JPH0552849B2 - - Google Patents

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing polyarylene sulfide, and more specifically, a method for easily obtaining a high molecular weight polyarylene sulfide with a small melt flow. The present invention relates to a method for producing polyarylene sulfide.

[Prior art and its problems] Polyarylene sulfide such as polyphenylene sulfide is a thermoplastic resin that has some thermosetting properties, and has excellent chemical resistance and good mechanical properties over a wide temperature range. It has excellent properties as an engine nearing plastic, such as heat resistance and rigidity.

However, conventional polyarylene sulfide has a small molecular weight, so in order to make a high molecular weight final product, it is necessary to harden the low molecular weight polyarylene sulfide by heat treatment, which makes the operation complicated. .

In addition, as a method for producing branched polyphenylene sulfide having a high molecular weight, a method in which a compound having three or more halogens is present in the reaction system (Japanese Patent Publication No. 54-87919, Japanese Patent Application Laid-open No. 59-879-1989, 197430
(see publication).

[Object of the Invention] This invention has been made based on the above circumstances.

That is, an object of the present invention is to provide a novel manufacturing method capable of manufacturing a high molecular weight polyarylene sulfide with a small melt flow.

In order to achieve the above object, the present inventor conducted various studies and found that, unlike the case described in the above publication, the use of an active hydrogen-containing dihalogen aromatic compound can easily achieve the above object with a small amount of use. This invention was achieved by discovering that it is possible to achieve the following.

[Means for achieving the above object] The outline of this invention for achieving the above object is as follows:
A method for producing polyarylene sulfide by contacting a dihalogen aromatic compound and an alkali metal sulfide in a polar solvent, characterized by the presence of an active hydrogen-containing dihalogen aromatic compound in the reaction system. This is a method for producing polyarylene sulfide.

Examples of the polar solvent that can be used in the method of the present invention include amide compounds, lactam compounds, urea compounds, and cyclic organic phosphorus compounds.

Among these, specific examples of suitable solvents include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dipropylacetamide, N,N- -Dimethylbenzoic acid amide, caprolactam, N-methylcaprolactam, N-ethylcaprolactam, N-isopropylcaprolactam, N-isobutylcaprolactam, N-propylcaprolactam, N-butylcaprolactam, N-cyclohexylcaprolactam, N-methyl-2-pyrrolidone , N-ethyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-
Isobutyl-2-pyrrolidone, N-propyl-2
-pyrrolidone, N-butyl-2-pyrrolidone, N
-Cyclohexyl-2-pyrrolidone, N-methyl-3-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N-methyl-3-methyl-2-pyrrolidone, N-methyl-3,4,5-trimethyl -2-pyrrolidone, N-methyl-2-piperidone, N-ethyl-2-piperidone, N-isopropyl-5-piperidone, N-isobutyl-
2-piperidone, N-methyl-6-methyl-2-
piperidone, N-methyl-3-ethyl-2-piperidone, N-ethyl-2-oxo-hexamethyleneimine, N-ethyl-2-oxo-hexamethyleneimine, tetramethylurea, 1,3-dimethylethyleneurea, 1,3-dimethylpropyleneurea, 1-methyl-1-oxosulfolane, 1-ethyl-1-oxosulfolane, 1-phenyl-1
-oxosulfolane, 1-methyl-1-oxophosphane, 1-propyl-1-oxophosphane, 1-phenyl-1-oxophosphane, and the like.

Furthermore, among the various polar solvents mentioned above, N-alkyl lactams are preferred.

Examples of the dihalogen aromatic compound include dihalogenated benzenes such as m-dichlorobenzene, p-dichlorobenzene, p-dibromobenzene, m-dibromobenzene, and 1-chloro-4-promobenzene; 2,5-dichlorotoluene; ,
2,5-dichloroxylene, 1-ethyl-2,5
-dichlorobenzene, 1-ethyl-2,5-dibromobenzene, 1-ethyl-2-bromo-5-chlorobenzene, 1,2,4,5-tetramethyl-
3,6-dichlorobenzene, 1-cyclohexyl-2,5-dichlorobenzene, 1-phenyl-
2,5-dichlorobenzene, 1-benzyl-2,
5-dichlorobenzene, 1-phenyl-2,5-
Dibromobenzene, 1-p-tolyl-2,5-
Dichlorobenzene, 1-p-toluyl-2,5-
Examples include substituted dihalogenated benzenes such as dibromobenzene and 1-hexyl-2,5-dichlorobenzene. Among these, dihalogenated benzenes are preferred, and p-dichlorobenzene is particularly preferred.

