JPH0245527A - Aromatic ether ketone-based copolymer and production thereof - Google Patents

Abstract

PURPOSE:To obtain the subject readily moldable and processable copolymer, containing two specific recurring units in a specific proportion and having a high glass transition temperature and excellent heat resistance with a low crystal melting point and improved in mechanical strength, corrosion resistance and electrical properties. CONSTITUTION:The objective copolymer, obtained by reacting (A) 1mol% 4,4'-dihalobenzophenone with (B) 0.5-0.95mol% 4,4'-dihydroxydiphenyl and (C) 0.05-0.5mol% [based on the component (B)] dihydric phenol with (D) an alkaline metal compound, containing recurring units expressed by formulas I and II (Ar is formula III, IV, V, VI, VII, VIII, IX, X, XI or XII) at (50:50)-(95:5)mol% and having a low crystal melting point in spite of a high glass transition temperature and suitable as engineering resin materials for use in aerospace, atomic energy, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application 1] The present invention relates to an aromatic ether ketone copolymer and its production method υ = 17, y et al., i''F L < is particularly, It is a heat-resistant engineering resin with a high glass transition temperature and excellent mechanical strength and heat resistance. An aromatic ether ketone copolymer having a novel structure (polymer) and an aromatic ether ketone copolymer having the excellent properties listed in 1-, using a manufacturing raw material that is easy to enter into the industry. can be done easily and efficiently under mild conditions.
This invention relates to a method for producing a highly advantageous aromatic ether ketone copolymer.

[Prior art and problems] In recent years, so-called engineering resins with various chemical structures have been used in a wide range of industries and fields, but even these have not yet been fully satisfactory, and even new materials are needed. In particular, the development of engineering resins with excellent heat resistance is desired.

One of these engineering resins is aromatic ether ketone polymers, such as "J, Po
lym, Sci,, Polym, Che Feng,
Ed, 1983°2D8), 2283-2289
A comonomer of hensifhenone and dihydroxyphenyl is disclosed in J.J.

The structure of the polybiphenylene ether polymer is expressed by the following formula (a
).

(b) (a) The polymer represented by the temperature formula (a) is a crystalline polymer with a glass transition temperature (g) of 167°C and a melting point of 422°C, and its crystal melting point is too high, so it cannot be molded. There are problems when the temperature is high.

Therefore, in order to solve this problem, JP-A-61-1
Publication No. 38626-3 describes the repeated copolymerization of benzophenone and dihydroxydiphenyl. An aromatic ether ketone consisting of the i-position and a repeating unit obtained by combining hensifhenone and hydroquinone.
-ffi coalescence is disclosed. The repeating units in the J (polymer are shown in the following formulas (b) and (c).

[However, n in the formula is 0.4 to 0.05 and 1m is 0
．． 6 to 0.95. ] This copolymer contains a repeating unit represented by formula (b) i
ii is 0.4 to 0.05 mol%, and the content of the repeating unit represented by formula (c) is 0.6 to 0.95 mol%. Although this copolymer has a low crystalline melting point, it also has a low glass transition temperature and has the disadvantage that it does not have sufficient heat resistance.

Therefore, it has been a challenge to develop a new aromatic ether ketone copolymer that has a higher glass transition temperature and lower crystal melting point than conventional aromatic ether ketone polymers.

Unoccurred IJI was developed to solve the above problem.

That is, the object of the invention as set forth in Claim A11 of the present application is to solve the above-mentioned problems, to have excellent mechanical strength, heat resistance as high as 1 minute, and especially a high glass transition temperature and a low crystal melting point. Lutocorono with excellent properties, aromatic etherke with a novel structure that is an engineering resin,
The object of the invention as set forth in Claim 12 of the present application is to provide an aromatic etherketone-based copolymer as set forth in Claim 1 of the present application which has the excellent properties listed in item I-. To provide a practical method for producing an advantageous aromatic ether ketone copolymer that can be easily and efficiently synthesized by using production raw materials that are technically easy for humans to produce. There is a particular thing.

