JPS62141024A - Thermoplastic aromatic polyether anthraquinone and its production - Google Patents

Abstract

PURPOSE:To obtain the titled polymer excellent in thermal and mechanical properties and useful as a material for high-performance moldings, films, fibers, etc., by reacting at least one dihalogen compound with an alkali metal diphenolate. CONSTITUTION:A dihalogen compound mixture (A) formed by mixing dihalogen compounds (a), (b) and/or (c) of formulas I, II and/or III (wherein X is Cl or F) together at such a ratio that 100-50mol% component (a) is used per 0-50mol% components (b) and/or (c) is mixed with an alkali diphenolate (B) of formula IV (wherein M is an alkali metal and Ar is a bivalent aromatic residue) at an A to B molar ratio about 1, and the monomers are polymerized at 50-450 deg.C and at atmospheric or superatmospheric pressure for 0.5-50hr in anhydrous conditions in an inert gas atmosphere to obtain the titled polymer comprising 50-100mol% structural units of formula V and 0-50mol% structural units of formula VI (wherein Y is a group of formula VII and/or SO2) and having an inherent viscosity >=0.5 (as measured in 98% sulfuric acid at 0.5g/dl concentration and 30 deg.C).

Description

Detailed Description of the Invention <Industrial Application Field> The present invention relates to an aromatic polymer having excellent thermal properties and mechanical properties, and more specifically, 2.6-
This invention relates to a novel thermoplastic aromatic polyether anthraquinone containing a bonded anthraquinone ring and a method for producing the same. <Prior art> Aromatic cybarides activated with an electron-withdrawing group, such as 4,4'-dichlorodiphenyl. Sulfone, 4.
It is already well known that aromatic polyethers can be obtained by the nucleophilic substitution reaction of 4'-difluorobenzophenone and dihydric phenols with alkali metal salts (
For example, Japanese Patent Publication No. 42-7799, Japanese Patent Publication No. 46-7799,
1814t1, Japanese Patent Publication No. 60-32642, etc.).

Furthermore, a proposal has already been made to produce an aromatic polyether having an anthraquinone ring by reacting a tricyclic condensed ring dinitro compound with an alkali metal salt of an aromatic polyhydric phenol (Japanese Unexamined Patent Publication No. 60-71636 Publication No.).

<Problems to be solved by the invention> Among the aromatic polyethers synthesized by a nucleophilic substitution reaction between an aromatic cybaride activated with an electron-withdrawing group and an alkali metal salt of a dihydric phenol, this There are four types that have been put into practical use so far:

A, Union Carbide Company 1 Needle', Tg=1
90℃B, United States Union Carbide Co., Ltd. Radel','
rg-224℃C0 UK ICI 1 Pictrex',
Tg = 225°C, PEEK manufactured by ICI, UK, Tg = 143°C Among these, A, B and C have a relatively high glass transition temperature (Tg), which is a measure of heat resistance. , have excellent thermal properties, but since they are essentially non-quality ether polymers, they have problems with solvent resistance, which greatly limits their practical use in industry. be. continue,
For the purpose of improving the solvent resistance of these three, studies have been conducted to crystallize ether polymers, and as a result, the above-mentioned PEEK has been put into practical use. PEEK
Since it is a crystalline aromatic ether polymer, it has extremely excellent solvent resistance, but since its Tg is not so high, it remains at a somewhat unsatisfactory level as a heat-resistant material.

, Subsequently, in the industrial world, efforts are being actively made to develop materials that are better than PEEK in terms of the balance between thermal properties and solvent resistance, and proposals for 2.3 have begun to appear (for example, Publication No. 58-167622, JP-A-58-
173127, JP-A-60-71636, etc.).