As the alkali metal sulfide, for example,
Lithium sulfide, sodium sulfide, potassium sulfide,
Examples include rubidium sulfide, cesium sulfide, and mixtures thereof. In the method of this invention, it can usually be used as a hydrate or an aqueous mixture. Suitable alkali metal sulfides include lithium sulfide and sodium sulfide.

Examples of the active hydrogen-containing dihalogen aromatic compound include compounds represented by the following formulas (1) to (3).

[In the above formula (1), X represents a halogen atom such as fluorine, chlorine, or bromine, and Y represents -NHR (however, R
represents an alkyl group or an aryl group. ), −
It represents _NH2 , -SH, and -OH, and n represents an integer of 1 to 4. ] [However, in the above formula (2), X, Y and n represent the same meanings as above, and Z is -O-, -S-, -SO
−, −SO ₂ −, (—CH ₂ ) _n --, and m is an integer of 1 or more. ] [However, X, Y, and Z have the same meanings as above, o is an integer of 1 to 3, and p is an integer of 1 to 5. ] As the active hydrogen-containing dihalogen aromatic compound represented by the above formula (1), for example, 2,6-
dichloroaniline, 2,5-dichloroaniline,
2,4-diuroloaniline, 2,3-dichloroaniline, 2,4-dibromoaniline; 2,6-dichlorothiophenol, 2,5-dichlorothiophenol, 2,4-dichlorothiophenol,
2,3-dichlorothiophenol; 2,6-dichlorophenol, 2,5-dichlorophenol,
2,4-dichlorophenol, 2,3-dichlorophenol, 3,4-dichlorophenol, 3,
5-dichlorophenol, 2,4-dibromophenol, 2,6-dibromophenol; 2,6-
Dichloro(phenyl)aminobenzene, 2,5-
Dichloro(phenyl)aminobenzene, 2,4-
Dichloro(phenyl)aminobenzene, 2,3-
Examples include dichloro(phenyl)aminobenzene.

Examples of the active hydrogen-containing dihalogen aromatic compound represented by the above formula (2) include 2,2'-
Diamino-4,4'-dichlorodiphenyl ether, 2,4'-diamino-2'4-dichlorodiphenyl ether; 2,2'-diamino-4,4'-dichlorodiphenylthioether, 2,4'- Diamino
2',4-dichlorodiphenylthiaether; 2,
2'-Diamino-4,4'-dichlorodiphenyl sulfoxide, 2,4'-diamino-2',4-dichlorodiphenyl sulfoxide; 2,2'-diamino-
4,4'-dichlorodiphenylmethane, 2,4'-diamino-2',4-dichlorodiphenylmethane;
2,2'-dimercapto-4,4'-dichlorodiphenyl ether, 2,4'-zircapto-2',4-dichlorodiphenyl ether; 2,2'-dimethylcapto-4,4'-dichlorodiphenyltheo ether,
2,4'-dimercapto-2',4-dichlorodiphenylthioether;2,2'-dimercapto-4,
4'-dichlorodiphenyl sulfoxide, 2,4'-
Dimercapto-2',4-dichlorodiphenyl sulfoxide; 2,2'-dimercapto-4,4'-dichlorodiphenylmethane-2,4'-dimethylcapto-2'4-dichlorodiphenylmethane;2,2'-dihydroxy-4,4'-dichlorodiphenyl ether, 2,4'-dihydroxy-2',4-diclodiphenyl ether; 2,2'-dihydroxy-4,
4'-dichlorodiphenylthioether, 2,4'-
Dihydroxy-2',4-dichlorodiphenyl thioether; 2,2'-dihydroxy-4,4'-dichlorodiphenyl sulfoxide; 2,4'-dihydroxy-2',4-dichlorodiphenyl sulfoxide; 2,2'-dihydroxy-4,4'-dichlorodiphenylmethane,2,4'-dihydroxy-2',4
-dichlorodiphenylmethane and the like.