[Means for Solving the Problems] As a result of extensive research in order to solve the problems described above, the present inventors have discovered that an aromatic ether ketone co-1n polymer having a repeating unit with a specific new chemical structure has been developed. We discovered that it is an engineering resin that has excellent properties such as excellent mechanical strength and heat resistance, particularly a high glass transition temperature, and a low crystalline melting point, and based on this knowledge, we have developed Claim 1 of the present application. As a result of completing IJJ and conducting various studies on a practical and advantageous method for producing the aromatic ether ketone copolymer, we found that 4,4'-dihalobenzophenone and 4,4'- Practical Example 1: A method of condensation polymerization of dihydroxydiphenyl and dihydric phenol in a specific ratio in a specific solvent in the presence of an alkali metal compound can easily and efficiently produce the above polymer. We found that this method is extremely advantageous, and based on this knowledge, we completed the invention of claim 2 of the present application.

In other words, the invention according to claim 1 is based on the following formula (1) and formula (n) (II) (where r represents 6 H5), and the formula (I) Middle G expression (H) No? Contains l'-position c7);';h'? Ka50
:50-95:5 (mol%)
) (However, X in one person represents halogen g; < r-, and two Xs may be the same or different as !f) Dihalobenzophenone and Kono 4
, 0.0 for 1 mole of 4'-dihalobenzophenone.
5 to 0.95 mol of 4.4'-dihydroxydiphenyl and 0.05 to 0.5 mol of the formula (IT) HO-Ar-O per 1 mol of this 4,4'-dihalobenzophenone.
H (TV) (However, Ar is (raigong, below is the margin.

This is a method for producing an aromatic ether ketone copolymer, which comprises reacting a dihydric phenol represented by 6H5 in a neutral polar solvent in the presence of an alkali metal compound.

The aromatic ether ketone covalent polymer according to claim 1,
The repeating intermediate represented by the formula (I) [this
(U-I) may be written. ],
The repeating intermediate represented by the above formula (II) [hereinafter, this may be written as (U-U). ], and the repeating middle (U-I) and the (U-n) have a ratio of 50:50 to 95:5 (mol%),
Preferably it is 80:40 to 80:20 (mol%).

In addition, the repeating middle position (υ−■) is the two phenolic trees N from the dihydric phenol S represented by the formula (17).
It varies depending on the type of residue A" excluding the I group. A" in the middle position (U-111) may be - type or two or more types.

The composition of the aromatic ether ketone copolymer is such that if the repeating intermediate (II-I) exceeds 95 mol%, the crystal melting point will become high and the moldability will deteriorate, and if it is less than 50 mol%, the crystal will deteriorate. properties are lost and heat resistance decreases.

Further, the aromatic ether ketone copolymer in the present invention may be a random copolymer, a block copolymer, a cross-linked copolymer, or a mixture thereof, most preferably a mixture thereof. , a random copolymer is preferable in consideration of the manufacturing method and the like.

Although the aromatic ether ketone copolymer described in claim 1 of the present application can be produced by various methods, it can be suitably produced by the method described in claim 2 of the present application.

In the invention of claim 2, h represented by formula (III)
Specific examples of the halogen atom in the 4,4°-dihalobenzophenone include a fluorine atom, a chlorine atom, a bromine atom, and the like.

Among these, fluorine atoms and salt atoms are particularly preferred in consideration of reactivity, economy, etc.

Specific examples of 4°-dihalobenzophenone include 4.4'-difluorobenzophenone, 4.4°-dichlorohensiphenone, 4-chloro-41-fluorobenzophenone, and the like. . Among these, 4°4°-difluorobenzophenone, 4,4°-cyclobenzophenone, etc. are preferred.

By the way, are these 4,4'-dihalobenzophenones one type? It may be used alone or in combination with a tether.

In the invention of Claim 12 of the present application, the 4.4-dihydroxydiphenyl can be used as a monomer as it is, but if desired, the 4.4'-dihydroxydiphenyl can be converted into an alkali metal salt or the like. It can also be used as a metal salt and serve as both a hexamer component and an alkali metal compound component.

Note that among the alkali metal salts, sodium salts, potassium salts, and the like are preferred.

These various alkali metal salts can be used alone, or in combination with 4.4'dihydroxydiphenyl (dihydroxy form). It can also be used as a mixture in any proportion.

In the IJI described in claim J312, HO-Ar-
Dihydric phenols represented by OH(ff) can be used.

