reactor.
6g (0,008 mol), 4゜4゛-dichlorodiphenylsulfone 2.297g (o,ooa mol), 4.
4°-biphenol 7.374 g (0.04 mol),
Add 6.634 g (0-048 mol) of potassium carbonate and 80 mJL of N-methyl-2-pyrrolidone, and heat from room temperature to 195°C over 1 hour while blowing argon gas.
The temperature rose to . After raising the temperature, a small amount of toluene was added and the produced water was removed by azeotropy. Next, after carrying out a reaction at 195°C for 30 minutes, 7.736 g (0,024 mol) of 1,4-bis(4-fluorobenzoyl)benzene was reacted with N-methyl-2
- A solution dissolved in 80 mJl of pyrrolidone was added, and the reaction was further carried out for 1 hour. After the reaction is complete, transfer the product to a blender (manufactured by Warning).
After crushing with water and washing with methanol in that order,
After drying, a white powder was obtained. This white powder was found to be a polyether copolymer from the analysis results described below, and the yield was 16.3 g (98% yield). When the IR measurement of the white powder was carried out, it was found to be 2220 am.
Absorption by nitrile group at position -' is 1650cm
-” absorption due to carbonyl group is 1240c■
Absorption due to an ether bond was confirmed at the -1 position. The polyether copolymer obtained from this result and the elemental analysis result was confirmed to be composed of repeating units having the following structure. (Ib) (mb) (Ib) : (nb) : (mb)=0.
6 : 0.2 : 0.2 When the properties of this polyether copolymer were measured, it was found that at a temperature of 400
The melt viscosity (zero shear viscosity) at °C was 31,000 voids, the glass transition temperature was 191 °C, the crystal melting point was 364 °C, and the thermal decomposition onset temperature was 534 °C (5% weight loss in air). An attempt was made to measure the solution viscosity, but the solution could not be measured as it did not dissolve in any organic solvent. We also made a press film at 400℃ and held it close to the flame of a lighter for 10 seconds to check its flame retardancy. When I moved it away, the flame quickly disappeared and there was no melt dripping. Further, the mechanical strength of a test piece obtained by injection molding this polyether copolymer was measured. Tensile strength 930kg/cm"Tensile modulus
31000kg/c■2 elongation
The 60% measurement method was based on ASTM D63B. (Example 9) In Example 8, 0.61HIg (0,004 mol) of 2,6-dichlorobenzonitrile, 4°4'-
3.446g (0,0
The same procedure as in Example 8 was carried out except that the amount was changed to 12 mol). The yield of the obtained polyether copolymer was 17.1 g (
The yield was 100%). When the properties of this polyether copolymer were measured, the glass transition temperature was 191°C, the melting point was 334°C, the thermal decomposition onset temperature was 525°C, and the melt viscosity at 400°C was 37.0°C.
It was 00 voice. An attempt was made to measure the solution viscosity, but it could not be measured as it did not dissolve in any organic solvent. In addition, when a press film was prepared at 400° C. and exposed to a lighter's flame to check its flame retardance, the flame disappeared immediately and there was no melting and dripping. From the results of IR and elemental analysis, it is recognized that the obtained polyether copolymer consists of repeating units having the following structure. (Ib) : (IIb) : (mb)=0
．． 6 = 0.1 : 0.3 Furthermore, the mechanical strength of a test piece obtained by injection molding this polyether copolymer was measured. Tensile strength 910kg/cm" Tensile modulus 31000kg/cm2 elongation
and 90% (Ib) The measurement method was based on ASTM D63B. (Example 10) Instead of 4.4-dichlorodiphenylsulfone, 2,
7-bis(4-fluorobenzoyl)benzofuran 31
．． Polymerization and post-treatment were carried out in the same manner as in Example 1, except that 06 g (0,075 mol) was used to obtain a solid (polymer). According to the analysis results described below, the obtained poly 7- (solid content) is a polyether copolymer, and the yield is 187
g (yield 9g%). The IR measurement results of the polymer (solid content) are shown in FIG. From the IR results and the elemental analysis results, the obtained polymer was recognized as a polyether copolymer consisting of repeating units having the following structure. (Ia) + (IIa): (mc)=0
．． 7: 0.15 + 0.15 When the properties of this polyether copolymer were measured, the glass transition temperature was 1.