Examples of the active hydrogen-containing dihalogen aromatic compound represented by formula (3) include 2,5-
dichloro-4'-aminodiphenyl ether, 2,
5-dibromo-4'-aminodiphenyl ether;
2,5-dichloro-4'-aminodiphenyl thioether, 2,5-dibromo-4'-aminodiphenyl thioether; 2,5-dichloro-4'-aminodiphenyl sulfoxide, 2,5-dibromo-
4'-aminodiphenyl sulfoxide; 2,5-dichloro-4'-aminodiphenylmethane, 2,5-
Dibromo-4'-aminodiphenylmethane; 2,5
-dichloro-4'-mercaptoodiphenyl ether, 2,5-dibromo-4'-mercaptodiphenyl ether; 2,5-dichloro-4'-mercaptodiphenyl thioether, 2,5-dibromo-
4'-Mercaptodiphenylthioether; 2,5
-dichloro-4'-mercaptodiphenyl sulfoxide, 2,5-dibromo-4'-mercaptodiphenyl sulfoxide; 2,5-dichloro-4'-mercaptodiphenylmethane, 2,5-dibromo-
4'-Mercaptodiphenylmethane;2,5-dichloro-4'-hydroxydiphenyl ether, 2,
5-dibromo-4'-hydroxydiphenyl ether; 2,5-dichloro-4'-hydroxydiphenylthyl ether, 2,5-dibromo-4'-hydroxydiphenylthioether;2,5-dichloro-4'- Hydroxydiphenyl sulfoxide 2,5
-dibromo-4'-hydroxydiphenyl sulfoxide; 2,5-dichloro-4'-hydroxydiphenylmethane, 2,5-dibromo-4'-hydroxydiphenylmethane and the like.

In this invention, in addition to the active hydrogen-containing dihalogen aromatic compounds represented by formulas (1) to (3) above, the naphthalene nucleus is substituted with an active hydrogen-containing group such as an amino group, a mercapto group, a hydroxy group, etc. In addition, compounds that substitute halogen atoms can also be used.

Among the various active hydrogen-containing dihalogen aromatic compounds exemplified above, those represented by the above formula (1) are preferred, and dichloroaniline is particularly preferred.

In the method of the present invention, the dihalogen aromatic compound (A) and the alkali metal sulfide (B) are mixed in the polar solvent (D) in the presence of the active hydrogen-containing dihalogen aromatic compound (C). Polyarylene sulfide can be produced by reacting therein.

During the reaction, it is desirable that the mixing ratio of each of the above components be as usual.

That is, the molar ratio of component (A)/component (B) is 0.75 to
2.0, preferably 0.90-1.2. Since the reaction between the dihalogen aromatic compound and the alkali metal sulfide is an equimolar reaction, the amount is usually within the above range.

The above (C) component is 0.005 to 2.0 relative to the above (A) component.
It is mol%, preferably 0.01 to 1.5 mol%. When the component (C) is less than 0.005 mol%,
It may be difficult to produce a high molecular weight polyarylene sulfide, and if the amount exceeds 2.0 mol%, gelation may occur in some cases.

The molar ratio of component (D)/component (B) is 1-15, preferably 2-10. If this molar ratio is less than 1, the reaction may become non-uniform;
If it is larger than 15, productivity may decrease.

In addition, when producing this polyarylene sulfide, an alkali metal hydroxide (E), a catalyst, a known reducing agent (F), and a carboxylic acid metal salt or an aromatic sulfonate are coexisting in the reaction system. is preferred.

Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide. Among these, preferred are lithium hydroxide, sodium hydroxide, and potassium hydroxide.

Examples of the reducing agent include hydrazine,
Examples include hydrides, alkali formates, hydrogen sulfide, etc., and those that are favorable include hydrides, especially borohydrides [lithium borohydride, sodium borohydride (NaBH ₄ ), potassium borohydride], hydrides Calcium (CaH ₂ ).

Examples of the carboxylic acid metal salt include lithium acetate, lithium propionate, lithium 2-methylpropionate, lithium butyrate, lithium 3-methylbutyrate, lithium valerate, lithium hexanoate, lithium heptanoate, lithium benzoate, and benzoate. Among them, lithium carboxylate is preferred, and lithium acetate is particularly preferred. A hydrate of such a carboxylic acid metal salt may be used.

Furthermore, examples of the aromatic carboxylate include sodium p-toluenesulfonate.

The molar ratio of component (E)/component (B) is 2.0 or less,
Preferably it is 0.01 to 1.5. If this molar ratio is greater than 2.0, the resulting polymer may not have a small melt flow.

Since the alkali metal hydroxide is used to make the reaction system alkaline, there is no particular restriction on the amount added.

During the reaction, these components may be contacted all at the same time or separately. There are no particular restrictions on the contact of each component.

The reaction is usually carried out at 180-320°C, preferably
It is carried out at a temperature range of 220-300°C.

The reaction time is usually within 20 hours, especially 0.1 to 8
Within hours.

After the reaction is complete, the polyarylene sulfide can be separated directly from the reaction solution by standard methods, e.g. by filtration or centrifugation, or
For example, it can be obtained by adding water and/or diluted acid and then fractionating it from the reaction solution.

The filtration step is generally followed by washing with water to remove any inorganic components that may adhere to the polymer, such as alkali metal sulfides and hydroxides. It is also possible to perform washing or extraction using other washing liquids that may be performed in addition to or after this washing step. The polymer can be recovered by distilling off the solvent from the reaction vessel followed by washing as described above.

