JPH0676486B2 - Heat resistant resin and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel amorphous aromatic polyether ketone and a method for producing the same. More specifically,
The present invention has a chemical structure in which a phenylene group is linked via an ether group and a ketone group alternately, and a part of the phenylene group is substituted with a phenyl group, heat resistance, solvent resistance, low hygroscopicity, The present invention relates to a novel polymer having excellent low dielectric constant, flame retardancy, mechanical properties and the like, and a method for industrially producing the same.

Conventional technology There are two types of heat-resistant resins, crystalline and amorphous.
Each of these has advantages and disadvantages, and is used properly according to the application.

Amorphous heat-resistant resins include, for example, polysulfone, polyether sulfone, and polyetherimide. Since these have sulfone groups or imide groups as polar groups in the molecule, they are easily attacked by polar solvents and easily absorb moisture. It has the drawback of

On the other hand, as the crystalline heat-resistant resin, for example, polyphenylene sulfide, polyether ketone, etc. are known,
These are less susceptible to polar doubling, and have the advantage of low hygroscopicity because they do not contain a strong polar group, but on the other hand, they have a glass transition temperature higher than that of the above amorphous resins. It is low and has a drawback that the rigidity is lowered above this temperature.

Problems to be Solved by the Invention The object of the present invention is to improve the drawbacks of the conventional crystalline heat-resistant resin, in addition to the advantages that the crystalline heat-resistant resin inherently has a low hygroscopicity and is not easily attacked by a polar solvent, Another object of the present invention is to provide a heat resistant resin which has the advantage of having a high glass transition temperature.

Means for Solving the Problems As a result of intensive studies conducted by the present inventors, 4-halogeno-3′-phenyl-4′-hydroxybenzophenone or an alkali metal salt thereof was used as a raw material and obtained by polymerization. The novel phenyl-substituted aromatic polyether ketone thus obtained was surprisingly amorphous, and it was found that the above-mentioned object can be achieved thereby, and the present invention was completed based on this finding.

That is, the present invention has the formula And a phenyl-substituted aromatic polyether ketone having an intrinsic viscosity of 0.15 or more, which comprises a repeating unit represented by the general formula: (Wherein X is a halogen atom), a phenyl-substituted aromatic halophenol represented by the formula: is polymerized in the presence of an alkali, or an alkali metal salt of a phenyl-substituted aromatic halophenol represented by the general formula (II). Can be produced by polymerizing.

In the present invention, the phenyl-substituted aromatic halophenol represented by the general formula (II) used as a raw material monomer is a novel compound, and for example, p-halogenobenzoyl chloride and o-phenylphenol such as aluminum chloride are used. It can be prepared by a Friedel-Crafts reaction using a catalyst, or by a Fries rearrangement of 2-phenyl-phenyl-4'-halogenobenzoate.

In addition, another raw material monomer used in the present invention, the general formula The alkali metal salt of a phenyl-substituted aromatic halophenol represented by the formula (wherein X is a halogen atom and M is an alkali metal) is, for example, a phenyl-substituted aromatic halophenol and an alkali metal represented by the general formula (II). It can be produced by reacting with a hydroxide of.

Examples of the raw material monomer represented by the general formula (II) include 4-fluoro-3'-phenyl-4'-hydroxybenzophene and 4-chloro-3'-phenyl-4'-hydroxybenzophenone. There is. In producing the polyetherketone of the present invention, these may be used alone or in combination of two or more kinds.
Examples of the raw material monomer represented by the general formula (III) include 4-fluoro-3'-phenyl-4'-hydroxybenzophenone sodium salt and potassium salt,
There are sodium salts and potassium salts of 4-chloro-3′-phenyl-4′-hydroxybenzophenone, which may be used alone or in combination of two or more kinds.