Dihydric phenols represented by the formula (■) [hereinafter sometimes referred to as dihydric phenols (IV)]. ] Specific examples include 2°7-hydroxynaphthalene, bis(4-hydroxyphenyl)ketone, bis(4-hydroxyphenyl)sulfone, and 1,1-diphenyl-■.

l-bis(4-hydroxyphenyl)methane, phenolphthalein, 1.1-bis(4-hydroxyphenyl)indane, 9.9-bis(4-hydroxyphenyl)fluorene, 9.9-bis(4-hydroxy phenyl)−
Examples include 10H-anthracene, 1.1-bis(4-hydroxyphenyl)phthalane, 9.9-his(4-hydroxyphenyl)-10-xanthine, and the like. In addition.

These dihydric phenols may be reacted alone, or two or more thereof may be reacted.

In addition, the dihydric phenols (IT) can be used as is as a comonomer, but if desired, f
It may be used as an alkali metal salt of the dihydric phenol (IV) by converting it into an alkali metal salt. Note that among the alkali metal salts of the dihydric phenols (■), sodium salts, potassium salts, etc. are preferable, and these various alkali metal salts of heptavalent phenols (IT) may be used alone. It is also possible to use one or more of them together as a mixture, or to combine them with the above-mentioned dihydric phenols (■) (dihydroxy form).
It can also be used as a mixture in 11.1 of 1.

What is important in claim 2 of the present application is that 0.50 to 0.9 of the 4.4°-dihydroxydiphenyl is added to 1 mole of the dihalobenzophenone represented by the formula (tn).
in a proportion of 5 mol, preferably 0.60 to 0.80 mol,
and the dihydric phenol represented by the formula (IV) is 0
．． 05-0.50 mol, preferably 0.20-0.40
The reaction is carried out in molar proportions. However, in order to react at such a ratio, the charging ratio should be 4.4.
The molar ratio of °-dihalobenzophenone to the total molar capacity of 4.4゛-dihydroxydiphenyl and dihydric phenols is 0.98 to 1.02, preferably 1.00 to 1.0.
It is preferable that such a preparation is made to have a value of 1;
, by combining the repeating unit (U-I) and the repeating unit (U-11) in the aromatic ether ketone system to 50:50.
It can be within the range of 95:5 (mol %).

In the present invention, 4,
4°-Dihydroxydiphenyl and dihydric phenol are dehydrohalogenated and polycondensed in an aprotic polar solvent in the presence of an alkali metal compound.

In the invention of claim 2 of the present application, as the alkali metal salt compound, 4.4°-dihydroxydiphenyl or a compound capable of converting the dihydric phenol (1'V) used into an alkali metal salt is used. However, usually alkali metal carbonates and/or alkali metal bicarbonates are used.

However, the alkali metal salts of the 4,4'-dihydroxytetraphenylmethanes or the -valent phenols (
When the alkali metal salt of IV) is used as a monomer or a comonomer, these can also be used in combination with the alkali metal compound.

Examples of the alkali metal carbonate include:

Mention may be made of lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate and cesium carbonate. Among these, sodium carbonate and potassium carbonate are preferred.

Examples of the alkali metal bicarbonate include lithium carbon hydrogen, sodium hydrogen carbonate, potassium hydrogen carbonate,
Mention may be made of rubidium hydrogen carbonate and cesium hydrogen carbonate. Among these, sodium 5-hydrogen and potassium carbonate are preferred.

The alkali metal carbonates and alkali metal bicarbonates are usually preferably used as anhydrides, but if desired, they can also be used as hydrates, concentrated aqueous solutions, and the like containing water. In addition, the water added to the reaction system and the water generated by the reaction are
It is preferable to appropriately remove the compound from the reaction system during or prior to the reaction.

The alkali metal salts mentioned above may be used alone, or two or more of them can be used together as a mixture or the like in a ratio of 1.1 to 1.1.

The use of the alkali metal salt X-1 is such that the alkali metal salt is used in an amount of 1.00 to 3.00 per 1/2 mole of the total mole j4 of 4,4'-dihydroxydiphenyl and dihydric phenol.
Gram equivalent, preferably 1.05-2.00 grams S
, + is suitable for use within the acceptable range.