The melting point was 92°C, the melting point was 354°C, the thermal decomposition start temperature was 570°C (5% reduction in air), and the melt viscosity at 400°C was 32,000 voids. A tensile test was conducted on a test piece obtained by injection molding this polyether copolymer at 400°C in accordance with ASTM D-638. M (Ia) Tensile strength 950kg/c1 Tensile modulus: 15. (100kg/c ■2 elongation
50% (mc) Also, using this test piece, the solubility in various solvents was investigated and found to be acetone and chloroform. It was insoluble in carbon tetrachloride, methylene chloride, ethanol, toluene, and xylene, and no stress cracks occurred. Furthermore, when the flame of a lighter was brought close to this test piece for 10 seconds and then immediately removed, the quality of the test piece disappeared immediately, and there was no melting and dripping. (Examples 11 to 16) In Example 1, the usage ratios of 2,6-cyclobenzonitrile, 2,7-bis(4-fluorobenzoyl)benzofuran and 4,4'-difluorobenzophenone are shown in Table 2. The same procedure as in Example 1 was carried out except that the proportions shown were changed. Table 2 shows the melt viscosity at 400° C. and thermal properties of the polyether copolymer obtained. (Hereafter, blank space) (Example 17) 22. instead of 4,4'-dichlorodiphenyl sulfone.
6-bis(4-fluorobenzoyl)pyridine 24.2
A solid substance (polymer) was obtained by carrying out the polymerization reaction and subsequent treatment in the same manner as in Example 1 except that 100 g (0.07 S mol) was used. According to the analysis results described below, the obtained polymer (type I) is a polyether copolymer, and the yield is: 1
The amount was 78.6 g (yield: 8%). The IR measurement results of the polymer (solid content) are shown in FIG. Furthermore, this! From the R results and the elemental analysis results, the obtained polymer was recognized to be a polyether copolymer consisting of repeating units having the following structure. (Ia) (md) (Ia) : (na) : (md)=0.
7: 0.15: 0.15 When the properties of this polyether copolymer were measured, the glass transition temperature was 17.
9°C, melting point 350°C, thermal decomposition start temperature 556°C (in air, 5% reduction), and melt viscosity at 400°C 32,000 voids. A tensile test was conducted on a test piece obtained by injection molding this polyether copolymer at 400°C in accordance with ASTM D-638. Tensile strength 920kg/cm2 Tensile modulus
28.000kg/cm”
40% Also, when this test piece was used to examine its solubility in various solvents, it was found to be insoluble in acetone, chloroform, carbon tetrachloride, methylene chloride, ethanol, toluene, and xylene, and no stress cracks occurred. Ta. Furthermore, when the flame of a lighter was brought close to this test piece for 10 seconds and immediately removed, the flame on the test piece quickly went out and there was no melting and dripping. (Example 18) 1290 g of 2,6-cyclopenzonitrile (0
0075 mol), 4.4'-bis(4-fluorobenzoyl)diphenylthioetherco, z4g (0,0
075 mol), 4.4'-biphenol 921 g (0
050 mol), 4,4'-difluorobenzophenone 7
．． 64g (7.64 mol), potassium carbonate 11.29
g (0,06 mol) and diphenylsulfone 100
g and heated to 250℃ while blowing argon gas.
The mixture was reacted for 30 minutes at 330° C. for 20 minutes. During the process of raising the temperature to 1250°C, a small amount of toluene was added to the reaction system, and the produced water was removed by azeotropic distillation. After the reaction was completed, the mixture was cooled to near room temperature, wood was added and crushed, washed with water and methanol, and then dried. According to the analysis results described below, the obtained solid content (polymer) is a polyether copolymer, and the yield thereof is: 18.