Among these monomers, 4-fluoro-3'-phenyl-4'-hydroxybenzophenone and its alkali metal salt are highly reactive and a polymer having good thermal stability can be obtained. Therefore, it is preferable. Further, in the present invention, a small amount of 4 is used as long as the characteristics of the obtained polymer are not impaired.
-Fluoro-3 ', 5'-diphenyl-4'-hydroxybenzophenone or an alkali metal salt thereof is respectively combined with the 4-fluoro-3'-phenyl-4'-hydroxybenzophenone or an alkali metal salt thereof. Can also be used.

In the present invention, the polymerization reaction can be carried out in the presence or absence of a solvent, but it is generally desirable to carry out it in the presence of a lysis ratio. Examples of the solvent used at this time include xanthone, benzophenone, phenoxybenzophenone,
Ketone compounds such as dibenzoylbenzene, sulfone compounds such as diphenyl sulfone, ditolyl sulfone and sulfolane, and the like, and aromatic compounds are particularly preferable.

Examples of the alkali used in the present invention include alkali metal carbonates, alkali metal bicarbonates, and alkali metal hydroxides. Of these, alkali metal carbonates and alkali metal bicarbonates are particularly preferred. Examples of such compounds include sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, rubidium hydrogen carbonate, cesium hydrogen carbonate. These may be used alone or in combination of two or more. Of these, sodium carbonate, potassium carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate are particularly preferable.

These alkalis are used in a ratio such that the amount of alkali metal atoms is 0.3 to 2 gram atom, preferably 0.5 to 1.2 clam atom, relative to 1 mol of the monomer represented by the general formula (II). If the alkali is used in excess, the reaction becomes too violent, which causes a harmful side reaction, and is disadvantageous in terms of cost. Therefore, it is desirable to use as little amount as possible. However, the amount of alkali metal atoms is 0.3
When it is less than gram atom, the reaction rate is slow and it becomes difficult to obtain a polymer having a desired high molecular weight.

Next, for the polymerization in the present invention, an example of a preferred embodiment will be shown. In a desired solvent, a mixture of a predetermined amount of the monomer represented by the general formula (II) and an alkali, or in a desired solvent A mixture obtained by adding a predetermined amount of the monomer represented by the general formula (III) to, for example, nitrogen, heated under an inert gas atmosphere such as argon, 200 ~ 400 ℃, preferably in the range of 250 ~ 350 ℃. The polymerization reaction is performed at the temperature of. If the reaction temperature is lower than 200 ° C., it is difficult to obtain a high molecular weight polymer, while if it exceeds 400 ° C., the coloration due to the deterioration of the formed polymer becomes remarkable, such being undesirable.

It is important to gradually raise the temperature during the polymerization and devise such that the polymerization system is maintained at a uniform temperature in order to obtain a good polymer without gelation or coloring. Further, in order to obtain a polymer having a high molecular weight, it is necessary to finally set the polymerization temperature to 200 ° C. or higher, but prepolymerization at a temperature lower than that is also an advantageous method.

When the monomer represented by the general formula (II) is polymerized in the presence of an alkali, water is generated during the polymerization, but this water is preferably removed outside the system. The removal method is
There are a method of introducing a dry inert gas into the polymerization system or replacing the gas phase with the inert gas, a method of adding a solvent azeotropic with water to the polymerization system, and distilling it out of the system together with the solvent.

The polymerization reaction is carried out by adding an appropriate terminal stopper, for example, a monofunctional or polyfunctional halide, specifically dichlorodiphenyl sulfone, difluorobenzophenone, monofluorobenzophenone, methyl chloride, etc., to the reaction system and reacting. Can be terminated by means of which the end of the polymer chain can be stabilized.

The polymer of the present invention thus obtained has the formula It is an amorphous high molecular weight polymer composed of repeating units represented by

The polymer of the present invention has an ultimate electric field of 0.15 or more, and particularly preferably 0.3 or more for obtaining a film. Those having an intrinsic viscosity of less than 0.15 are not suitable because they do not show the properties as a polymer.

