JPH06100689A - Production of polyaryl ether - Google Patents

Abstract

PURPOSE:To obtain a polyaryl ether excellent in heat resistance and mechanical strengths and low in coloration. CONSTITUTION:A dispersion of an alkali metal compd. in an org. solvent is mixed with an org. polar solvent in the process for producing a polyaryl ether wherein a soln. of a dihalogenodiphenyl compd. and a dihydric phenol compd. in the polar solvent is thermamlly stirred in the presence of the alkali metal compd.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polyaryl ether having excellent heat resistance, mechanical strength and reduced coloring degree.

[0002]

2. Description of the Related Art Polyaryl ethers are obtained by reacting a dihydric phenol, an alkali metal compound and a dihalogenodiphenyl compound in an organic polar solvent,
In the reaction system, synthesize an alkali metal di-salt of dihydric phenol,
Alternatively, it is known that an alkali metal disalt of a dihydric phenol is previously synthesized, and a polyhalogenation reaction is performed with a dihalogenodiphenyl compound in an organic polar solvent to produce the salt. (JP-B-42-7799, JP-B-45-21318, JP-A-48-19700
No.). In the polycondensation reaction, when the reaction temperature is high, there is a problem that deterioration of the solvent, polymer raw material, oxidation, etc. occur and the resulting polymer is colored brown.

In order to solve the above problems, a method using an alkyl-substituted amide or urea as a solvent (Japanese Patent Publication No. 46-1).
8146), polycondensation reaction in an organic amide solvent, and then removing this solvent by distillation (JP-A-59-74123) and a method using an inert organic highly polar amide as a reaction solvent (JP-A-59-74123).
1-245018) has been proposed. Further, generally, only a method of introducing an inert gas such as nitrogen gas into the reaction system is adopted.

[0004]

The present invention relates to a method for producing a polyaryl ether by heating and stirring an organic polar solution of a dihalogenodiphenyl compound and a dihydric phenol compound in the presence of an alkali metal compound. The present invention relates to a method for producing a polyaryl ether, characterized in that the organic polar solution is mixed with an organic solvent dispersed in an organic solvent.

The alkali metal compound used in the present invention includes alkali metal carbonates, alkali metal hydroxides,
Examples thereof include alkali metal hydrides and alkali metal alkoxides. Particularly, sodium carbonate and potassium carbonate are preferable.

In the present invention, by mixing an alkali metal compound dispersed in an organic solvent and an organic polar solution of a dihalogenodiphenyl compound and a dihydric phenol compound, coloring of the polyaryl ether produced can be achieved. Remarkably reduced.

The organic solvent in which the alkali metal compound is dispersed is not particularly limited, but an organic solvent that does not inhibit the polymerization reaction, an organic solvent that can be discharged outside the reaction solution during the reaction, or an organic solvent having a boiling point lower than the reaction temperature. A solvent can be used. Preferably, the same organic polar solvent used for preparing an organic polar solution of a dihalogenodiphenyl compound and a dihydric phenol compound, or an organic solvent azeotropic with water can be used.

The organic polar solvent is not particularly limited as long as it dissolves the produced polymer at the polycondensation temperature. For example, dimethyl sulfoxide, sulfoxide solvent such as diethyl sulfoxide, N, N-dimethylformamide, amide solvent such as N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone and other pyrrolidone -Based solvents, piperidone-based solvents such as N-methyl-2-piperidone, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl
Examples thereof include 2-imidazolidinone-based solvents such as -2-imidazolidinone, hexamethylene sulfoxide, γ-butyrolactone, sulfolane, and diphenyl compounds such as diphenyl ether and diphenyl sulfone.
In particular, amide-based solvents, pyrrolidone-based solvents, and imidazolidinone-based solvents are preferably used for reducing coloration.