When the polyarylene sulfide obtained by the method of this invention is molded into various products, other polymers, pigments and fillers such as graphite,
metal powder, glass powder, quartz powder or glass fiber,
Alternatively, it can be mixed with additives customary for polyarylene sulfides, such as customary stabilizers or mold retardants.

The polyarylene sulfide obtained by the method of this invention has a small melt flow and a high molecular weight, so it can be used as a matrix resin for molded products and composite materials, and can also be used for various molded products, films, fibers, etc. It is an excellent engineering plastic that can be suitably used for mechanical parts, electronic parts, etc.

[Effects of the Invention] According to the present invention, a high molecular weight polyarylene sulfide with a small melt flow can be produced. In addition, in the method of this invention, compared to the conventional method, by adding an active hydrogen-containing dihalogen aromatic compound at about half the amount of trichlorobenzene used in the conventional method, can be manufactured.

[Example] Next, examples and comparative examples of the present invention will be shown.

Example 1 81.5 g (0.56 mol) of p-dichlorobenzene, 25.0 g (0.54 mol) of lithium sulfide, 0.164 g (0.001 mol) of 2,5-dichloroaniline and 0.914 g (0.024 mol) of sodium borohydride were added, 306 ml of N-methyl-2-pyrrolidone (2.93
2 moles) into an autoclave and 10 moles of nitrogen.
After flowing at room temperature for a minute, the temperature was raised while stirring.
After raising the temperature to 120°C, the inside of the autoclave was sealed, the temperature was raised to 266°C, and the reaction was carried out for 3 hours. After the reaction was completed, the mixture was cooled to 190° C. with stirring, and then left to warm to room temperature. The reaction mixture was poured into 1 water, and filtered, washed with water, and washed with methanol in this order.

The polyphenylene sulfide obtained had a melt flow value of 0.034 ml/sec. However, the conditions for measuring the melt flow value were 300° C., a load of 50 kg/cm ² , a nozzle diameter of 1 mm, and a flow rate of 10 mm.

Example 2 0.772g of 2,5-dichloroaniline used
(0.0048 mol) was carried out in the same manner as in Example 1 above.

The melt flow value of the polyphenylene sulfide obtained was 0 ml/sec.

Comparative Example 1 The same procedure as Example 1 was carried out except that 2,5-dichloroaniline was not used.

The flow value of the obtained polyphenylene sulfide is
It was 0.79ml/sec.

Comparative Example 2 The same procedure as in Example 1 was carried out except that 0.001 mol of trichlorobenzene was used instead of 0.001 mol of 2,5-dichloroaniline.

The flow value of the obtained polyphenylene sulfide is
It was 0.69ml/sec.

Example 3 2 In an autoclave, add sodium sulfide nonahydrate.
130.4g (0.54mol), lithium acetate 35.8g (0.54mol)
mol), lithium carbonate 40.1 (0.54 mol) and N-
370 ml of methyl-2-pyrrolidone was added and 88 ml of water was removed by azeotropic distillation. Then, 81.5 g (0.56 mol) of p-dichlorobenzene, 0.161 g (0.001 mol) of 2,5-dichloroaniline, and 150 ml of N-methyl-2-pyrrolidone were added, and the mixture was heated under a nitrogen atmosphere.
The reaction was carried out at 265°C for 3 hours. reaction product 0.1
The mixture was poured into normal hydrochloric acid, filtered, washed with water, and washed with methanol in this order.

The melt flow value of the polyphenylene sulfide obtained was 0.40 ml/sec.

Example 4 The amount of 2,5-dichloroaniline used was 0.733g
The same procedure as in Example 3 was carried out except that the amount was changed to (0.0045 mol).

The melt flow value of the polyphenylene sulfide obtained was 0.06 ml/sec.

Comparative Example 3 Same as Example 3 except that 0.001 mol of trichlorobenzene was used instead of 2,5-dichloroaniline.
I did the same thing.

The melt flow value of the polyphenylene sulfide obtained was 0.65 ml/sec.

Claims (1)

[Claims] 1. In a method for producing polyarylene sulfide by contacting a dihalogen aromatic compound and an alkali metal sulfide in a polar solvent, an active hydrogen-containing dihalogen aromatic compound is added to the reaction system. A method for producing polyarylene sulfide, characterized in that it is present in the polyarylene sulfide. 2. The method for producing polyarylene sulfide according to claim 1, wherein the dihalogen aromatic compound is p-dichlorobenzene. 3. The method for producing a polyarylene sulfide according to claim 1 or 2, wherein the active hydrogen-containing dihalogen aromatic compound is dichloroaniline.