For example, in Japanese Patent Application Laid-Open No. 60-71636,
- A method for synthesizing anthraquinone ring-containing aromatic ethers by reacting dinitroanthraquinone with bisphenol A or the disodium salt of hydroquinone is disclosed. However, although the aromatic ethers synthesized by this method have improved heat resistance, the raw material, dinitroanthraquinone, can be produced at an economical high yield based on the principle of chemical synthesis reaction. - and 1.
Since it is limited to the 8-isomer, the polymer structure itself has large internal strains, and only extremely brittle materials can be obtained.

Therefore, the present inventors introduced an anthraquinone structure as a heat resistance improving factor into an aromatic ether polymer, and as a result of intensive studies with the aim of ensuring toughness, introduced a 2,6-substituted anthraquinone structure. The present invention was achieved by discovering that it is important to do so and that it is extremely effective to utilize 2,6-cyhaloanthraquinone in the manufacturing method.

Means for Solving the Problems〉 That is, the present invention solves the following problems:
It consists of a structural unit represented by 2-÷be=)-Y÷0-Ar-Chii (where Ar represents a divalent aroma) from 0 to 50 mol%, and in 98% sulfuric acid, at a concentration of o, sp/ag. , temperature 3
Thermoplastic aromatic polyether anthraquinone and t-+kheco)←so,(3-x (where x is a chloro group or a fluoro dihalogen compounds represented by a group) and alkali metal dihydric phenols represented by the general formula MO-Ar-OM (where M is an alkali metal and Ar is a divalent aromatic residue) When reacting salts (a), 6:I) and/or Q → (a)
100-50 mol%, 6:I) and/or (c)0
The present invention provides a method for producing a thermoplastic aromatic polyether anthraquinone, characterized in that the thermoplastic aromatic polyether anthraquinone is used in a proportion of 50 mol %.

The thermoplastic aromatic polyether anthraquinone of the present invention has general formula structural units of 50 to 100 mol% and general formula B,
←Structural unit 0 to 50 expressed as Y÷0−Ar−0shi
(where Ar is a divalent aromatic residue; Y, yoshioyo, /yo□yo-so, -ya).

The polymer of the present invention is characterized by having both good fluidity due to ether bonds and heat resistance/toughness due to 2,6-anthraquinone bonds, especially by incorporating 2,6-cyoxane. Therefore, A unit plays the leading role, and A
/B is 50-1OO10-50 (preferably 70-1o
o10-30) molar ratio. If the B unit is used in an amount of 50 mol% or more, the heat resistance/toughness characteristics of the A unit will be diminished, which is not preferable.

Ar is an aromatic residue of dihydric phenols and is represented by. Here, Z is a direct bond, -〇-1〇-5-1-to1-so2-1 carbon number 2 to 10 (1!o
ylkyl group, cycloalkyl group or aralkyl group, fluorine-substituted alkyl group having 2 to 10 carbon atoms, R is an alkyl group having 1 to 4 carbon atoms, alkyl ether group, halogen group, b is 0 or 1 to 4 integer, a is 0 or 1 to 20
indicates an integer. Specific examples of these will be detailed later as specific examples of dihydric phenols.

The polymer of the present invention is a tough high polymer having a logarithmic viscosity (vinh) of 0.5 or more. If the logarithmic viscosity is less than 0.5, the toughness will be significantly reduced, which is not preferable. The logarithmic viscosity (yinh) herein refers to the logarithmic viscosity number measured in 98% m-acid at a polymer concentration of C=0.5 t/ri (1° and a measurement temperature of 30°C).

The dihalogen compound used in the present invention is represented by the following general formula.

t, +X-CnsO,-Q-X (In the formula, X represents a chloro group or a fluoro group.

) and these are (a) for 100 to 50 mol%
) and/or tqo to 50 mol%. Specific examples of (a) include 2.6-difluoroanthraquinone, 2.6-dichloroanthraquinone, 2.7
-difluoroanthraquinone and 2,7-dichloroanthraquinone are specific examples of 6:I), such as 4,4'-
Specific examples of Ql) include difluorobenzophenone and 4,4'-dichlorobenzophenone, and 4,4'-difluorodiphenylsulfone and 4,4'-dichlorodiphenylsulfone.