Examples of the organic solvent azeotropic with water include aromatic hydrocarbon compounds such as benzene, toluene, xylene, and ethylbenzene, aromatic halogen hydrocarbon compounds such as chlorobenzene, and aliphatic carbon compounds such as heptane and octane. Examples thereof include hydrogen compounds, and aliphatic halogenated hydrocarbon compounds such as chloroform and tetrachlorohydrocarbon. In addition to the above solvents, alcohols such as methanol, ethanol and heptanol, ketones such as acetone, and ethers such as dibutyl ether and anisole can be used.

It is preferable that the alkali metal compound of the present invention dispersed in an organic solvent is further deoxidized and then added to an organic polar solution in order to reduce coloration. There is no particular limitation on the method of the deoxidation treatment, and for example, a method in which an alkali metal compound is dispersed in an organic solvent is heated to boiling, a method of passing an inert gas such as nitrogen gas, or under reduced pressure. A method such as degassing can be used.

The dihalogenodiphenyl compounds are represented by the general formulas (I) and (II)

[0012]

[Chemical 1] (In the formula, X and X ′ are the same or different halogen atoms.)

[0013]

[Chemical 2] (In the formula, X and X ′ are the same or different halogen atoms.).

Specific examples of the dihalogenodiphenyl compound include 4,4'-dichlorodiphenisulfone and 4,4'-
Examples thereof include difluorodiphenyl ketone and 4,4′-difluorodiphenyl sulfone. Particularly, dihalogenodiphenyl sulfone represented by the general formula (I) is preferable.

The dihydric phenol compound has the following general formula (III)

[Chemical 3] (N represents 1 or 2), bis (hydroxyphenyl) alkanes, dihydroxydiphenylsulfones, dihydroxydiphenyl ethers, or a compound thereof, in addition to hydroquinone, catechol, resorcin, 4,4′-biphenol represented by Examples thereof include those in which at least one hydrogen atom of the benzene ring is substituted with a lower alkyl group such as a methyl group, an ethyl group, a propyl group, or a lower alkoxy group such as a methoxy group and an ethoxy group.

Alternatively, two or more of the above dihydric phenol compounds may be mixed and used. In particular, the general formula (I
A polyaryl ether containing the dihydric phenol represented by II) in an amount of 1% by weight or more based on the total amount of the dihydric phenol used is preferable.

The dihydric phenol compound is generally used in a substantially equimolar amount with the dihalogenodiphenyl compound, but in order to control the molecular weight of the polyaryl ether, a slight excess or an excessively small amount is used. May be used in. For this purpose, a small amount of monohalogenodiphenyl compound or monohydric phenol compound can be added to the polymerization solution.

There is no particular limitation on the method for mixing the dispersion of the above-mentioned alkali metal compound in an organic solvent and the organic polar solution of the dihalogenodiphenyl compound and the dihydric phenol compound, and the dihalogenodiphenyl compound is not particularly limited. Method of adding an alkali metal compound dispersed in an organic solvent to an organic polar solution of a dihydric phenol compound and vice versa, or conversely, a dihalogenodiphenyl compound added to an alkali metal compound dispersed in an organic solvent You may add the organic polar solution of and a dihydric phenol compound.

The polycondensation temperature is usually 140 to 270 ° C.
Water produced as a by-product during the reaction is accompanied by an inert gas flow outside the system,
Alternatively, it is preferable to distill off with an azeotropic dehydrating agent in order to produce a high molecular weight polyaryl ether. Examples of azeotropic dehydrating agents include benzene, toluene, xylene, and aromatic halogen compounds. At the end of the polycondensation, a methylating agent such as chloromethane may be added to the reaction solution as a polymer terminal stopper at 90 to 150 ° C.

The inorganic solid such as the alkali metal compound or the alkali metal halide remaining in the reaction solution can be separated by filtering or centrifuging the reaction solution. After separating the inorganic solid contained in the reaction solution by filtration or centrifugation, or without separating the inorganic solid, a poor solvent can be added to the reaction solution to separate the polyaryl ether as a precipitated solid. .

