JPH0749477B2 - Aromatic polyether and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to an aromatic polyether and a method for producing the same, and more specifically, it has improved heat resistance and excellent solvent resistance and mechanical strength. In addition, an aromatic polyether that has good moldability and can be suitably used as a material in the fields of electronics and electricity, machines, etc.,
The present invention relates to a production method capable of efficiently obtaining this aromatic polyether by a simple process.

[Prior Art and Problems to be Solved by the Invention] In recent years, engineering resins having various structures have been developed. For example, in the fields of automobiles, electric / electronics, precision machinery, office automation equipment, optical communication equipment, etc. Although it is used in a wide range of fields, its performance has not been satisfactory in all respects, and moreover, the required performance has become strict, and therefore the development of new materials is desired.

On the other hand, aromatic polyetherketone, which is one of the engineering resins, is a resin having crystallinity and particularly excellent heat resistance, and various proposals have been made for this aromatic polyetherketone.

For example, in JP-A-54-90296, the following formula; Disclosed is a thermoplastic aromatic polyether ketone containing a repeating unit represented by the formula (1) alone or in combination with other repeating units and having an intrinsic viscosity of 0.7 or more.

In JP-A-61-138626, a repeating unit A represented by the following formula: -O-Ph-O-Ph-CO-Ph- and the following formula: -O-Ph-Ph-O-Ph. A repeating unit B represented by —CO—Ph—, and the molar ratio of repeating unit A to repeating unit B (repeat unit A): (repeat unit B) is 95: 5.
~ 60:40 with a melt viscosity of 0.06 measured at a temperature of 400 ° C.
Disclosed is a thermoplastic aromatic polyether ketone having a kN.sm ⁻¹ or more and Ph being a phenylene group.

However, these aromatic polyether ketones have a relatively low glass transition temperature of, for example, about 143 ° C. to 155 ° C., and cannot maintain rigidity in a temperature range exceeding the glass transition temperature, resulting in heat resistance. The sex is not enough.

Further, these aromatic polyethers have a high crystallization temperature, it is necessary to raise the temperature of the molding die during the molding process, and the melting point is high, for example, 400 ° C. or higher, so that the molding processability is difficult.

The present invention has been made based on the above circumstances.

The object of the present invention is to improve the heat resistance, solvent resistance, excellent mechanical strength, and good moldability aromatic polyether, and a method for efficiently producing this aromatic polyether. To provide.

[Means for Solving the Problems] In order to solve the above problems, as a result of extensive studies by the present inventors, an aromatic polyether having a specific repeating unit in a specific ratio and a specific melt viscosity. Is
Aromatic polyethers with high glass transition temperature and improved heat resistance, excellent solvent resistance and mechanical strength, and good moldability. The present invention has been accomplished by finding that the compound can be efficiently produced by a specific method using the above raw materials.

The structure of the invention of claim 1 is represented by the following formula (I); A repeating unit represented by the following formula (II); Having a repeating unit represented by the formula (I
(Except when the repeating unit represented by I) does not appear continuously), the repeating unit represented by the above formula (I) with respect to the total of the repeating unit represented by the above formula (I) and the repeating unit represented by the above formula (II). The molar ratio of repeating units {(I) / [(I) + (II)]} is 0.1 to 0.9, and the melt viscosity (zero shear viscosity) at a temperature of 400 ° C.
It is an aromatic polyether characterized by having a porosity of 2,500 to 50,000, and the constitution of the invention of claim 2 is dihalogenobenzophenone, sodium sulfide and 4,4'-biphenol in a neutral polar solvent. The method for producing an aromatic polyether according to claim 1, characterized in that

An aromatic polyether according to claim 1 and claim 2 below.
The manufacturing method described in 1) will be described in detail.

--Aromatic polyether according to claim 1--In the aromatic polyether according to claim 1, a repeating unit represented by the formula (I) and a repeating unit represented by the formula (II). With (but
Unless the repeating unit represented by the formula (II) does not appear continuously), the formula (I) with respect to the sum of the repeating unit represented by the formula (I) and the repeating unit represented by the formula (II). It is necessary that the molar ratio {(I) / [(I) + (II)]} of the repeating units represented by) is 0.1 to 0.9, preferably 0.2 to 0.8.