Further, as the aprotic polar solvent, known ones can be used, and specifically, for example, dimethylformamide, diethylformamide, dimethylacetamide, diethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, dimethyl Sulfoxide, sulfolane, diethylimidazolidinone, diphenylsulfone, etc. can be suitably used. Among these, N-methylpyrrolidone and sulfolane are preferred;
Particularly preferred is N-methylpyrrolidone.

Note that these aprotic polar solvents may be used alone, or may be used in combination with Otsu Shogi 1- as a mixed solvent, or may be used in combination with other inert solvents, especially water removed from the reaction system. By azeotropically removing , it can also be used as a mixed solvent with aromatic v M -based solvents such as Kirchensen, toluene, and xylene. The use of aprotic polar solvents -
For A-go, the type of nanatsuma used is 1, I, 1-go,
Although it cannot be specified uniformly because it varies depending on the reaction conditions, etc., it is recommended that the total C degree used be within the range of, for example, 0.25 to 4.0 mol/hydrocarbon. is suitable.

In the invention of claim 2 of the present application, the aromatic ether ketone copolymer is prepared by: (1) using any one or any two of the various dihalobenzophenones as one of the raw material monomers; - as the other one, using 4,4"-dihydroxydiphenyl and a dihydric phenol of formula (1'lr), and heating them in the aprotic polar solvent in the presence of the alkali metal salt. By doing so,
It can be suitably synthesized by a method in which hydrogen halide is eliminated and condensation polymerization is performed.

In addition, as a modification of 1-, (1), in the above, 4.4'-dihydroxydiphenyl, a part of the dihydric phenols, and a part of the alkali metal salt are replaced with 4.4'-dihydroxydiphenyl and a part of the alkali metal salt. A method of substituting dihydric phenols with alkali metal salts, in the method of (3) + ii), 4,4°-dihydroxydiphenyl and all of the dihydric phenols and an alkali metal carbonate and/or an alkali metal heavy salt It is also possible to adopt a method of substituting part or all of 4,4'-dihydroxyphenyl and alkali metal salts of dihydric phenols.

As the polymerization method, a known solution top method can be applied. There are no particular restrictions on the metal method, and a step or multi-step gravity method, a batch method, a continuous method, a continuous method, or a combination of one or two of these methods can be adopted.

In the invention of claim 2 of the present application, the temperature at which the reaction (condensation reaction) is carried out is usually 150 to 350°C, preferably 18
The temperature is preferably within the range of 0 to 250°C. In addition, the seven-mer concentration is: total monomer: +k (mol)/solvent (
0.25 to 4 mol/l is appropriate. In addition, the reaction time for carrying out the above-mentioned synthetic reaction cannot be uniformly prescribed because it varies depending on the type of monomer and alkali metal compound used, the proportion used, the reaction temperature, etc.
Usually, it is appropriate to set the time within a range of 0.1 to 10 hours, preferably 1 to 3 hours.

There is no particular restriction on the reaction pressure, and the reaction can be carried out under reduced pressure, normal pressure, or increased pressure, but it is usually preferable to carry out the reaction between reduced pressure and around normal pressure.

The reaction atmosphere is usually nitrogen or argon.

It is preferable to use an inert atmosphere such as under an inert gas flow such as helium or under reduced pressure exhaust.

The aromatic ether ketone copolymer according to claim 1 of the present application can be synthesized as follows.
The resulting polymer can be separated from the product mixture by using a known post-treatment method, and subjected to appropriate purification operations such as washing, and then recovered as an aromatic ether ketone polymer with a purity of 90%. can.

As a post-treatment method, for example, the polymerization reaction product mixture is cooled to around room temperature, the polymer is precipitated using an appropriate solvent such as acetone, the polymer is pulverized, and the polymer is washed with hot water or methanol. , drying methods can be suitably employed.

The method according to claim 2 of the present application can easily and efficiently obtain the aromatic ether ketone copolymer according to claim 1 of the present application under mild conditions using manufacturing raw materials that are easily industrially available. Practical Application 1 - This is an extremely excellent method for producing an aromatic ether ketone copolymer.

In addition, the reduced viscosity of the aromatic ether ketone copolymer obtained in this way is as follows:
．． The original viscosity [ηsp/c] was measured from 0.30 to
A range of 2.00 d sentences/g is appropriate. If this reduced viscosity is less than 0.30 dJL/g, the mechanical strength of the copolymer will be low or the heat resistance will be poor, and if it is greater than 2,00 dJJ/g, the moldability will be low. do.

