JPS62156133A - Production of polyarylene sulfide resin - Google Patents

Abstract

PURPOSE:To obtain the titled resin with significantly little content of salts such as sodium chloride, thus requiring no repurification, by polymerization, in a polar solvent between dihalogen aromatic compound and alkali metal sulfide at temperatures higher than the melting point of the resin produced. CONSTITUTION:The objective polyarylene sulfide resin can be obtained by polymerization, in a polar solvent, between (A) a dihalogen aromatic compound (p-dichlorobenzene) and (B) an alkali metal sulfide (sodium solfide) in a molar ratio A/B of 0.75-2.0 (pref. 0.90-1.2) at such temperature as to be higher than the melting point of the final resin (pref. +5 deg.C or more).

Description

Detailed Description of the Invention 3. Description of the Invention [Field of Industrial Application] The present invention relates to a method for producing polyarylene sulfide resin, and more specifically, the present invention relates to a method for producing polyarylene sulfide resin. The present invention relates to a method for producing easily obtainable polyarylene sulfide resin.

[Prior art and its problems] Polyarylene sulfide resins such as polyphenylene sulfide resins are thermoplastic resins that partially have thermosetting properties, and have excellent chemical resistance, good mechanical properties in a wide temperature range, and heat resistance. It has excellent properties as an engineering plastic, such as rigidity.

It is known that polyarylene sulfide resins such as polyphenylene sulfide resins are usually obtained by polymerizing a dihalogen aromatic compound and an alkali metal sulfide in a polar solvent. This is usually carried out by polymerizing p-dichlorobenzene and sodium sulfide in a polar solvent (Japanese Patent Publication No. 52-1224Q, etc.), but salts such as common salt produced by the polymerization reaction are usually
If salts such as t, ooo to 3,000 ppm of common salt remain in the resin, when polyarylene sulfide resins such as polyphenylene sulfide resins are applied to electrical and electronic fields, the moisture-resistant insulation of circuits will deteriorate. , causing malfunction. For this reason, food]′! ! There is a problem in that the resin needs to be regenerated in order to remove the salts.

In order to solve the above-mentioned problems, conventional methods for producing polyphenylene sulfide resins with low salt content, such as common salt, have been proposed, in which a polymerization reaction is carried out in the presence of polyoxyethylene ether (Japanese Patent Application Laid-Open No. 74127/1983). issue)
has been proposed, but there is a new problem in that it is practically disadvantageous because the polyoxyethylene ether)Ly(1) must be removed after the completion of the first polymerization reaction. On the other hand, a method for purifying polyphenylene sulfide resin after production (Japanese Patent Application Laid-Open No. 57-108138) has been proposed, but this method has other problems such as poor purification efficiency and disadvantages in terms of process.

[Purpose of Departure 1] This invention was made based on the above-mentioned "1.

That is, an object of the present invention is to solve the above-mentioned problems and reduce the amount of acetate remaining in the resin! There is no need for a re-purification process to remove salts such as salts, and even if the resin is purified, the purification efficiency is significantly improved and is of practical benefit.As a result, polyphenylene sulfide with minimal salt content such as common salt Polyarylene sulfide resins such as resins can be produced. The objective is to provide a new manufacturing method.

[Means for solving the above problems] In order to achieve the above object, the present inventor conducted extensive research on methods for producing polyphenylene sulfide resin with a low salt content such as common salt, and surprisingly found that polymerization The present invention was achieved by discovering that the above object can be easily achieved by carrying out the reaction at a temperature above the melting point of the resin to be produced.

The outline of the present invention for solving the above problems is a method for producing a polyaryl-1/sulfide resin by polymerizing a dihalogen aromatic compound and an alkali metal sulfide in a polar solvent. This is a method for producing a polyarylene sulfide resin, characterized in that it is carried out at a temperature higher than the melting point of the resin.

The polar solvents that can be used in the method of this invention include amide compounds, lactam compounds, urea compounds,
There are cyclic organic phosphorus compounds, etc.