7 g (yield 98%) was finished. The IR measurement results of the polymer (solid content) are shown in FIG. From the IR results and the elemental analysis results, the obtained solid content was recognized to be a polyether copolymer consisting of repeating units having the following structure. (Ia) (me) (Ia): (Ila): (me)=0.7
: 0-15 + 0.15 When the properties of this polyether copolymer were measured, the glass transition temperature was 189.
°C, melting point 351 °C, thermal decomposition start temperature 570 °C (in air,
5% reduction), and the melt viscosity at 400°C was 18,000 voids. A tensile test was conducted on a test piece obtained by injection molding this polyether copolymer at 400°C in accordance with ASTM D-638. Tensile strength: 950kg/Cs” Tensile modulus
28,000kg/c■! stretch
30% Also, using this test piece, the solubility in various solvents was investigated and found to be acetone and chloroform. It was insoluble in carbon tetrachloride, methylene chloride, ethanol, toluene, and xylene, and no stress cracks occurred. Furthermore, when the flame of a lighter was brought close to this test piece for 10 seconds and immediately removed, the flame on the test piece quickly went out and there was no melting and dripping. [Effects of the invention] ■According to the present invention, by containing repeating units with a specific chemical structure in a specific proportion, it has crystallinity, has a high glass transition temperature of 191°C, and has excellent heat resistance and mechanical properties. A good polyether copolymer can be provided. (1) According to the method of the present invention, there is provided a method for efficiently producing the polyether copolymer of the present invention, which is a novel polyether copolymer having the above-mentioned excellent properties, through simple steps. I can do it.

[Brief explanation of the drawing]

Figure 1 is an IR chart of the polyether copolymer obtained in Example 1, Figure 2 is an IR chart of the polyether copolymer obtained in Example 10, and Figure 3 is an IR chart of the polyether copolymer obtained in Example 10.
The figure is an IR chart of the polyether copolymer obtained in Example 17, and FIG. 4 is an IR chart of the polymer obtained in Example 18.

Claims (2)

[Claims] (1) The following formula (I); ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (However, n in the formula is 1 or 2) The repeating unit represented by the following formula (II); ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Repeating unit represented by (II) and the following formula (III); ▲ Mathematical formula,
There are chemical formulas, tables, etc. ▼ (III) (However, Y in the formula is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼、▲Mathematical formula, chemical formula,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Represents. ), and the composition ratio (molar ratio) of the repeating units represented by the above formula (I) [(I)/{
(I) + (II) + (III)}] is 0.65 to 0.85, and the sum of the repeating units represented by the formula (II) and the repeating units represented by the formula (III) Composition ratio (molar ratio) [{(II) + (III)}/{(I) + (II)
) + (III)}] is 0.15 to 0.35, and the composition ratio (molar ratio) of the repeating unit represented by the formula (II) [(
II)/{(I)+(II)+(III)}] is 0.05 or more, and the composition ratio (molar ratio) of the repeating unit represented by the above formula (III) [(III)/{( I ) + (II) + (III)
}] is 0.05 or more, and a melt viscosity (zero shear viscosity) at a temperature of 400° C. is 1,000 poise or more. (2) The following general formula [1]; ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [1] (However, in the formula, X is a halogen atom and n is 1 or 2.) is 1 or It is 2. ) and the following general formula [2]; ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [2] (However, X in the formula represents a halogen atom.) Dihalogenobenzonitrile represented by and the following general formula [3]; ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [3] (However, in the formula, X is a halogen atom, and Y is the formula (III) according to claim 1 above. It has the same meaning as Y in ) and 4,4'-biphenol,
2. The method for producing a polyether copolymer according to claim 1, wherein the reaction is carried out in a neutral polar solvent in the presence of an alkali metal compound.