JP2001247676A - Method for producing polyarylene sulfide resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a highly pure polyarylene sulfide resin efficiently in a short polymerization processing time. SOLUTION: The method for producing the polyarylene sulfide resin is characterized in that (a) an alkali metal sulfide and/or an alkali metal hydrosulfide, (b) a polyhalogenated aromatic compound and (c) a metal compound comprising a group VIII metal of the Periodic Table are reacted in an organic polar solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for efficiently producing a high-purity polyarylene sulfide resin in a short polymerization process time.

[0002]

2. Description of the Related Art Polyarylene sulfide resin represented by polyphenylene sulfide has heat resistance, chemical resistance,
It is an engineering plastic with excellent flame retardancy, electrical properties and mechanical properties, and is widely used for fibers, films, injection molding and extrusion molding.

A conventional method for producing a polyarylene sulfide resin is disclosed in, for example, JP-A-5-239210.
As disclosed in the official gazette, alkali metal sulfide,
In particular, by heating sodium sulfide having water of hydration in a polar organic solvent, the water contained in the sodium sulfide hydrate is removed, and a dihalogenated aromatic compound is added thereto, followed by heat polymerization. Although typical, it is desired to develop a polymerization method having higher productivity.

Further, low molecular weight components in the finally obtained polyarylene sulfide resin cause deterioration in quality such as an increase in volatile components and a decrease in strength upon heating.
It is also desired to reduce such low molecular weight components.

[0005]

DISCLOSURE OF THE INVENTION The present invention has been accomplished by further improving the above prior art and as a result of studying the establishment of a novel method capable of rapidly producing a high-purity polyarylene sulfide resin. It was done.

Accordingly, it is an object of the present invention to provide a method for efficiently producing a high-purity polyarylene sulfide resin in a short polymerization process time.

[0007]

In order to achieve the above object, a method for producing a polyarylene sulfide resin according to the present invention comprises: (a) an alkali metal sulfide and / or an alkali metal hydrosulfide; A polyhalogenated aromatic compound and (c) a metal compound containing a metal of Group VIII of the periodic table are reacted in an organic polar solvent.

In the method for producing a polyarylene sulfide resin according to the present invention, the (c) No. VIII of the periodic table is used.
(A) the metal compound containing a group metal is at least one selected from a complex of a group VIII metal of the periodic table and / or a salt of a halogen with a group VIII metal of the periodic table;
The molar ratio of the alkali metal sulfide and / or alkali metal hydrosulfide to the metal compound containing a metal of Group (VIII) of the periodic table (c) is in the range of 1: 0.00001 to 1: 0.1. And that the amount of the organic polar solvent in the reaction system is in the range of 0.5 to 10 mol per mol of the alkali metal sulfide and / or alkali metal hydrosulfide (a). No.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The method for producing the polyarylene sulfide resin of the present invention will be described below in detail.

The polyarylene sulfide in the present invention is a homopolymer having a repeating unit represented by the following formula as a main constituent unit,

[0011]

Embedded image The repeating unit and the repeating unit per mole,
It is a copolymer comprising 1.0 mol or less, preferably 0.3 mol or less of the following repeating unit.

[0012]

Embedded image The (a) alkali metal sulfide and / or alkali metal hydrosulfide used in the present invention acts as a sulfidizing agent. Therefore, for these (a) alkali metal sulfides and / or alkali metal hydrosulfides,
Hereinafter, it is referred to as (a) a sulfidizing agent.

Specific examples of the alkali metal sulfide include, for example, sodium sulfide, potassium sulfide, lithium sulfide, rubidium sulfide, and cesium sulfide. Of these, sodium sulfide is preferably used. These alkali metal sulfides, as hydrates or aqueous mixtures,
Alternatively, it can be used in the form of an anhydride.

Specific examples of the alkali metal hydrosulfide include:
For example, sodium bisulfide, potassium bisulfide, lithium bisulfide, rubidium bisulfide, and cesium bisulfide are exemplified, and among them, sodium bisulfide is preferably used. These alkali metal hydrosulfides can be used as hydrates or aqueous mixtures, aqueous solutions or in the form of anhydrides.

It is also possible to use an alkali metal hydroxide and / or an alkaline earth metal hydroxide together with the above sulfidizing agent. Specific examples of the alkali metal hydroxide include, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, and cesium hydroxide. Specific examples of the alkaline earth metal hydroxide include, for example, Examples thereof include calcium, strontium hydroxide, barium hydroxide, and magnesium hydroxide, and among them, sodium hydroxide is preferably used.