The alkali metal salt of dihydric phenol used in the present invention is represented by the general formula MO-Ar-OM (wherein M represents an alkali metal and Aro is the same as defined above).

The alkali metal salt of dihydric phenol of the present invention has the general formula HO
It can be synthesized by reacting a dihydric phenol represented by -Ar-OH (in the formula, Ar is the same as defined above) with a substantially equivalent amount of an alkali gold a compound, and it can be synthesized separately and polymerized. or used in the reaction immediately before or while being prepared at the same time as polymerization.

Examples of dihydric phenols used in the present invention include bis-(hydroxyphenyl) ethers, such as bis-
(4-hydroxyphenyl)ether, 4.3'-dihydroxydiphenyl ether, bis-(3-hydroxyphenyl)ether, 4.4'-dihydroxy-2,6
-Simethyl diphenyl ether, bis-(4-hydroxy-3-isopropylphenyl) ether, 4.4'-
Dihydroxy-3,6-simethoxydiphenyl ether, 4,4'-dihydroxy-2,5-jethoxydiphenyl ether, bis-(4-hydroxynaphthyl) ether, 1,4-bis-(4-hydroxyphenoxy)benzene , l, 3-bis-(4-hydroxyphenoxy)
benzene, 1,3-bis-(3-hydroxyphenoxy)benzene, etc., bis-(hydroxyphenyl)sulfones, such as bis-(4-hydroxyphenyl)sulfone, 2,4'-dihydroxydiphenylsulfone, 3-
Methyl-4,4'-dihydroxydiphenylsulfone,
3.5-dimethyl-4,4'-dihydroxydiphenyl sulfone, bis-(3-methyl-4-hydroxyphenyl) sulfone, bis-(3-ethyl-4-hydroxyphenyl) sulfone, bis-(3,5- dimethyl-4-hydroxyphenyl) sulfone, bis-(3,5-diethyl-4-hydroxyphenyl) sulfone, bis-(3,
Bis-(hydroxyphenyl)propanes such as 5-di-t-butyl-4-hydroxyphenyl)sulfone, e.g. 2,2-bis-(4-hydroxyphenyl)propane, 1,1-his-(4-hydroxy phenyl)ethane, 2,2-bis-(3-phenyl-4-hydroxyphenyl)furopane, 2,2-bis-(3-isopropyl-
4-hydroxyphenyl)propane, 2,2-bis-(
2-isopropyl-4-hydroxyphenyl)propane, 2,2-bis-(3'-methyl-4'-hydroxyphenyl)propane, 2,2-bis-(3',5'-dimethyl-4'-hydro) quinphenyl)propane, 2.2-
Bis-(3',5'-di-t-butyl-4'-hydroxyphenyl)propane, 2-(3',5'-dimethyl-4'-hydroxyphenyl)-2-(4'-hydroxyphenyl) ) propane, 2-(3'-methyl-4'-hydroxyphenyl)-2-(4'-hydroxyphenyl)propane, 1.1-bis-(3-methyl-4-hydroxyphenyl)propane, 2.2 -bis-(4-hydroxynaphthyl)propane, 2.2-bis-(4-hydroxyphenyl)pentane, 3.3-bis-(4-hydroxyphenyl)pentane, 2.2-bis-(4-hydroxyphenyl) ) hebutane, bis-(4-hydroxyphenyl)phenylmethane, 2.2-bis-(4-hydroxyphenyl)-1-phenylpropane, 2.2-bis-
(4-hydroxyphenyl) -1,1,1゜3.3.
3-heki fluoropropane, 1,1-his-(4-hydroxyphenyl) cyclohexane, 1,4-bis-
(4-hydroxyphenyl)cyclohexane, 4.4'
-(meta-phenylenediisopropylidene)bis-phenol, 4.4'-(para-phenylenediisopropylidene)bis-phenol, 1.1-bis-(4-hydroxyphenyl)-1-phenylethane, etc. 4.4'
-hydroquine benzophenone, bis-(4-hydroxyphenyl) sulfide, 4,4'-cyhydroxydiphenyl, 3.3',4.4'-tetramethyl-4,4
Examples include '-dihydroxydiphenyl, hydroquinone, resorcinol, etc., and these can be used alone or in a mixture of two or more.