Examples of the poor solvent for the polyaryl ether include alcohols such as methanol, ethanol, isopropanol, butanol and heptanol,
Examples thereof include nitriles such as acetonitrile, water and the like. Further, two or more kinds of the above compounds can be mixed and used. Further, the poor solvent may contain a good solvent for the polymer such as the above-mentioned polymerization reaction solvent, within the range where the polymer can be precipitated. The precipitated solid is washed with a poor solvent and dried to obtain a polyaryl ether powder.

[0022]

INDUSTRIAL APPLICABILITY In the present invention, by mixing a dispersion of an alkali metal compound in an organic solvent with the organic polar solution, excellent heat resistance and mechanical strength are obtained, and the coloring degree is lowered. Polyaryl ethers can be obtained.

[0023]

EXAMPLES Examples of the present invention will be described below. The reduced viscosity η _{SP / C} in the examples and comparative examples is represented by the following equation. η _{SP / C} = (tt ₀ ) / t ₀ / c where t is the transit time (sec) between the marked lines of the polymer solution in the viscometer, and t ₀ is the transit time between the marked lines of the pure solvent in the viscometer (Sec), c represents the concentration of the polymer solution (g / 100 ml solvent). The viscosity was measured at 30 ° C. using an N-methyl-2-pyrrolidone solvent at a polymer solution concentration of 0.5 g / 100 ml.

Example 1 73.3 g of 4,4'-dichlorodiphenyl sulfone, 13.7 g of hydroquinone and 23.2 g of 4,4'-biphenol were added to N, N-
Dimethylacetamide 200 ml and azeotropic dehydration toluene 3
The solution was added to 0 ml and dissolved, then degassed under reduced pressure, and nitrogen-substituted solution was prepared. 38 g of potassium carbonate to N, N-dimethylacetamide
The slurry liquid dispersed in 100 ml was degassed under reduced pressure at 23 ° C., nitrogen-substituted, was added to the above solution, and then under nitrogen flow,
The mixture was stirred at a temperature of about 160 ° C for 10 hours to obtain a polymerization solution. After the reaction was completed, nitrogen pressure was applied to separate the inorganic substances from the polymerization solution.
The mixture was filtered at 1.5 kg / cm ² to obtain a polymerization solution (polymer concentration: about 25% by weight). 300 g of the polymerization solution was poured into 2000 ml of ethanol, the polymer was precipitated while stirring at 5000 rpm, filtered with a centrifuge and separated to obtain a polymer. This polymer 5
0 g was washed twice with 500 ml of ethanol and then dried at 90 ° C. to obtain a powder of polyether sulfone. The reduced viscosity η _{SP / C} of the obtained powder of polyether sulfone was 0.50. This powder was melt-molded at 340 ° C. to prepare a plate having a thickness of about 0.2 mm, and the yellowness (YI) by transmission was measured. YI value is
It was 2.1.

Example 2 Polyamide was prepared in the same manner as in Example 1 except that 38 g of potassium carbonate was dispersed in 100 ml of N, N-dimethylacetamide, which was degassed under reduced pressure at 70 ° C. and replaced with nitrogen. A powder of ether sulfone was obtained. The reduced viscosity η _{SP / C} of the obtained powder of polyether sulfone was 0.50. About thickness
A 0.2 mm plate was prepared and the yellowness (YI) due to transmission was measured. The YI value was 2.1.

Example 3 Polyamide was prepared in the same manner as in Example 1 except that 38 g of potassium carbonate was dispersed in 100 ml of N, N-dimethylacetamide, which was degassed under reduced pressure at 100 ° C. and replaced with nitrogen. A powder of ether sulfone was obtained. The reduced viscosity η _{SP / C} of the obtained powder of polyether sulfone was 0.50. About thickness
A 0.2 mm plate was prepared and the yellowness (YI) due to transmission was measured. The YI value was 1.9.