Further, the various aromatic ether ketone copolymers according to the invention of claim 1 of the present application can be used alone or in combination as a polymer blend shade. However, if desired, various additives such as known modifiers or other polymers may be blended and used.

The aromatic ether ketone copolymer according to the invention of claims 1 and 2 of the present application can be molded into a desired shape by employing a known molding method, such as an extrusion molding method, an injection molding method, a compression molding method, etc. Can be added.

The aromatic ether ketone copolymer of the present claim obtained as described in 1- above has a high glass transition temperature and excellent heat resistance, but nevertheless has a low crystal melting point and is easy to process before molding. , moreover, it has great characteristics of mechanical strength,
Extremely excellent as a heat-resistant engineering resin.

Hereinafter, 1 will be explained in detail with reference to examples.

[Example] (Example 1) A separable flask with an internal volume of 32 equipped with an argon gas blowing tube, a stirring device, a Dean-Starck trap filled with toluene, and an octacouple, 110.19 g of 4.4°-difluorobenzophenone ( 0.5 mol), 4.4'-
83.79 g (0.45 mol) of dihydroxydiphenyl, 15.82 g (0.05 mol) of phenolphthalein, and 03.7 g of potassium carbonate I with N-methylpyrrolidone 1. Then, argon gas was blown into the reactor, and the temperature was raised from room temperature to 200° C. over 40 minutes while stirring. After raising the temperature, add 30 m of toluene and perform dehydration for 30 minutes by azeotropic distillation.
The reaction was continued at a temperature of 200° C. with stirring and heating for 2 hours. After the reaction is completed, the reaction product is cooled, and the resulting polymer is precipitated in methanol.
A copolymer powder was obtained by pulverizing with a blender manufactured by Warning Co., Ltd., washing three times with 10 mung beans and once with 5 methanol, and then drying.

The yield of the copolymer obtained was 197g (yield: 498%).
)Met. The physical properties of this copolymer were measured, and the glass transition degree Tg (manufactured by Toyo Baldwin Co., Ltd., /< Yvlon-c
"lll constant) is 180℃, melting point T m (DEC-12
80) was 401°C, and the thermal decomposition start temperature Td (temperature when 5% of xl decreased when heated in air at 10°C/in) was 527°C. In addition, the reduced viscosity Jiff is for a polymer solution in C sulfuric acid with a density of 1.84 g/Hotomata containing 0.2 g of polymer per 100 mg of solution.
Immediately after completion of dissolution to minimize the effects of sulfonation,
When A is constant at 0°C, the reduced viscosity [ηsp/c] is 1
．． It was 35dM/g.

Further, the structure of the obtained polymer was analyzed by infrared absorption spectrum and lH-NMR, and the results confirmed that it was an aromatic ether ketone consisting of the following repeating units.

(Raiko, hereafter blank) O [However, m = 0.9, , m = O, l] (Examples 2 to 11) Table 1 for 4.4-difluorobenzophenone and 44'-dihydroxydiphenyl Copolymers were obtained by carrying out the same procedure as in Example 1, except that the dihydric phenol of formula (IV) was used as shown in +if formula (IV), and the type was changed. As a result of measuring the properties of these co-K combinations, the original viscosity [ηsp/c] and thermal properties such as glass transition temperature (Tg), melting point (Tm), and thermal decomposition onset temperature (Td) are shown in Table 1. show.

In addition, the structure of the obtained copolymer was determined by infrared absorption spec I.
Analyze by H-NMR and repeat the following? It was confirmed that the copolymer was an aromatic ether ketone copolymer having a structure at the li position.

Example 2: The repeating unit is the same as in Example 1.