Effect of the Invention The aromatic polyether ketone of the present invention has a novel amorphous structure having a chemical structure in which a phenylene group is linked via an ether group and a ketone group, and a part of the phenylene group is substituted with a phenyl group. The polymer (1) has a glass transition temperature higher than that of the conventional aromatic polyetherketone and is less likely to be attacked by a polar solvent which is attacked by polysulfone, polyethersulfone and the like. In addition, the polyetherketone is composed entirely of benzene rings except for the bonding group, and does not contain any heat-labile alkyl group. Therefore, the heat resistance of the aromatic polyetherketone does not include a substituent. It is exceptionally good.

Therefore, the phenyl-substituted aromatic polyether ketone of the present invention is suitable as a molding material used under severe conditions of high temperature. This polymer can be used in any desired shape, for example, molded products, coatings, film fibers and the like, and further various engineering plastics, heat resistant resins such as polyetherketone and polyethersulfone, glass fibers and carbon fibers. , Can be mixed with an inorganic substance or the like to be alloyed or composited for use.

EXAMPLES Next, the present invention will be described in more detail with reference to the present invention, but the present invention is not limited to these examples.

Since the polymer of the present invention is insoluble in general organic solvents, it is difficult to obtain a uniform molecular weight. Therefore, the intrinsic viscosity is used as a measure of the molecular weight.

The physical properties of the polymer were measured as follows.

(1) Intrinsic viscosity Concentrated sulfuric acid with a density of 1.84 g / cm ³ was used to prepare a solution containing 0.1 g of polymer per 100 cm ^{3 of} solution and a solution containing 0.5 g of polymer per 100 cm ^{3 of} solution, and the viscosity was 25 ° C. The intrinsic viscosity = {(ηrel-1) / C} c → o [where ηrel is relative viscosity, c is concentration (g / 100 ml), and c → o is (ηrel-1) / C. It means that the value of was extrapolated to the point where the density C was 0].

(2) Glass transition temperature (Tg) The glass transition temperature (Tg) was measured by a DSC (differential scanning calorimeter) at a heating rate of 10 ° C / min.

Reference Example 1 Production of 4-fluoro-3'-phenyl-4'-hydroxybenzophenone In a three-necked flask of 1, nitrobenzene 200 ml, p-
After charging 16.3 g (103 mmol) of fluorobenzoyl chloride and 15.1 g (113 mmol) of aluminum chloride and purging the reaction system with nitrogen, 17.5 g of o-phenylphenol was added.
(103 mmol) was gradually added, and the mixture was reacted at 80 ° C for 8 hours. After completion of the reaction, hydrochloric acid was added, and the reaction mixture was steam-distilled to distill off nitrobenzene. Then, a solid matter was separated from the steam distillation residual liquid by filtration, washed with acetone and recrystallized with toluene for purification. It had a melting point of 200.0 to 201.0 ° C. and was confirmed to be 4-fluoro-3′-phenyl-4′-hydroxybenzophenone from elemental analysis, IR spectrum (FIG. 1) and NMR spectrum. .

Elemental analysis results CHOF measurement value (%) 77.9 4.4 11.1 6.6 calculation value (%) 78.1 4.5 10.9 6.5 (as C ₁₉ H ₁₃ O ₂ F) Reference Example 2 4-Fluoro-3′-phenyl-4′- Preparation of potassium salt of hydroxybenzophenone 4-fluoro-3'-phenyl-4'-hydroxybenzophenone 1N KO containing equimolar potassium hydroxide
After being dissolved in an aqueous solution of H, water was distilled off with an evaporator and then vacuum dried at 90 ° C for 10 hours to give 4-fluoro-
A potassium salt of 3'-phenyl-4'-hydroxybenzophenone was obtained.

Example 1 In a separable flask equipped with a stirrer, a nitrogen inlet tube and a condenser, 4-fluoro-3'-phenyl-4'-hydroxybenzophenone (17.5 g, 0.06 mol) and anhydrous potassium carbonate (4.2 g, 0.03) were added. Mol) and 30 g of benzophenone, start heating under a nitrogen atmosphere, raise the temperature to 300 ° C. while removing water in the system to the outside by nitrogen gas, and carry out polymerization at that temperature for 6 hours, 4, at this temperature
2 g of 4'-difluorobenzophenone was added and reacted for 30 minutes.

