JPS62253618A - Heat-resistant resin and production thereof - Google Patents

Abstract

PURPOSE:To obtain the titled resin suitable as a molding material under high temperature, consisting of a specific repeating unit, having intrinsic viscosity of >=specific value and high glass transition temperature, by polymerizing a phenyl-substituted aromatic halophenol in the presence of an alkali. CONSTITUTION:A 4-halogeno-3'-phenyl-4'-hydroxybenzophenone shown by formula I (X is halogen) or an alkali metallic salt thereof (e.g. 4-fluoro-3'-phenyl-4'- hydroxybenzophenone, etc.) is polymerized in the presence of an alkali (preferably sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, sodium hydrogencarbonate, etc.) to give a phenyl-substituted aromatic polyether ketone consisting of a repeating unit shown by formula II and having >=0.15 intrinsic viscosity. The compound shown by formula I as a starting raw material is a novel substance.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a novel non-grade aromatic polyetherketone and a method for producing the same. In more detail, 7
The present invention has a chemical structure in which phenylene groups are connected alternately through ether groups and ketone groups, and a part of the phenylene groups are substituted with phenyl groups, and has high heat resistance and solvent resistance. The present invention relates to a novel polymer having excellent mechanical properties, low hygroscopicity, low dielectric constant, flame retardancy, etc., and a method for industrially producing the same.

Conventional technology There are two types of heat-resistant resins: crystalline ones and non-crystalline ones.
Each of these has advantages and disadvantages, and they cannot be used properly depending on the purpose.

Examples of non-quality heat-resistant resins include polysulfone.

There are polyether sulfones, polyetherimides, etc., and since these have sulfone groups or imide groups as polar groups in their molecules, they have the drawback of being easily attacked by polar solvents and easily absorbing moisture.

Examples of crystalline heat-resistant resins include polyphenylene sulfide and polyether keto/1. These are polar solvents.

It also has the advantage of having low hygroscopicity because it does not contain strong polar groups, but on the other hand, it has a lower glass transition temperature than the above-mentioned non-grade resins, and its rigidity decreases above this temperature. I am nurturing my flaws.

Problems to be Solved by the Invention The purpose of the present invention is to improve all of the drawbacks of conventional crystalline heat-resistant resins, and to improve upon the inherent advantages of crystalline heat-resistant resins, such as resistance to attack by polar solvents and low hygroscopicity. In addition, it is an object of the present invention to provide a heat-resistant titanium fat that exhibits the advantage of a high glass transition temperature.

Means for Solving the Problems As a result of extensive research, the present inventors found that 4-halogeno-3'-phenyl-4'-hydroxybenzophenone or its alkali metal salt was used as a raw material and obtained by polymerization. It was discovered that the novel phenyl-substituted aromatic polyetherketone was surprisingly non-poor, and that the above object could be achieved by this method, and based on this knowledge, the invention was completed.

That is, the present invention provides a phenyl-substituted aromatic polyetherketone that is composed of repeating units represented by the formula and has an intrinsic viscosity of 15 or more; is a halogen atom) in the presence of a total alkali, or polymerize an alkali metal salt of a phenyl-substituted aromatic halophenol represented by the general formula (n) above. It can be manufactured by

In the present invention, the phenyl-substituted aromatic halophenol represented by the general formula (n) used as a raw material monomer is a new compound. For example, p-halogenobenzoyl chloride and 0-phenylphenol are combined with aluminum chloride or It can be produced by Friedel-Crafts reaction using a catalyst, or by Fries rearrangement of 2-phenyl-phenyl-4'-halogenobenzoate.

In addition, another raw material monomer used in the present invention, an alkali metal salt of a phenyl-substituted aromatic halophenol represented by the general formula (wherein X is a halogen atom and M is an alkali metal), is 1. For example, it can be produced by reacting a phenyl-substituted aromatic halophenol represented by the general formula (II) with an alkali metal hydroxide.