However, m = 0.8, n = 0.2, Example 3; the eel turning unit is the same as Example 1, but m =
0.7, n=0.3 Example 4: &) The repeat unit is the same as Example 1, but m
= 0.8, n = 0.4, Example 5; repeating unit is the same as Example 1, but m = 0.5, n = 0.5
, Example 6: 1 & repeating medium 6H5, but m=0.8, n=0.2 Example 7: Repeating 11th place is the same as Example 6, but m=
0.7, n = 0.3, Example 8: The repeat middle is the same as Example 6, but m = o
, 6 n=0.4 Example 9; Reworked 11th place However, m = 0.7, n = 0.3 Example + 1. Repeating unit: m = 0.7, n = 0.3 Example 1O: Moderate repetition: m = 0.7, n = 0.3 (Comparative Example 1) A 500-liter separable flask was equipped with a stirrer and argon. Equipped with gas blowing pipe and Dean-Starck trap, 4
．． 4°-difluorobenzophenone 44.0?8g (0
, 20 mol), 4,4'-dihydroxydiphenyl 26
．． 0[i9g (0.14 mol), hydroquinone 6.60
7g (0.06 mol), sodium carbonate 21.198g
(0.20 mol), potassium carbonate 1.382 g ((LO
mol) and 150 g of diphenylsulfone,
Heated to 200℃ and held for 1 hour, then heated to 280℃ for 3 hours.
The temperature was raised for 0 minutes, and then the reaction was incubated at 320°C for 2 hours.
The reaction solution was stopped by adding 2 g of 4.4"-dichlorodiphenyl sulfone and then heating at 350°C for 05 hours. After the reaction, the product was cooled to solidify and pulverized with a hammer mill. The copolymer was then washed twice with acetone and twice with hot water to obtain a copolymer.

The obtained copolymer was measured, reduced viscosity, thermal properties (Tg
, Tm Td) are shown in Table 1. Furthermore, the structure of the copolymer was analyzed in the same manner as in Example 1, and it was confirmed that it was an aromatic ether ketone consisting of the following repeating unit structure.

0'S1 Table However, m = 0.7, n = 0.3 From Table 1, Examples 1 to 11 of undeveloped IJI have higher glass transition temperature Tg, lower crystal melting point Tm, and lower thermal resistance than Comparative Example 1. It is clear that the decomposition start temperatures Tm are approximately the same, and that the heat resistance and moldability are excellent.

[Effects of IJI] The aromatic ether ketone copolymers according to claims 1 and 2 of the present application contain a repeating unit formed by copolymerization of dihalobenzophenone and 4,4'-dihydroxydiphenyl, and a specific dihalobenzophenone. It is a new crystalline aromatic ether ketone copolymer with a structure containing repeating units copolymerized with dihydric phenols, and has a particularly low glass transition temperature compared to conventional aromatic ether ketone copolymers. It has high heat resistance, has a low crystal melting point despite a high glass transition temperature, and has a high
It also has excellent mechanical strength, electrical properties, corrosion resistance, etc., and is suitable as an engineering resin for materials that require heat resistance, especially in the aerospace and preload fields.
It is.

In addition, the aromatic ether ketone complex having the excellent properties listed in Section 1 can be industrially produced using easily produced raw materials.
It is possible to provide a practical method for producing aromatic ether ketone copolymers that can be easily and efficiently obtained under mild conditions, and their industrial value is extremely high.

r Addendum 1 [2 + 1 q (November 2011, 2211 4\ Director General of the License Agency) - 19 indications V (Wa 1963 4\ Fraudulent Application No. 19858'H; 2 Name of Invention Toko Family Ether Ketone Person responsible for system polymers and their manufacturing method 112 Relationship with 11ji1 Address Name Representative

Claims (2)

[Claims] (1) The following formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) and Formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (However, Ar is ▲Mathematical formulas, chemical formulas, tables, etc.) There are 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. ▼, ▲ 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. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables etc. ▼ Represents. ), and the content ratio of units of formula (I) and units of formula (II) is 50:50 to 95:5 (
mol%). (2) The following formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) (However, X in the formula represents a halogen atom, and two X
may be the same or different. ) 4,4'-dihalobenzophenone represented by
, 0.5 to 1 mole of 4'-dihalobenzophenone
0.95 mol of 4,4'-dihydroxydiphenyl;
0 per mole of this 4,4'-dihalobenzophenone
．． 05 to 0.5 mol of formula (IV) HO-Ar-OH(I
V) (However, Ar has ▲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. ▼, ▲ 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. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables etc. ▼ Represents. ) A method for producing an aromatic ether ketone copolymer, which comprises reacting a dihydric phenol represented by the following in a neutral polar solvent in the presence of an alkali metal compound.