After the completion of the reaction, the solid substance obtained by cooling was crushed, washed twice with warm acetone, twice with warm water, and once with warm acetone to obtain a polymer powder with a yield of 93%.

The obtained polymer was completely dissolved in concentrated sulfuric acid, contained no gel, and had an intrinsic viscosity of 0.70. 320 ° C of this polymer
When the glass transition temperature (Tg) was measured using a film obtained by rapidly melting and then rapidly cooling, Tg was 178 ° C, and no endothermic peak or crystal melting point due to crystallization temperature crystallization was observed. The product was an amorphous polymer. No peak due to crystals was observed in the X-ray diffraction chart of this polymer.

No peak due to crystals was observed in the X-ray diffraction chart of this polymer.

The IR analysis chart of this polymer is shown in the second.

In addition, the elemental analysis result is C H 2 O 2 measured value (%) 83.8 4.4 11.8 calculated value (%) 83.7 4.6 11.7 (as C ₁₉ H ₁₂ O ₂ ). It was confirmed to have the structure of.

This polymer dissolves or corrodes commercially available polysulfone (registered trade name Udel, manufactured by UCC) or polyether sulfone (registered trade name Victrex PES, manufactured by ICI), which are amorphous heat-resistant resins, at room temperature. Methylene chloride and benzene,
Alternatively, it was not dissolved at all in a polar solvent such as acetone, dimethylacetamide or N-methylpyrrolidone, and was not attacked.

The film obtained by pressing this polymer at 340 ° C. for 4 minutes was extremely strong against repeated bending, and the film had a tensile strength of 910 kg / cm ³ and an elongation at break of 100% (measurement method ASTM D882). ).

Further, the thermal loss of this polymer was measured and showed no weight loss up to 501 ° C, and the 5% by weight thermal loss temperature was 552 ° C. Furthermore, the water absorption of this polymer (40% RH for 24 hours) is 0.
It was good at 14%.

Examples 2 to 5 Regarding the monomer, alkali, polymerization solvent, polymerization temperature and polymerization time, the polymerization was carried out under the conditions shown in the following table, and the other conditions were the same as in Example 1. The intrinsic viscosity and glass transition temperature of the obtained polymer are shown in the table.

Example 6 19.8 g (0.06 mol) of potassium salt of 4-fluoro-3′-phenyl-4′-hydroxybenzophenone and 40 g of diphenyl sulfone were placed in a separable flask, and the same method as in Example 1 was used to prepare 300 After reacting at 6 ° C. for 6 hours to carry out an end-terminating reaction, the produced polymer was separated.

The obtained polymer had an intrinsic viscosity of 0.85 and a Tg of 182 ° C.

[Brief description of drawings]

FIG. 1 is an IR spectrum chart of 4-fluoro-3′-phenyl-4′-hydroxybenzophenone used in the present invention, and FIG. 2 is an IR spectrum chart of an example of the polymer of the present invention.

Claims (3)

[Claims] 1. A formula A phenyl-substituted aromatic polyether ketone having a limiting viscosity of 0.15 or more, comprising a repeating unit represented by: 2. The general formula in the presence of alkali (Wherein X is a halogen atom), a phenyl-substituted aromatic halophenol represented by the formula: A process for producing a phenyl-substituted aromatic polyether ketone, which comprises a repeating unit represented by the formula (1) and has an intrinsic viscosity of 0.15 or more. 3. General formula Wherein X is a halogen atom and M is an alkali metal, and an alkali metal salt of a phenyl-substituted aromatic halophenol represented by the formula: is polymerized. A process for producing a phenyl-substituted aromatic polyether ketone, which comprises a repeating unit represented by the formula (1) and has an intrinsic viscosity of 0.15 or more.