Among these dihydric phenols, bis-(4-hydroxyphenyl) ether, 4,3'-dihydroxydiphenyl ether, Bis-(3-hydroxyphenyl) ether, 2.2-bis-(4-hydroxyphenyl)propane, 2.2-bis-(3',5'-dimethyl-4'-hydroxyphenyl)propane, 4.4 '-dihydroxydiphenyl, 3'
, 3', 4, 4'-tetramethyl-4,4'-dihydroxydiphenyl, 1,4-bis-(4-hydroxyphenoxy)benzene, l,3-bis-(4-hydroxyphenoxy)benzene, 1. 3-bis-(3-hydroxyphenoxy)benzene and the like are preferred.

In the present invention, the alkali metal compounds that can be reacted with divalent phenols include, for example, hydrides of lithium, sodium, potassium, rubidium, and cesium;
These include hydroxides, carbonates, bicarbonates, alkoxides, and alkyl compounds. Among these, sodium and potassium hydroxides and carbonates are particularly preferred.

The thermoplastic aromatic polyether anthraquinone which is the object of the present invention is produced by reacting the above-mentioned specific dihalide and an alkali metal salt of a dihydric phenol in a substantially equimolar ratio. However, if the logarithmic viscosity of the polymer is in a range of 0.5 or more, this molar ratio is, for example, 1:0.95 to LO5, preferably 1:0.9.
It may deviate from about 8 to LO2.

Furthermore, when two or more dihalogen compounds are added to the alkali metal salt of dihydric phenol and reacted, the two or more dihalogen compounds can be added at the same time, or each can be added separately in sequence. . According to this method, in the former case, the random copolymer is also
In the latter case, a block copolymer is produced.

The polymer of the present invention can be produced by various methods shown below.

(1) A separately prepared alkali metal salt of dihydric phenol and a dihalogen compound are heated and stirred in the absence of a solvent.

(2) A separately prepared alkali metal salt of dihydric phenol and a dihalogen compound are heated and stirred in a solvent in the presence and absence of a dehydration entrainer.

(3) A dihydric phenol, an alkali metal compound, and a dihalogen compound are heated and stirred in a solvent.

(4) Dihydric phenol and alkali metal compound are reacted in a solvent, and after azeotropic distillation of dehydration is performed in the presence of a dehydration azeotropic agent, a dihalogen compound is added and stirred with heating.

(b) A dihydric phenol, an alkali metal compound, and a dihalogen compound are added to a solvent, and the mixture is heated and stirred in the presence of a dehydration entrainer.

(6) Dihydric phenol, alkali metal compound, dihalogen compound, and dehydration azeotropic agent are heated and stirred while performing dehydration azeotropic distillation in the absence of a reaction solvent.

When actually carrying out a reaction, the solubility of reactants and polymers,
It is necessary to select the most suitable method from among the methods shown here in consideration of reactivity, thermal characteristics, etc.

The production of the polymer of the present invention can be carried out depending on the combination of reaction raw materials.
Although it can be carried out under solvent-free conditions, it is more preferable to use a solvent.

Examples of solvents used in the polymerization reaction of the present invention include 1
．． 3-dimethyl-2-imidazolidinone, N-methyl-
2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylacetamide, N,N -N'
, N'-tetramethylurea, amide solvents such as hexamethylphosphoramide, dimethyl sulfoxide, dimethyl sulfone, diethyl sulfoxide, diethyl sulfone,
Examples include sulfoxide and sulfone solvents such as diisopropylsulfone, diphenylsulfone, tetrahydrothiophene-1,1-dioxide, and tetrahydrothiophene-1-monoxide, particularly 1,3-dimethyl-2-imidazolidinone. , N-methyl-2-pyrrolidone and N-cyclohexyl-2-pyrrolidone are preferred.