When an alkali metal hydrosulfide is used as the sulfidizing agent, it is particularly preferable to use the alkali metal hydroxide at the same time. 0.95 to 1.20 mol, preferably 1.00 to 1.15 mol, more preferably 1.005 to 1.10.
A range of 0 mol can be exemplified.

(A) There are no particular restrictions on the timing of the development of the sulfide agent, and it can be introduced into the system in any of the following steps: a pre-process, between the pre-process and the main process, and at any stage of the main process. Most preferably, it is introduced at

The polyhalogenated aromatic compound (b) used in the present invention refers to a compound having two or more halogen atoms in one molecule and having a molecular weight of 1,000 or less. Specific examples include p-dichlorobenzene, m-dichlorobenzene, o-dichlorobenzene, 1,3,5-trichlorobenzene, 1,2,4-trichlorobenzene,
2,4,5-tetrachlorobenzene, hexachlorobenzene, 2,5-dichlorotoluene, 2,5-dichloro-
p-xylene, 1,4-dibromobenzene, 1,4-diiodobenzene, 1,4-dichloronaphthalene, 1,5
-Dichloronaphthalene, 1-methoxy-2,5-dichlorobenzene, 4,4'-dichlorobiphenyl, 3,5-
Dichlorobenzoic acid, 4,4′-dichlorodiphenyl ether, 4,4′-dichlorodiphenylsulfone, and 4,4′-dichlorodiphenylketone, and the like.
Among them, p-dichlorobenzene, m-dichlorobenzene, o-dichlorobenzene, 1,3,5-trichlorobenzene, 1,2,4-trichlorobenzene, 4,
4'-dichlorodiphenyl sulfone, and 4,4'-
Dichlorodiphenyl ketone and the like are preferably used, and especially p-dichlorobenzene is more preferably used. It is of course possible to form a copolymer by combining two or more different polyhalogenated aromatic compounds, but it is preferable to use a p-dihalogenated aromatic compound as a main component.

(B) The amount of the polyhalogenated aromatic compound used is from 0.9 to 2.0 moles per mole of the (a) sulfidizing agent, in order to obtain a polyarylene sulfide resin having a viscosity suitable for processing. Preferably 0.95 to 1.5
Mole, more preferably in the range of 1.005 to 1.2 mole.

(B) The method of adding the polyhalogenated aromatic compound is not particularly limited, but it is preferable to introduce the compound into the system in a pre-step described later and / or between the pre-step and the present step. .

The present invention is characterized in that (c) a metal compound containing a metal of Group VIII of the periodic table (hereinafter, referred to as (c) metal compound) is mainly used for accelerating the reaction.

The (c) metal compound used herein is specifically an organic phosphorus compound represented by tetrakis (triphenylphosphine), bis (diphenylphosphino) ethane, bis (diphenylphosphino) ferrocene, Organic nitrogen compounds such as tris (ethylenediamine), triethylenetetramine and bipyridine; organic oxygen compounds such as acetylacetonate and salicylate; organic compounds such as bis (cyclopentadiene) and bis (pentamethylcyclopentadiene) And at least one selected from a complex of a ligand selected from the group consisting of a group VIII metal and / or a salt of a group VIII metal and a halogen.

Specific examples of Group VIII metals of the periodic table include:
Palladium, nickel, cobalt, ruthenium, rhodium and platinum. More preferred VI of the Periodic Table
Examples of the compound containing a Group II metal include a zero-valent palladium or nickel complex.

The complex of the Group VIII metal of the Periodic Table has the formula L
nM (0) wherein M is a metal of Group VIII of the periodic table, L is R3P wherein R is independently selected from hydrocarbyl group moieties such as alkyl, aryl and cycloalkyl;
R3N, and n is 1-4). Specific examples of such a complex include, for example, tetrakis (triphenylphosphine) palladium (0), tetrakis (triphenylphosphine) cobalt (0), tetrakis (triphenylphosphine) nickel (0), bis [ Screw (1,
2-diphenylphosphino) ethane] palladium (0) and bis [bis (1,2-diphenylphosphino) ethane] nickel (0).