Examples of the raw material monomer represented by the general formula (n) include 4-fluoro-3'-phenyl-4'-hydroxybenzophene/4-chloro-3'-phenyl-4'-
Examples include hydroxybenzophenone. When producing the polyetherketone of the present invention, each of these may be used alone, or two or more may be used in combination. As the raw material monomer represented by the general formula 〇), for example, 4-fluoro-31-phenyl-4'-
There are sodium salts and potassium salts of hydroxybenzophenone, sodium salts and potassium salts of 4-chloro3'-phenyl-4'-hydroxybenzophenone, and each of these may be used alone or in combination of two or more. It may also be used.

Among these monomers, 4-fluoro-3'-phenyl-4'-hydroxybenzophenone and its alkali metal salts are preferred because they are highly reactive and provide polymers with good thermal stability. . Furthermore, in the present invention, a small amount of 4-
Fluoro-3: s/-diphenyl-4'-hydroxybenzophenone or an alkali metal salt thereof is combined with the aforementioned 4-fluoro-3'-phenyl-4'-hydroxybenzophenone or an alkali metal salt thereof. It can also be used.

In the present invention, the double 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 solvent. Examples of the solvent used in this case include Xa7ton and benzophenol.

Ketone compounds such as phenoxybenzophenone and dibenzoylbenzenato, sulfone compounds such as diphenylsulfone, ditolylsulfone, and sulfolane, and aromatic compounds are particularly preferred.

Examples of the alkali used in the present invention include alkali metal carbonates, alkali metal bicarbonates, and alkali metal hydroxides, among which alkali metal carbonates and alkali metal bicarbonates are particularly preferred. Examples of such compounds include sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, sodium bicarbonate, potassium bicarbonate, rubidium bicarbonate, cesium bicarbonate, and the like. Each of these may be used alone or in combination of two or more.

Among these, particularly preferred are sodium carbonate, potassium carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate.

These alkalis have an amount of alkali metal atoms of 0.3 to 1 mole of the monomer represented by the general formula (II) above.
The proportions used are such that there are 2 gram atoms, preferably 0.5 to 1.2 gram atoms. If the alkali is used in excess, the reaction will be too vigorous,9 causing harmful side reactions and also being disadvantageous in terms of cost, so it is desirable to use as little amount as possible. However, if the amount of alkali metal atoms is less than 3 gram atoms, the reaction rate is slow and it becomes difficult to obtain a desired high molecular weight polymer.

Next, examples of preferred embodiments of the polymerization in the present invention include a mixture in which a predetermined amount of the monomer represented by the general formula (■) and an alkali are added to a desired solvent, or a desired solvent. A mixture to which a predetermined amount of the monomer represented by the general formula @) is added.

For example, the polymerization reaction is carried out by heating under an inert gas atmosphere such as nitrogen or argon at a temperature in the range of 200 to 400°C, preferably 250 to 350°C. The reaction temperature is 200
If it is below ℃, it is difficult to obtain a polymer with a high molecular weight;
If the temperature exceeds 0°C, the resulting polymer will become significantly colored due to deterioration, which is not preferable.

It is important to raise the temperature gradually during polymerization and to maintain a uniform temperature in the monopolymerization system in order to obtain a good polymer without gel or coloration.

In addition, in order to obtain a high molecular weight polymer, it is necessary to ultimately raise the polymerization temperature to 200°C or higher;
Prepolymerization at temperatures below is also an advantageous method.

When the monomers represented by general formula (n) are polymerized in the presence of a total alkali, water is generated during the polymerization, but it is desirable to remove this water from the system. The way to remove it is
There are methods such as introducing a dry inert gas into the polymerization system or replacing the gas phase with the inert gas, and methods in which a solvent azeotropic with water is added to the entire polymerization system and distilled out of the system together with the solvent.

The polymerization reaction is stopped by adding to the reaction system a suitable terminal terminator, such as a monofunctional or polyfunctional halide, specifically dichlorodiphenylsulfone, difluorobenzophenone, monofluorobenzophenone, methyl chloride. can be made, and by this,
It can stabilize the ends of polymer chains.