Since the polymerization reaction for producing the polymer of the present invention is carried out under substantially anhydrous conditions, if water is brought into the polymerization system from the outside or condensation water is generated in the polymerization system, water is removed from the polymerization system. This is necessary, and the combined use of an azeotropic agent is effective. Examples of entrainers that can be used for dehydration include benzene, toluene, xylene, chlorobenzene, ortho-dichlorobenzene, and the like.

The polymerization reaction of the present invention is carried out at 50 to 450°C, preferably at 100°C.
It is carried out at a temperature range of ~400°C, and when actually carrying out the polymerization, the solubility, reactivity,
It is important to select optimal temperature conditions from the above temperature range depending on thermal characteristics and the like.

The polymerization reaction of the present invention is usually carried out at normal pressure, but depending on the type of reaction, it may be carried out under increased pressure.

Further, the polymerization time is usually 0.5 to 50 hours, and is set so that the logarithmic viscosity of the polymer is 0.5 or more, preferably 0.7 or more.

The polymerization reaction of the present invention is preferably carried out under an inert gas atmosphere to remove the influence of oxygen and moisture.

The polymerization reaction of the present invention can be stopped by simply cooling the reaction system, but it is also effective to add an alkyl halide, aryl halide, etc. to stop the reaction and stabilize the terminal phenoxide group moiety. . Examples of such alkyl halides and aryl halides include methyl chloride, methyl bromide, ethyl chloride, and 4,4'-dichlorodiphenyl sulfone.

When the polymer solution obtained from the polymerization reaction is mixed with a precipitant,
The polymer can be isolated. As the precipitant, a liquid that is miscible with the polymerization solvent but in which the polymer is insoluble, such as methanol, ethanol, isopropanol, acetone, water, etc., is employed.

If the reactant system solidifies after the polymerization reaction is completed or if the polymer is precipitated in the solution, it is possible to purify and separate the polymer by removing the alkali metal salt and reaction solvent by water extraction, solvent extraction, etc. can.

The polymer of the present invention can be utilized for various purposes as described below.

Compression molding is performed by adding a different polymer, if necessary, to the polymer of the present invention.
After tri-blending additives, fillers, reinforcing agents, etc.
It is usually carried out under conditions of 300 to 400°C and a pressure of 50 to 500 #/d.

In addition, extrusion molding and injection molding can be carried out by adding different polymers, additives, fillers, λ negative and pro l fr ν to the polymer of the present invention as required.
ノ v 1 Su-e n) Lie Su- God This is pelletized by an extruder, and the pellets are fed to an extrusion molding machine or an injection molding machine, and 3. ) It is carried out under the conditions of 0 to 400°C and an injection pressure of 800 to 2000 9/d.

For film and fiber manufacturing applications, the polymerization termination solution can be applied in dry or wet-dry extrusion processes;
Furthermore, the isolated polymer can be melt-molded by adding suitable additives as necessary. A laminate is made by laminating a cloth or mat made of glass fiber, carbon fiber, asbestos fiber, etc. and a polymer film or isolated polymer, and then laminating this at 200-400℃ and 30-300℃ under 9/d conditions. Manufactured by pressing.

Furthermore, for paint and coating purposes, it can be produced by applying or impregnating a molten polymer, or by removing the solvent from a polymer solution in a coating machine.