Among these, specific examples of suitable solvents are:
For example, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide,
N,N-dipropylacetamide, N,N-dimethylbenzoic acid amide, caprolactam, N-methylcaprotictam, N-ethylcaprolactam, N-inpropylcaprolactam, N-inbutylcaprolactam, N-
Propyl caprolactam, N-butyl caprolactam,
N-cyclohexylcaprolactam, N-methyl-2-
Pyrrolidone, N-ethyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-inbutyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-butyl-2-pyrrolidone
-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-)samethyl-2-pyrrolidone, N-methyl-2-piperidone, N-
Ethyl-2-piperidone, N-isopropyl-2-piperidone, N-methyl-6-methyl-2-piperidone, N
-Methyl-3-ethyl-2-piperidone, N-methyl-
2-oxo-hexamethyleneimine, N-ethyl-2-
Oxo-hexamethyleneimine, tetramethylurea, 1
．． 3-dimethylethyleneurea, 1,3-dimethylpropyleneurea, l-methyl-1-oxosulfolane, 1-ethyl-1-oxosulfolane, l-phenyl-1-oxosulfolane, 1-methyl-1-oxophos fan, 1
-propyl-1-saigo sofosphan, l-phenyl-1
-Oxophosphan and the like. These solvents are
They may be used alone or in combination of two or more.

Furthermore, among the various polar solvents mentioned above, N-furkyllactam and N-furkylpyrrolidone are preferred, and N-methylpyrrolidone is particularly preferred.

As the dihalogen aromatic compound, for example, m-
Dichloro is benzene, p-dichlorobenzene, p-dibromobenzene, m-dibromobenzene, p-shortbenzene, 1-chloro-4-bromobenzene, l-chloro-
Dihalogenated benzenes such as 4-iodobenzene: 2,
5-dichlorotoluene, 2,5-dichloroxylene, 1
-ethyl-2,5-dichlorobenzene, l-ethyl-2
, 5-dibromobenzene, l-ethyl-2-bromo 5
-chlorobenzene, 1,2,4.5-tetramethyl-
3,6-dichlorobenzene, l-cyclohexyl-2,
5-'; Chlorobenzene, l-phenyl-2,5-dichlorobenzene, 1-benzyl-2,5-dichlorobenzene, l-phenyl-2,5-dibromobenzene, 1-P
-toluyl-2,5-dichlorobenzene, 1-p-)silyl-2,5-dibromobenzene, l-hexyl-2,
dihalogen-substituted benzenes such as 5-dichlorobenzene,
Examples include dihalogen-substituted biphenyls such as 4.4°-dichlorobiphenyl, dihalogen-substituted naphthalenes such as 1,4-dichloronaphthalene, and 1,8-dichloronaphthalene. Among these, preferred are dihalogen-substituted benzene tearyl, particularly p-dichlorobenzene.

Examples of the alkali metal sulfide include lithium sulfide, sodium sulfide, and potassium sulfide.

Examples include rubidium sulfide, cesium sulfide, and mixtures thereof. In the method of this invention, 1 usually:
It can also be used as permanent product or aqueous mixture. Preferred alkali metal sulfides are lithium sulfide and sodium sulfide, with sodium sulfide being particularly preferred.

The method of this invention comprises the dihalogen aromatic compound (A)
Polyarylene sulfide can be produced by polymerizing and the alkali metal sulfide (B) in the polar solvent (C).

During the polymerization reaction, the blending ratio of each component is preferably as follows.

That is, the no molar ratio of (A) r&min/(B) component is 0.
75-2.0. Preferably it is 0.90-1.2. Since the reaction between the dihalogen aromatic compound (A) and the alkali metal sulfide (B) is an equimolar reaction, it is usually within the above range.

(C) L&, min/molar ratio of component (B) is 1-15,
Preferably it is 2-10. If this molar ratio is smaller than 1, the reaction may become non-uniform;
If it is larger than 5, productivity may decrease.

In the present invention, in the production of polyarylene sulfide, in addition to the components (A), CB), and (G), a polyhalogen aromatic compound (such as an active hydrogen-containing dihalogen aromatic compound) is further added to the polymerization reaction system. D) and/or a dihalogen aromatic nitro compound (E) may also be added.

By carrying out the polymerization reaction in the coexistence of component (D) and/or component (E), a high molecular weight polyarylene sulfide resin with a small melt flow can be produced.

Examples of the dihalogen aromatic compound as an example of the component ([l)] include compounds represented by the following formulas (1) II to (3).

[In the above formula (1), X represents a halogen atom such as fluorine, chlorine, or bromine, and Y represents -NHR (provided that R represents an alkyl group or an aryl group), -N'H2, -
3H1-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, Z is a single bond, -〇-1 -S-1-S
O-5-502-1-CO-.