If this molar ratio is less than 0.1, the glass transition temperature of the copolymer may be lowered, and the heat resistance may be lowered. on the other hand,
If it exceeds 0.9, the melting point tends to be too high and the moldability may deteriorate.

Further, in the aromatic polyether according to claim 1, the melt viscosity at a temperature of 400 ° C. (zero shear viscosity) is 2,5.
Must be between 00 and 50,000 poise.

A low molecular weight copolymer having a melt viscosity of less than 2,500 poise may not be able to achieve sufficient heat resistance and mechanical strength. On the other hand, if it exceeds 50,000 poise, the moldability may be deteriorated.

The glass transition temperature (Tg) of the aromatic polyether according to claim 1 is usually 160 to 175 ° C. The crystal melting point (Tm) is 360 to 380 ° C.

Therefore, the aromatic polyether according to claim 1 has improved heat resistance, excellent solvent resistance, mechanical strength, and improved moldability, and is a field of application requiring high heat resistance. Can also be suitably used.

The aromatic polyether described in claim 1 having such excellent characteristics can be efficiently obtained by suitably adopting the production method described in claim 2 described in detail below.

--Production method according to claim 2 --- Raw material-- In the method for producing an aromatic polyether according to claim 2, dihalogenobenzophenone, sodium sulfide, and 4,4'-biphenol are used as raw materials. To use.

In the method of the present invention, among the dihalogenobenzophenones, the following formulas; (However, in the above formula, X is a halogen atom.) 4,4'-dihalogenobenzophenone represented by the following can be preferably used. Specifically, 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone,
4-chloro-4'-fluorobenzophenone etc. can be mentioned.

Among these, 4,4'-difluorobenzophenone and 4,4'-dichlorobenzophenone are particularly preferable.

The sodium sulfide to be used is not particularly limited and may be an anhydrous salt, for example, 9-hydrate,
It may be a hydrous salt such as a hexahydrate or a pentahydrate.

Specifically, for example, an anhydrous salt obtained by directly reacting sulfur with sodium or by heating and dehydrating a hydrated salt in a hydrogen stream, or saturated aqueous solution of sodium hydroxide with saturated hydrogen sulfide, and then equivalent amount Sodium hydroxide is added to concentrate and then cooled and solidified to obtain a hydrated salt.

In the method of the present invention, sodium hydrofluoride can be used instead of the sodium sulfide or together with the sodium sulfide.

-Solvent etc.-In the method of the present invention, the dihalogenobenzophenone, the sodium sulfide and the 4,4'-biphenol are reacted in a neutral polar solvent. Then, this reaction is preferably performed in the presence of an alkali metal compound.

Examples of the neutral polar solvent to be used include N,
N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dipropylacetamide, 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-isopropyl-2-piperidone, N-methyl-6-methyl-2-piperidone, N
-Methyl-3-ethylpiperidone, dimethyl sulfoxide, diethyl sulfoxide, 1-methyl-1-oxosulfolane, 1-ethyl-1-oxosulfolane, 1-phenyl-1-oxosulfolane, N, N'-dimethylimidazolidinone, Examples thereof include diphenyl sulfone.

These may be used alone or in combination of two or more.

Among these, N, N'-dimethylimidazolidinone is particularly preferable.

The alkali metal compound is not particularly limited as long as it can convert the 4,4′-biphenol into an alkali metal salt, and is preferably an alkali metal carbonate or an alkali metal hydrogen carbonate.

Examples of the alkali metal carbonate include lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate,
Examples include cesium carbonate.

Among these, sodium carbonate and potassium carbonate are preferable.

Examples of the alkali metal hydrogen carbonate include lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate,
Examples thereof include rubidium hydrogen carbonate and cesium hydrogen carbonate.

Among these, sodium hydrogen carbonate and potassium hydrogen carbonate are preferable.

In the method of the present invention, sodium carbonate and potassium carbonate can be particularly preferably used among the various alkali metal compounds.

-Feeding ratio-In the method of the present invention, the feeding ratio of the dihalogenobenzophenone to the sodium sulfide and the 4,4'-biphenol is (dihalogenobenzophenone) / (4,
The molar ratio of 4'-biphenol + sodium sulfide) is usually 0.98 to 1.02, preferably 1.00 to 1.01. If this molar ratio is less than 0.98, the coloring may become remarkable and only an oligomer may be obtained. on the other hand,
If it exceeds 1.02, only an oligomer may be obtained.