If necessary, the composition of the present invention may contain the following fillers in an amount of 70% by weight or less based on the entire composition. (a) Abrasion resistance properties and agents: graphite, carborundum, silica powder, molybdenum disulfide, fluororesin, etc. (1) Reinforcement agents: glass fiber, carbon fiber, boron fiber, silicon carbide fiber, carbon whisker, asbestos fiber, Asbestos, metal fibers, etc., (c) Flame retardant improvers: antimony ditrioxide, magnesium carbonate, calcium carbonate, etc., c) Electrical property improvers: clay, mica, etc., (e) Tracking resistance improvers: asbestos, silica,
graphite, etc., (f) Acid-resistant soil additives: barium sulfate, silica, calcium metasilicate, etc., (g) Thermal conductivity improvers: metal powders such as iron, zinc, aluminum, copper, etc.
Other Nigaras beads, glass bulbs, calcium carbonate,
Includes synthetic and natural compounds that are stable at temperatures above 300°C, such as alumina, talc, diatomaceous earth, hydrated alumina, mica, shirasu balloons, asbestos, various gold R oxides, and inorganic pigments.

<Examples> Hereinafter, the present invention will be further described in detail using Examples and Comparative Examples.

Note that the glass transition temperature (Tg) in this example was measured using a PerkinElmer Model IB DSC device. The infrared absorption spectrum was measured using an IR device manufactured by JASCO Corporation. Thermogravimetric analysis was performed using a GA device manufactured by Rigaku Denki. Moreover, the logarithmic viscosity (rinh) is the polymer concentration C=0.5f/d6. in 98% sulfuric acid. Measurement temperature 30℃
It is the logarithmic viscosity number measured at

Measurements of various physical properties were performed according to the following methods.

Bending strength (FS)...AS"I'M D79
Flexural modulus (FM),... ASTM D
790 Heat Distortion Temperature (HDT) ...ASTM
D648-56 (18, E) 6 to 9/i) In addition, unless otherwise specified, the values of %, parts, and ratios used in this example indicate the values of weight %, parts by weight, and weight ratio, respectively.

Example 1 Bis-(4-hydroxyphenyl) ether 1O11F (0,5 mole) and 1,3-dimethyl-2
-Imidazolidinone le was charged and uniformly dissolved. Next, while stirring the system, the temperature was gradually raised to 80°C, and then a 4596 sodium hydroxide aqueous solution 88.9°C was added under a nitrogen stream.
(10 mol) was added from the dropping funnel, and then the inside of the dropping funnel was washed with 20 wt of pure water and added to the system. Next, when toluene 5001 was added dropwise from the dropping funnel and the temperature inside the system was further increased, a toluene-water azeotrope began to distill from an internal temperature of around 130°C. The distilled azeotropic mixture was separated into a toluene layer and an aqueous layer, and when the temperature was continued to rise without returning the toluene layer to the system, the distillation of water ended at an internal temperature of around 150°C, so toluene was removed. The dripping of the solution was stopped, and the internal temperature was finally raised to around 171 J°C to completely drain out the remaining toluene. At this time, the inside of the system was a reddish-brown liquid.

Next, after cooling the inside to around 130℃,
(,6)+1. +rtma・+[=> +-,+ n n
I + to, 5 mol) was added to the system, and the temperature was raised again to an internal temperature of 220°C for 6 hours with stirring to complete the polymerization reaction. Subsequently, after cooling the inside to around 100° C., chlorobenzene 2e was added and stirred for several minutes, and a polymer was precipitated in powder form. The polymer powder obtained by passing through the suction port was thoroughly washed with ethanol and then water, and the solvent was removed in step 1.
After removing 3-dimethyl-2-imidazolidinone, the precipitant chlorobenzene, and the by-produced sodium chloride, the washed polymer powder was collected by filtration and vacuum-dried at 130°C for 12 hours. .2y (yield 90.6%) was obtained. The logarithmic viscosity of the polymer obtained here was 120, and the glass transition temperature (Tg) was 189°C.
Met. This polymer consists of the structural units shown below, and the results of elemental analysis showed good agreement with the theoretical values as shown in Table 1.

Table 1 Elemental analysis results The infrared spectrum of this polymer was as shown in FIG.