The polymer of the present invention thus obtained is a non-quality high molecular weight polymer consisting of 9 repeating units represented by the formula 1.

The polymer of the present invention has an intrinsic viscosity of 0.15 or more, and particularly preferably 0.3 or more for obtaining a film. A polymer having an intrinsic viscosity of less than 0.15 exhibits no properties as a polymer and is unsuitable.

Effects of the Invention The aromatic polyetherketone of the present invention has a novel chemical structure in which phenylene groups are connected via an ether group and a ketone group, and a part of the phenylene group is substituted with a phenyl group. It is an inferior polymer with a higher glass transition temperature than conventional aromatic polyetherketones.
It also has the characteristic of not being attacked by colored solvents that attack polysulfone, polyether sulfone, and the like. In addition, the polyetherketone is entirely composed of benzene rings except for the bonding group, and does not contain any heat-labile alkyl groups, so its heat resistance is higher than that of an aromatic polyether containing no substituents. As good as ketones.

Therefore, the phenyl-substituted aromatic polyetherketone of the present invention is suitable as a molding material used under severe conditions at high temperatures. The polymers can be used in any desired shape, such as molded articles, coatings, film fibers, etc., as well as various engineering/engineering plastics, polyetherketones, etc.

Heat-resistant resins such as polyether sulfone, glass fibers,
It can be mixed with carbon fiber, inorganic materials, etc., and used as an alloy or composite.

EXAMPLES Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way.

In addition, since the polymer of the present invention is insoluble in general M solvents, it is difficult to determine the average molecular weight of the polymer. Therefore, the intrinsic viscosity is used as a measure of molecular weight.

Further, the physical properties of the heptapolymer were measured as follows.

(1) Concentrated sulfuric acid with an intrinsic viscosity density of 1.84 y/- is used, and a solution containing 0.12 polymer per 100 mm of solution and a solution containing 0.12 polymer per 100 mm of solution and 0.12 mm of polymer per 100 mm of solution are used. A solution containing FM'i was prepared, and its viscosity was measured at 25°C, using the formula % [where 17ret is the relative viscosity and C is the concentration (y/io
□-), and c-+o means that the value of (ηret-1)/C, the degree of total collapse C is extrapolated to the point O].

(2) Glass transition temperature (Tg) DSO (differential scanning calorimeter) with rising rate of 10°C/mi
Measured at n.

Nitrobenzene 2007 in a 1 ton three-bottle flask!1
p-fluorobenzoyl chloride 16.3 F (10
3 mmol) and aluminum chloride 15.19 (113
After replacing the reaction system with nitrogen,
-Phenylphenol 17.59 (103 mmol)
was gradually added and reacted at 80°C for 8 hours. After the reaction was completed, hydrochloric acid was added and the reaction mixture was steam distilled to remove nitrobenzene.

Solid matter was filtered from the steam distillation residue, washed with acetone, and purified by recrystallization with toluene. This thing.

Melting point is 200.0-201.0℃, elemental analysis, I
R spectrum (Fig. 1), NMR spectrum, 4-
It was confirmed that it was fluoro-3'-phenyl-4'-hydroxybenzophenone.

Elemental analysis result HOF Actual value (%) 77.9 4.4 11.1 6
．． 6 Calculated value (chi) 78.1 4.5 , lO,
96,5 (as C19H1302F) Reference N2 4-fluoro-31-F22-14'-1:
Preparation of 4-fluoro-3'-phenyl-4'-hydroxybenzophenone in l normal K containing equimolar potassium hydroxide
After dissolving in an OH aqueous solution, water was distilled off using an evaporator, and then heated at 90°C for 10 hours. By drying, a potassium salt of 4-fluoro-3'-7enyl-4'-hydroxybenzophenone was obtained.

Example 1 17.5 f (0.06 moles) of 4-fluoro-3'-phenyl-4'-hydroxybenzophenone and anhydrous potassium carbonate 4. 29 (0.03 mol) and benzophenone 30f were introduced, heating was started under a nitrogen atmosphere, and the temperature was raised to 300'C while removing moisture in the system to the outside of the yarn with nitrogen gas, and at that temperature for 6 hours. After polymerization, 4°4'-difluorobenzophenone 2? was added and allowed to react for 30 minutes.