When the alkali metal compound is used, the amount of the alkali metal compound used is usually 1.00 to 4.00 gram equivalent per 1 mol of the hydroxyl group of 4,4′-biphenol,
It is preferably 1.20 to 3.00 gram equivalent.

The amount of the neutral polar solvent used is not particularly limited, but is usually the dihalogenobenzophenone and 4,
It is selected in the range of 200 to 2000 parts by weight based on 100 parts by weight of 4'-biphenol and optionally the above-mentioned alkali metal compound.

In order to obtain the aromatic polyether according to claim 1 by the method of the present invention, for example, the dihalogenobenzophenone, the sodium sulfide, and the 4,4′-biphenol are added to the neutral polar solvent. In some cases, the alkali metal compound is further added at the same time to carry out a series of reactions at a temperature usually in the range of 150 to 350 ° C, preferably 180 to 250 ° C. If the reaction temperature is lower than 150 ° C, the reaction rate is too slow to be practical, and if it exceeds 350 ° C, a side reaction may occur.

The reaction time of this series of reactions is usually 0.1 to 10 hours, preferably 1 to 5 hours.

The aromatic polyether thus obtained has a repeating unit represented by the formula (I) and a repeating unit represented by the formula (II) (provided that the repeating unit represented by the formula (II) is Is not present continuously), the molar ratio of the repeating unit represented by the above formula (I) to the total of the repeating unit represented by the above formula (I) and the repeating unit represented by the above formula (II) { (I) /
[(I) + (II)]} is 0.1 to 0.9, and the temperature is
Melt viscosity (zero shear viscosity) at 400 ℃ is 2,500 to 50,0
It is a copolymer that is 00 poise.

Therefore, according to the manufacturing method of claim 2, the aromatic polyether of claim 1 having the above-mentioned excellent features can be efficiently obtained by a simple process.

[Examples] Next, the present invention will be described more specifically with reference to Examples and Comparative Examples of the present invention.

(Example 1) 4,4'-difluorobenzophenone (22.038 g (0.1%) was added to a reactor having an internal volume of 1 equipped with a Dean Stark trap filled with toluene, a stirrer, and an argon gas blowing tube.
Mol), sodium sulfide pentahydrate (Na ₂ S ・ 5H ₂ O) 8.406g
(0.05 mol), 4,4'-biphenol 9.311 g (0.05 mol), potassium carbonate 13.821 g (0.1 mol) and dimethyl imidazolidinone 400 ml were added, and while blowing an argon gas, the temperature was changed from room temperature to 215 ° C over 1 hour. The temperature was raised to.

Here, toluene was refluxed using a Dean Stark trap, and water in the reactor was azeotropically removed.

Then, after carrying out the reaction at a temperature of 195 ° C. for 1 hour, toluene was extracted, and the mixture was further heated and stirred at 220 ° C. for 2 hours.

After completion of the reaction, the product was crushed with a blender (manufactured by Warning Co., Ltd.), washed twice with water and twice with methanol, and then dried to obtain 32.8 g of white powder (yield 9
7%).

As a result of elemental analysis of this white powder, it was found to be a copolymer composed of the following repeating units.

In addition, the properties of this copolymer were measured, and the glass transition temperature (Tg) was 174 ° C, the crystallization temperature (Tcc) was 186 ° C,
The crystal melting point (Tm) was 370 ° C., the thermal decomposition starting temperature (Td) was 560 ° C. (5% weight loss in air), and the melt viscosity (zero shear viscosity) at a temperature of 400 ° C. was 14,000 poise.

(Example 2) In Example 1, the amount of sodium sulfide pentahydrate used was changed from 8.406 g (0.05 mol) to 11.772 g (0.07 mol), and the amount of 4,4'-biphenol used was changed to 9.311 g (0.05 mol). Mol) to 5.586 g (0.03 mol), and the amount of potassium carbonate used from 13.821 g (0.1 mol) to 8.293 g (0.06 mol)
Mol), and the same procedure as in Example 1 was repeated.

The yield of the obtained copolymer was 25.3 g (yield 98%). In addition, as a result of elemental analysis, it was found to have the following repeating units.