−+−CH2→, − is represented, and m is an integer greater than or equal to l. ] Y o Y p...(3)
[However, x, y, and z have the same meanings as above, 0 is an integer of 1 to 3, and p is an integer of 1 to 5. ] Examples of the active hydrogen-containing dihalogen aromatic compound represented by the above formula (1) include 2.8-dichloroaniline, 2.5-dichloroaniline, 2.4-dichloroaniline, and 2.3-dichloroaniline. , 2.4-dibromoaniline: 2,8-dichlorothiophenol, 2.
5-dichlorothiophenol, 2.4-dichlorothiophenol; 2.6-dichlorophenol, 2.5-dichlorophenol, 2,4-dichlorophenol, 2.3
-dichlorophenol, 3,4-dichlorophenol,
3,5-dichlorophenol, 2,4-dibromophene/
-l, 2,6-dichlorophenol, 2,6-dichloro(phenyl)aminobenzene, 2,5-dichloro(phenyl)aminebenzene, 2,4-dichloro(phenyl)
Examples include aminebenzene, 2,3-dichloro(phenyl)aminobenzene, and the like.

Examples of the active hydrogen-containing dihalogen aromatic compound represented by 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-dichlorodiphenylthioether: 2,2'-diamino-4,4
°-dichlorodiphenyl sulfoxide, 2.2'-diamino-4,4'-dichlorodiphenylmethane, 2.4
'-diamino-2°, 4-dichlorodiphenylmethane,
2.2'-dimercapto-4,4'-dichlorodiphenyl ether, 2,4'-dimercapto-2',4-dichlorodiphenyl ether; 2.2'-dimercapto-4,4'-dichlorodiphenylthioether, 2,4
°-Dimercapto-2°,4-dichlorodiphenylthioether: 2,2°-dimercapto-4,4'-dichlorodiphenyl sulfoxide 2°. 4-dichlorodiphenyl sulfoxide, 2.2'
-dimercapto-4.4'-dichlorodiphenylmethane, 2.4°-dimercapto-2°,4-dichlorodiphenylmethane, 2.2'-dihydroxy-4.4'-dichlorodiphenyl ether, 2.4'-dihydroxy-2° ,4-dichlorodiphenyl ether; 2,2°-
Dihydroxy-4.4°-dichlorodiphenylthioether, 2,4°-dihydroxy-21.4-dichlorodiphenylthioether; 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 −
Examples include dichlorodiphenylmethane.

Examples of the active hydrogen-containing dihalogen aromatic compound represented by formula (3) include 2,5-dichloro-
4°-7 minodiphenyl ether, 2,5-dibromo-
4'-7 minodiphenyl ether; 2,5-dichloro-
4'-7 minodiphenyl thioether, 2,5-dibromo-4'-aminodiphenyl thioether; 2,5-dichloro-4'-aminodiphenyl sulfoxide, 2.5
-dibromo-41-aminodiphenylsulfoxide; 2
．． 5-dichloro-4′-aminodiphenylmethane, 2.
5-dibromo-4°-aminodiphenylmethane; 2,5
-dichloro-4'-mercaptodiphenyl ether, 2
．． 5-dibromo-4°-mercaptodiphenyl ether; 2.5-dichloro-4°-mercaptodiphenylthioether; 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'-hydroxydiphenylthioether, 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, as the (D) component, the (1)
) to (3) In addition to the active hydrogen-containing dihalogen aromatic compounds represented by the formulas, 1.2.3 to trichlorobenzene, 1
, 2.4-) dichlorobenzene, 1.3-dichloro-
5-bromobenzene, 2,4.8-trichlorotoluene, 1,2,3.5-tetrabromobenzene.

het-410 lobenzene, 1,3.5- ) IJ7
0el-2,4,6-)limethylbenzene, 2.2°,
4.4°-tetrachlorobiphenyl, 2.2',
J8°-tetrabromo-3,3°,5,5°-tetramethylbiphenyl, 1,2,3°4-tetrachloronaphthalene, 1,2,4-)dibromo-6-methylnaphthalene, etc. can also be used. Furthermore, compounds in which active hydrogen-containing groups such as Amitsuno group, mercapto group, hydroxyl group, etc. are substituted on the naphthalene nucleus and halogen atoms can also be used.