Example 4 As dihydric phenol, 45.5 g of bisphenol A and
A powder of polyethersulfone was obtained in the same manner as in Example 1 except that 9.3 g of 4,4'-biphenol was used. The reduced viscosity η _{SP / C} of the obtained polyethersulfone powder was 0.48.
Met. A plate having a thickness of about 0.2 mm was prepared and the yellowness (YI) due to transmission was measured. The YI value was 1.9.

Example 5 4,4'-dichlorodiphenyl sulfone 73.3 g, hydroquinone 13.7 g, and 4,4'-biphenol 23.2 g were added to 300 ml of N-methyl-2-pyrrolidone, dissolved and degassed under reduced pressure. ,
A nitrogen-substituted solution was prepared. A slurry solution prepared by dispersing 38 g of potassium carbonate in 80 ml of toluene was degassed under reduced pressure at 70 ° C, and nitrogen-substituted was added to the above solution, which was then stirred under a nitrogen stream at a temperature of about 180 ° C for 8 hours to give a polymerization solution. Got
After the reaction was completed, in order to separate the inorganic matter from the polymerization solution, the mixture was filtered under a nitrogen pressure of 1.5 Kg / cm ² to obtain a polymerization solution (polymer concentration: about 24% by weight). A powder of polyethersulfone was obtained in the same manner as in Example 1. The reduced viscosity η _{SP / C} of the obtained powder of polyether sulfone was 0.56. Create a plate with a thickness of about 0.2 mm and set the yellowness (Y
I) was measured. The YI value was 3.5.

Comparative Example 1 Without preparing a potassium carbonate slurry, that is,
7,4 g of 4,4'-dichlorodiphenyl sulfone, 13.7 g of hydroquinone, 23.2 g of 4,4'-biphenol, and 38 g of potassium carbonate at the same time, 300 ml of N, N-dimethylacetamide
Further, a powder of polyethersulfone was obtained in the same manner as in Example 1 except that the polymerization was carried out by adding 30 ml of toluene for azeotropic dehydration. The reduced viscosity η _{SP / C} of the obtained polyethersulfone powder was 0.49. Create a plate with a thickness of about 0.2 mm,
The yellowness (YI) due to transmission was measured. The YI value was 7.5.

Comparative Example 2 Without preparing a potassium carbonate slurry, that is,
4,4'-dichlorodiphenyl sulfone 73.3g, bisphenol A 28.4g, 4,4'-biphenol 23.2g, and potassium carbonate 38g at the same time, N, N-dimethylacetamide 300
Polyether sulfone powder was obtained in the same manner as in Example 1 except that the polymerization was performed by adding 30 ml of azeotropic dehydration toluene and 30 ml of azeotropic dehydration toluene. The reduced viscosity η _{SP / C} of the obtained polyethersulfone powder was 0.47. A plate having a thickness of about 0.2 mm was prepared and the yellowness (YI) due to transmission was measured. YI value is
It was 6.9.

Comparative Example 3 Without preparing a potassium carbonate slurry, that is,
7,4 g of 4,4'-dichlorodiphenyl sulfone, 13.7 g of hydroquinone, 23.2 g of 4,4'-biphenol and 38 g of potassium carbonate were added simultaneously to 300 ml of N-methyl-2-pyrrolidone and 30 ml of azeotropic dehydration toluene. Except polymerized
A powder of polyethersulfone was obtained in the same manner as in Example 1. The reduced viscosity η _{SP / C} of the obtained polyethersulfone powder was 0.55. A plate having a thickness of about 0.2 mm was prepared and the yellowness (YI) due to transmission was measured. The YI value was 12.5.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shigeru Yamamoto 8-1 Goi Minamikaigan, Ichihara City, Chiba Ube Industries Ltd. Chiba Research Institute

Claims (1)

[Claims] 1. A method for producing a polyaryl ether by heating and stirring an organic polar solution of a dihalogenodiphenyl compound and a dihydric phenol compound in the presence of an alkali metal compound, wherein the alkali metal compound is dispersed in an organic solvent. And a method for producing a polyaryl ether, which comprises mixing the organic polar solution with the organic polar solution.