After the reaction was completed, it was cooled and the solid material obtained was pulverized and washed twice with hot acetone, twice with hot water, and once with hot acetone to obtain a polymer powder with a yield of 93%.

The obtained polymer was completely dissolved in concentrated sulfuric acid, did not form a gel, and had an intrinsic viscosity of 0.70"t". The glass transition temperature (Tg) was measured using a film obtained by melting this polymer at 320°C and then rapidly cooling it.
The temperature was 178°C, and no endothermic peak or crystal melting point due to temperature crystallization was observed, indicating that this polymer was of poor quality. Moreover, no peak due to crystals was observed in the X-ray diffraction chart of this polymer.

An IR analysis chart of this polymer is shown in FIG.

Also, what are the results of elemental analysis? , HO actual value (%) 83.8. 4.4 11.
8 Calculated value (%) 83.7 4.6 11.7
(C19H1 meeting), and it was confirmed that this substance has the structure of .

This polymer is a commercially available polysulfo resin, which is a non-grade heat-resistant resin.
IC! It did not dissolve at all in polar solvents such as methylene chloride, benzene, acetate, dimethylacetamide, N-methylpyrrolidone, etc., which would attack when dissolved at room temperature.

The film obtained by pressing this polymer at 340°C for 4 minutes was extremely strong against repeated bending, with a tensile strength of 910 K9/d and a groan at break of 100% (measured). ASTM D 882)
.

In addition, when the thermal loss of this polymer was measured from 1 to 1, it was found to be 501.
45 weight fly fever loss temperature is 552℃ without showing any loss up to ℃
Met. Furthermore, the water absorption rate of this polymer (24 hours 40
%RH) was 0.14 cm, which was good.

Examples 2 to 5 Regarding the monomer, alkali, polymerization solvent, N@temperature, and polymerization time, the entire polymerization was carried out using the conditions shown in the following table, and the polymerization portion was carried out in the same manner as in Example 1 for other flexibility conditions. . The intrinsic viscosity and glass transition temperature of the obtained rL polymer polymer are shown in the coating.

Example 6 Potassium salt of 4-fluoro-3'-phenyl-47-hydroxybenzophenone (19.8 F (0.06 mol)) and hydriphenylsulfonate were charged in a 740 rl separable flask, and in the same manner as in Example 1, 300 ℃6
After a period of reaction and terminal termination reaction, the produced polymer was separated.

The obtained refined polymer has an intrinsic viscosity of 0.85 and a T6 of 182.
It was ℃.

[Brief explanation of drawings]

Figure 1 is an IR spectrum chart of 4-fluoro-3'-phenyl-4'-hydroxybenzophenone (7) used in the present invention, and Figure 2 is an IR spectrum chart of (R
This is a spectrum chart. Figure 1-IWI/aow acw JI5CJC
l gooo I#OO# j400 aO
O to w &X) m ■

Claims (1)

[Claims] 1. A phenyl-substituted aromatic polyetherketone consisting of a repeating unit represented by the formula ▲ Numerical formula, chemical formula, table, etc. ▼ and having an intrinsic viscosity of 0.15 or more. 2 Formula ▲Mathematical formula characterized by polymerizing phenyl-substituted aromatic halophenol represented by the general formula ▲Mathematical formula, chemical formula, table, etc.▼ (X in the formula is a halogen atom) in the presence of an alkali. , chemical formula, table, etc. ▼ A method for producing a phenyl-substituted aromatic polyetherketone that is composed of repeating units represented by and has an intrinsic viscosity of 0.15 or more. 3. It is characterized by polymerizing an alkali metal salt of a phenyl-substituted aromatic halophenol represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (X in the formula is a halogen atom, M is an alkali metal) , a method for producing a phenyl-substituted aromatic polyether ketone consisting of a repeating unit represented by the formula ▲ There are mathematical formulas, chemical formulas, tables, etc.