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

In this invention, the component (D) is the component (A).
It can be used usually in a range of 0 to 2.0 mol% with respect to Ijj, min. In addition to the purpose of the present invention, when the purpose is to produce a polyarylene sulfide resin of polymer FB, the amount of the component (D) is 0.005 to 2% relative to the component (A). It is preferable to set it as 0.0 mol%, and 0.0 mol%. It is more preferable to set the content to 1 to 1.5 mol % of O. (It) If the It content is less than 0.005 mol%, it may be difficult to produce a polymeric polyarylene sulfide resin, and
If the amount exceeds mol%, gelation may occur in some cases.

In this invention, the (E) It portion is the (A)
) It can be used usually in a range of 0 to 3.0 mol % with respect to the component. In addition to the purpose of the present invention, furthermore,
Small polymers with melt flow! - If the purpose is to produce the polyarylene sulfide resin of (E),
) component to the component (A) in an amount of 0.025 to 2.
It is suitable to be 6 mol%, and 0.08 to 1.1 mol%
It is even more preferable to do so. The component (E) is 0.02
If it is less than 5 mol%, the resulting polymer may not have a small melt flow, while if it is more than 2.6 mol%, the polymer may gel.

In addition, in this invention, when producing polyarylene sulfide, alkali hydroxide (F
), at least one of a carboxylic acid metal salt, an aromatic sulfonate, and a reducing agent may be present as the catalyst (G).

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

Examples of the carboxylic acid metal salts include lithium acetate, lithium propionate, lithium 2-methylpropionate, lithium 2-methylpropionate, lithium acetate, lithium 3-methyl acetate, lithium valerate, lithium hexanoate, and heptanoate. Examples of such carboxylic acid metal salts include lithium, ammonium, lithium alpha fragrant, sodium ammonium, q fragrant, zinc acetate, tricalcium phosphate, etc. Among these, lithium carboxylate is preferred, and lithium acetate is particularly preferred. may also be used as a hydrate.

Further, examples of the aromatic sulfone #salt include sodium P-1 luenesulfonate.

Examples of the reducing agent include hydrazine, hydrides, alkali formates, etc., and preferred ones include hydrides, especially borohydrides [lithium borohydride, sodium borohydride (Na BF2), hydride] potassium] and calcium hydride (CaH2).

The molar ratio of component (G)/component (B) is 1, usually 2.0 or less, and preferably 0.01-1.5.

Since the purpose is to make the acyal hydroxide polymerization reaction system alkaline, there is no particular restriction on the amount added.

All of these components may be contacted simultaneously or separately during the polymerization reaction, and there are no particular restrictions on the order or method of contacting each component.

One of the important points in this publication '51 is that the polymerization reaction is carried out at a reaction temperature higher than the melting point of the resulting resin, preferably at least 5° C. higher than the melting point. 1! If the reaction temperature is below the melting point, salt, etc. remaining in the polyarylene sulfide resin produced! The northern limit of the reaction temperature of the polymerization reaction described in 1Fi, which does not reduce the content of R, cannot be uniformly defined because it varies depending on various other conditions such as the type of the dihalogen aromatic compound, but it is usually 320°C, preferably 300°C. When the reaction temperature in °C is higher than 320 °C,
This may induce side reactions or reduce the production of polyarylene sulfide resin.

For example, the melting point of a typical polyphenylene sulfide resin is around 284°C, so when producing this resin, the reaction temperature of the polymerization reaction in the undeveloped IJI method is 284-285°C, preferably 289-282°C. It is.

The reaction pressure of the polymerization reaction is not particularly limited, but usually
Self-pressure of polymerization reaction system such as solvent ~50Kg/c (absolute pressure)
, preferably the autogenous pressure of one polymerization reaction system ~10Kg/crry
' (absolute pressure).

The polymerization reaction may be performed in an atmosphere of an inert gas such as nitrogen, carbon dioxide, or water vapor.

The reaction time of the polymerization reaction is usually within 20 hours, particularly within 0.1 to 8 hours.

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

Filtration [after moderation generally adheres to the polymer and 1! ) to remove any inorganic components such as alkali metal sulfides and alkali hydroxides. In addition to or after this washing step, washing or extraction with other washing liquids such as methanol may also be carried out by distilling off the solvent from the reaction vessel, followed by washing as described above. The polymer can also be recovered.

The content of salts such as common salt remaining in the polyarylene sulfide resin recovered in this way is extremely small, at 1/4 or less, compared to polyarylene sulfide resin produced by conventional methods. The resin can then be molded and processed without any particular desalination treatment and can be suitably used in the electrical and electronic fields; however, if necessary, in addition to or after the washing step,
It is also possible to further reduce the concentration of salt such as common salt in the resin by performing various desalting treatments.