Next, 1ouf of the polymer powder obtained above was heated at 360°C for 1 hour.
Create a molded test piece by compression molding under the conditions of tJO#/d,
When the physical properties were measured, the bending strength was 1,500#/d,
The flexural modulus was excellent: 40.000h97dSHDT 192°C.

Example 2 2.6-difluoroanthraquinone l 22.1 f(
Example 1 except that 2,6-dichloroanthraquinone 138.7y (0.5 mol) was used instead of 0.5 mol).
A similar operation was performed to obtain a polymer having the following properties.

pinh = 0.80 Tg = 189 °C F S , = 1.4 0 0 kq / c4F
M = 38.000 kg/dHDT=19
0°C Example 3 Bis-(4-hydroxyphenyl)ether 1011f
The same operation as in Example 1 was carried out except that 4,4'-dihydroxydiphenyl 93.1f (0.5 mol) was used instead of (0.5 mol) and the compression molding temperature was changed from 360°C to 380°C. A polymer having the following structural unit was obtained.

The results of elemental analysis are shown in Table 2 and showed good agreement with the theoretical values.

The properties of this polymer were as follows.

7+1nh=0.77 Tg=215°C FS=1,200#/d FM=40,000ky/d HDT=216°C Comparative Example 1 2.6-difluoroanthraquinone l 22.1 y(
Example 1 except that 1,5-dichloroanthraquinone 138.7F (0.5 mol) was used instead of 0.5 mol)
A similar operation was performed to obtain a polymer having the following structural unit.

The properties of this polymer were as follows: not only was the polymerizability poor, but the strength of the molded product of the resulting polymer was also extremely low.

-Pinh = 0.36 =l'g =190℃ F'-+ H'4 11 n k/I/
AFM = 3 5,000 kg/d HDT = 191'C Comparative Example 2 2.6-Difluoroanthraquinone 122. l f(
0.5 mol) to 1,8-dichloroanthraquinone 138
．． A polymer having the following structural unit was obtained by carrying out the same operation as in Example 1 except that the amount was changed to 7 g (0.5 mol).

The properties of this polymer were as follows: not only was the polymerizability poor, but the strength of the molded product of the resulting polymer was also extremely low.

Pinh = 0.27 Tg = 195℃ FS = 400 to 9/d FM = 37.000 kq / dHDT =
197°C Example 4 Into the same apparatus as in Example 1, 114.1r (0.5 mol) of 2,2-bis-(4-hydroxyphenyl)propane and 2 dimethyl sulfoxide were charged and uniformly dissolved. Next, while stirring the system, the temperature was gradually raised to 50°C, and then a 45% aqueous sodium hydroxide solution (88%) was added under a nitrogen stream.
9IC (1.0 mol) was added from the dropping funnel, followed by 20
The inside of the dropping funnel was washed with 1 m of pure water and added to the system.

Next, when the temperature of the system was further increased while dropping 500 f of toluene from the dropping funnel, a toluene-water azeotrope began to be distilled from an internal temperature of around 110°C. The distilled azeotropic mixture is separated into a toluene layer and an aqueous layer, and if the temperature continues to rise without returning the toluene layer to the system, the internal temperature reaches 12
Distillation of water was completed at around 5°C, so dropping of toluene was stopped, and the internal temperature was finally raised to 169°C to distill off all remaining toluene. Next, after cooling the inside to around 80°C, 2,6-dichloroanthraquinone 97. I
F (0.35 mol) and 4,4'-dichlorodiphenylsulfone 43.1F (0.15 mol) were added to the system, and the temperature was raised again to 170°C for 5 hours with stirring to initiate a polymerization reaction. finished. After cooling the inside to around 80℃,
Chlorbenzene 2e was added and stirred for several minutes. When the solution after the by-produced metal salt was separated by filtration was gradually poured into ethanol under high speed stirring, the polymer precipitated out in the form of powder. This polymer powder was collected by mouth and vacuum-dried at 13LI℃ for 12 hours, resulting in a yellow polymer powder of 209
F (yield 96.0%) was obtained. Here, the logarithmic viscosity of the obtained polymer was 0.90, and the glass transition temperature was 21.
It was 0°C. This polymer consists of the structural units shown below, and the elemental analysis results also agreed well with the theoretical values.

m/n=70/30 molar ratio Next, this polymer powder 1fJOf was heated at 340°C, lUU#/
A molded test piece was created by compression molding under the conditions of d, and the physical properties were measured, and the bending strength was 1, 2 +j Okg/d,
Flexural modulus 30.000 kq/d.