In addition, the properties of this copolymer were measured, and the glass transition temperature (Tg) was 163 ° C, the crystallization temperature (Tcc) was 174 ° C,
The crystal melting point (Tm) was 367 ° C, the thermal decomposition starting temperature (Td) was 553 ° C (5% weight loss in air), and the melt viscosity (zero shear viscosity) at a temperature of 400 ° C was 16,000 poise.

(Example 3) In Example 1, the amount of sodium sulfide pentahydrate used was changed from 8.406 g (0.05 mol) to 5.046 g (0.03 mol),
In addition to changing the amount of 4,4'-biphenol used from 9.311g (0.05mol) to 13.035g (0.07mol), the amount of potassium carbonate changed from 13.821g (0.1mol) to 19.341g (0.14mol) Was carried out in the same manner as in Example 1 above.

The yield of the obtained copolymer was 31.3 g (yield 98%). In addition, as a result of elemental analysis, it was found to have the following repeating units.

In addition, the properties of this copolymer were measured, and the glass transition temperature (Tg) was 172 ° C, the crystallization temperature (Tcc) was 183 ° C,
The crystal melting point (Tm) was 372 ° C, the thermal decomposition initiation temperature (Td) was 560 ° C (5% weight loss in air), and the melt viscosity (zero shear viscosity) at a temperature of 400 ° C was 13,000 poise.

(Comparative Example 1) In the same apparatus as that used in Example 1,
21.820 g (0.1 mol) of 4'-dibroulobenzophenone,
4,4'-biphenol 18.621 g (0.1 mol), potassium carbonate 14.512 g (0.105 mol) and diphenyl sulfone 60 g
Was charged. Then, the temperature was raised to 180 ° C under an argon stream and maintained at 180 ° C for 30 minutes, then at 280 ° C for 1 hour and 30 minutes.
The temperature was raised to 380 ° C. over 30 minutes, the temperature was maintained at 380 ° C. for 30 minutes, and the temperature was maintained for 1 hour to carry out the reaction.

After completion of the reaction, the reaction product was poured into a stainless steel vat, cooled and solidified, pulverized with a blender (Warning), washed with acetone twice, and washed with water 2 times.
By washing once with methanol and once with acetone to remove diphenyl sulfone and inorganic salts and drying to obtain 35.7 g (yield 98%) of a white powdery polymer. It was

As a result of elemental analysis of this polymer, it was found to have the following repeating units.

In addition, the properties of this polymer were measured. As a result, the glass transition temperature (Tg) was 167 ° C, the crystallization temperature (Tcc) was 215 ° C, the crystal melting point (Tm) was 420 ° C, the thermal decomposition initiation temperature (Td) was 558 ° C (in air). 5% weight loss). The melting temperature could not be measured because the melting point was too high. Therefore, it was dissolved in concentrated sulfuric acid at a concentration of 0.5 g / dl and the reduced viscosity [ηsp / c] was measured at a temperature of 25 ° C. The reduced viscosity [ηsp / c]
Was 0.97 dl / g.

[Effect of the Invention] (1) According to the invention of claim 1, since it has a specific repeating unit in a specific ratio and exhibits a specific melt viscosity, the glass transition temperature is high and the heat resistance is improved. In addition, it is excellent in solvent resistance and mechanical strength, and has a low crystallization temperature and a low crystal melting point to improve moldability. For example, a novel material useful as a material in the fields of electric and electronic devices, machines, etc. Aromatic polyethers can be provided.

(2) Further, according to the invention of claim 2, the novel aromatic polyether having the above-mentioned excellent properties can be efficiently obtained by a simple process, and the industrially useful aromatic polyether is produced. A method can be provided.

Claims (2)

[Claims] 1. The following formula (I); A repeating unit represented by the following formula (II); Having a repeating unit represented by the formula (I
(Except when the repeating unit represented by I) does not appear continuously), the repeating unit represented by the above formula (I) with respect to the total of the repeating unit represented by the above formula (I) and the repeating unit represented by the above formula (II). The molar ratio of repeating units {(I) / [(I) + (II)]} is 0.1 to 0.9, and the melt viscosity (zero shear viscosity) at a temperature of 400 ° C.
Aromatic polyethers characterized by 2,500-50,000 poise. 2. The process for producing an aromatic polyether according to claim 1, wherein dihalogenobenzophenone, sodium sulfide and 4,4′-biphenol are reacted in a neutral polar solvent.