When molding the polyarylene sulfide resin obtained by the method of this invention into various products.

Other polymers, pigments and fillers, such as graphite,
additives commonly used for metal powders, glass powders, quartz powders or glass fibers, or polyarylene sulfides;
For example, it can be mixed with customary stabilizers or mold release agents.

Polyarylene sulfide resin such as polyphenylene sulfite resin obtained by the method of this invention has a low salt content such as common salt in the tree, so it has high moisture resistance and electrical insulation. Since it can be produced as a high molecular weight resin with low flow, it can be used as a matrix resin for various molded products and composite materials, and can also be made into various molded products, films, fibers, etc., and can be used for mechanical parts. It is an excellent engineering plastic that can be suitably used in electrical and electronic parts.

[Effects of the Invention] According to the present invention, a polyarylene sulfide resin such as a polyphenylene sulfide resin containing significantly less salt such as common salt can be produced. Polyphenylene sulfide obtained by the method of this invention
Polyarylene sulfide resins such as 'i' have less salt-containing needles such as common salt, so when used in the electrical and electronic fields, re-refining and de-refining, which was conventionally required to prevent the addition of moisture-resistant insulation to circuits, can be used in the electrical and electronic fields. Since a salting step is not necessarily required, it is extremely advantageous in terms of the process, and it also has the advantage that the efficiency of the process can be improved even when further repurification and desalting is performed as necessary.

[Examples] Next, Examples and Comparative Examples of the present invention will be shown to further specifically explain the present invention.

(Example 1) Sodium sulfide nonahydrate [0,4
g (0,54 mol) and N-methylpyrrolidone 36
88 m of water was removed by azeotropic distillation, and then 81.5 g of p-dichlorobenzene (0,5 m) was added.
6 mol), sodium borohydride 0.91 g (0,
024 mol), p-dichloroaniline 0.483 g (0
,0029 mol) and N-methylpyrrolidone 212m
The reaction product was reacted for 3 hours at 285° C. in a nitrogen atmosphere, and the reaction product was poured into ion-exchanged water in Step 11, followed by filtration, washing with water, and washing with methanol in this order. The solution viscosity ηLnh of the obtained polymer in 1-chloronaphthalene at 206°C was 0.13, and Na' contained in the polymer was 630 ppm as a result of atomic absorption analysis.

(Example?) The same operation as in Example 1 was performed except that the reaction temperature was changed to 230°C. ηinh = 0.12, Na content is 45
It was 0pp Otori.

(Example 3) The same procedure as in Example 1 was carried out without using sodium borohydride and p-dichloroaniline. η is 0.0
9. Na+ was 250 ppm.

(Comparative Example 1) The same operation as in Example 1 was carried out except that the same reaction was carried out at 283°C. ηI! Ih is 0.13, Na' is 240
0 ppm (Comparative Example 2) In Example 3, after reacting at 200° C., the same post-treatment was performed. ηinh is 0.09, Na・ is 250
It was 0 ppm. Further, this sample was boiled in boiling R ion exchange water for 2 hours, filtered, and washed with methanol. Na'' in the obtained sample was teoopp■.

(Comparative Example 3) 13.8g of lithium sulfide in a ti autoclave
(0.30 mol), p-dichlorobenzene 45.0 g
(0.31 mol), lithium acetate 19.8 g (0
, 30 mol) lithium carbonate (0,30 mol) and N-
Add 188 m of methylpyrrolidone and add 2 ml of methylpyrrolidone under nitrogen atmosphere.
The 0 reaction product reacted at 62-265°C for 3 hours was post-treated in the same manner as in Example 1. As a result of analyzing Lio by atomic absorption method, it was found to be 930 PP■. Furthermore, ηin
h was 0.14.

r, continuation 11th, I) January 1962 2c7 II

Claims (3)

[Claims] (1) A method for producing a polyarylene sulfide resin by polymerizing a dihalogen aromatic compound and an alkali metal sulfide in a polar solvent, characterized in that the polymerization reaction is carried out at a temperature equal to or higher than the melting point of the resin. A method for producing polyarylene sulfide resin. (2) The method for producing a polyarylene sulfide resin according to claim 1, wherein the polymerization reaction is carried out at a temperature 5° C. or more higher than the melting point of the resin. (3) The method for producing a polyarylene sulfide resin according to claim 1 or 2, wherein the dihalogen aromatic compound is p-dichlorobenzene.