HD′i” was 212°C.

Example 5 2.6-difluoroanthraquinone 1 i 2.1 F
(0.5 mol) instead of 2,6-dichloroanthra-
+/ :/ 97.11 (0.35 mol) Oyohi 4
．． 4'-dichlorodiphenylsulfone 43.1y (
0.15 mol) and 1 μL of bis-(4-hydroxyphenyl)ether (0.5 mol).
14'-dihydroquine diphenyl sulpon 125.1F
The same operation as in Example 1 was performed except that (0.5 mol) was used to obtain the main compound having the following structural unit. The results of elemental analysis of this polymer showed that the properties of this polymer were as follows.

pinh = 0.77 Tg = 240℃ F S = 1.450 kg / dF M =
35.000 kq/dHDT=242°C Example 6 In the same apparatus as in Example 1, 2,6-difluoroanthraquinone 85.5F (0.35 mol) and 4.4'-difluorobenzophenone 32.7F (0, t5 mol), hydroquinone 55.1 g (0.5 mol), diphenylsulfone 300 y and anhydrous potassium carbonate 71.9 y
(0.52 mol) was charged and the temperature was raised to 250°C while stirring. 251°C for 1 hour, 300°C for 2 hours, 35
After heating and stirring at U'C for 1 hour, the mixture was allowed to stand overnight under a nitrogen stream. The resulting solid was ground, extracted twice with acetone to remove diphenyl sulfone, and thoroughly washed with water to remove alkali metal salts. The obtained solid powder was vacuum dried at 130°C for 12 hours. <Effects of the Invention> The polymer of the present invention has good thermal properties and mechanical properties, and can be used for high-performance molded products, films, fibers, It is useful as a material for laminates, etc. Furthermore, it can be widely used as high-performance parts in cutting-edge industrial fields such as electrical and electronic parts, aerospace materials, automobile parts, and insulating materials.

[Brief explanation of drawings]

FIG. 1 is an infrared absorption spectrum of the polymer obtained in Example 1. Patent applicant Daito Shi Co., Ltd. S9 ((.-I) Patent applicant Daito Shi Co., Ltd.

Claims (2)

[Claims] (1) 50 to 100 mol% of structural units represented by general formula A, ▲ mathematical formulas, chemical formulas, tables, etc. ▼ and general formula B
, ▲ There are mathematical formulas, chemical formulas, tables, etc. The structural unit represented by ▼ (where Ar is a divalent aromatic residue, Y
▲There are mathematical formulas, chemical formulas, tables, etc.▼ and/or -
SO_2−) consists of 0 to 50 mol%, and 98
% sulfuric acid at a concentration of 0.5 g/dl and a temperature of 30°C, the thermoplastic aromatic polyether anthraquinone is characterized by having a logarithmic viscosity of 0.5 or more as measured at a temperature of 30°C. (2) General formula (a) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (b) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and/or (c) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (in the formula , X represents a chloro group or a fluoro group) and the general formula (d) MO-Ar-OM (wherein M is an alkali metal and Ar represents a divalent aromatic residue). When reacting the alkali metal salt of the dihydric phenol represented by (a), (b) and/or (c), (a)
0 to 50 mol%, (b) and/or (c) 0 to 50
A method for producing a thermoplastic aromatic polyether anthraquinone, characterized in that the thermoplastic aromatic polyether anthraquinone is used in a proportion of mol%.