Other preferred complexes of Group VIII metals of the Periodic Table include those of the formula LnM (II) X2, wherein M is
The Group VIII metal, L, can be represented as R, R3P, R3N wherein R is independently selected from alkyl, aryl, cycloalkyl, cycloalkenyl, diol, carbonyl, polyhydroxycarbonyl, hydroxyquinone, and the like; Is 1-4. X is a halogen, and n is 0, 1 or 2). Specific examples of such a divalent metal complex include bis (triphenylphosphine) dichloronickel (II), bis (triphenylphosphine) dichloropalladium (II), and bis (triphenylphosphine).
Dichlorocobalt (II), [1,2-bis (diphenylphosphino) ethane] dichloronickel (II),
[1,2-bis (diphenylphosphino) ethane] dichloropalladium (II), [1,2-bis (diphenylphosphino) ethane] dichlorocobalt (II),
[1,2-bis (diphenylphosphino) ferrocene] dichloropalladium (II), bis (pentamethylcyclopentadienyl) dichlororhodium (II), cis-
Dichlorobis (2,2-bipyridine) ruthenium (I
Examples thereof include I), palladium acetylacetonate (II), nickel acetylacetonate (II), and cobalt tetraphenylporphine (II).

Other (c) metal compounds which can be used in the present invention include salts of nickel, palladium and cobalt with halogens. For example, NiCl ₂ , P
Examples include metal halides such as dCl ₂ , CoCl ₂ and CoBr ₂ .

In the polymerization method of the present invention, an effective amount of (c) a metal compound is used for the reaction of (a) a sulfidizing agent with (b) a polyhalogenated aromatic compound to form a polyarylene sulfide resin. It is important that contact is included. That is, in the reaction mixture,
The molar ratio of (a) the sulfidizing agent: (c) the metal compound is
It is preferable to be contained in the range of 1: 0.00001 to 1: 0.1.

The above-mentioned reaction is carried out in an organic polar solvent at a temperature of at least 200 ° C., preferably about 210 ° C. to 300 ° C. And this reaction is generally performed under an inert atmosphere such as nitrogen. Reaction times will vary widely depending on other reaction conditions, but generally range from about 1 to 10
Time, preferably in the range of 2 to 5 hours.

In the present invention, an organic polar solvent is used as a polymerization solvent. Specific examples of the organic polar solvent include N
-Methyl-2-pyrrolidone, N-methylcaprolactam, 1,3-dimethyl-2-imidazolidinone, N, N
-Dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, dimethylsulfone, tetramethylenesulfoxide and the like, among which N-methyl-2-pyrrolidone is preferably used.

The amount of the organic polar solvent used is such that the amount of the organic polar solvent in the reaction system is 0.5% per mole of the (a) sulfidizing agent.
To 10 moles, preferably 2 to 8 moles, more preferably 3 to 7 moles, and even more preferably 3.8 to 6 moles. If the amount of the organic polar solvent is less than the above range, an undesirable reaction tends to occur. If the amount exceeds the above range, the degree of polymerization tends to be difficult to increase. here,
The amount of the organic polar solvent in the reaction system is an amount obtained by subtracting the amount of the organic polar solvent removed outside the reaction system from the amount of the organic polar solvent introduced into the reaction system. The organic polar solvent can be introduced into the system in a later step and / or between the preceding step and this step.

In the present invention, a polymerization aid can be used if necessary. Here, the polymerization aid means a substance having an action of increasing the viscosity of the obtained polymer. Specific examples of such polymerization aids include, for example, organic carboxylate, water, organic sulfonate, alkali metal sulfate, alkaline earth metal oxide, alkali metal phosphate and alkaline earth metal phosphate And the like. These can be used alone or in combination of two or more. Among them, organic carboxylate and / or water are preferably used.

Specific examples of the organic carboxylate include a compound represented by the formula R
(COOM) wherein R is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group, an alkylaryl group or an arylalkyl group, and M is an alkali selected from lithium, sodium, potassium, rubidium and cesium. Which is a metal). More specifically, lithium acetate, sodium acetate, potassium acetate, sodium propionate,
Examples include lithium benzoate, sodium benzoate, sodium phenylacetate and sodium p-toluate. The organic carboxylate is selected from the group consisting of an organic carboxylic acid and an alkali metal hydroxide, an alkali metal carbonate and an alkali metal bicarbonate in an organic polar solvent.
The compounds may be formed by adding approximately one or more compounds in substantially equal stoichiometric amounts and reacting them. One or more organic carboxylate salts can be used simultaneously.
Among them, lithium acetate and / or sodium acetate are preferably used, and sodium acetate is more preferably used because it is inexpensive and easily available.

Water is present in the reaction system as a hydrate or aqueous solution of an organic metal carboxylate, a hydrate or aqueous solution of an alkali metal sulfide, or an aqueous solution of an alkali metal hydrosulfide, or is directly added to the reaction system. Either one or both may be used.

There is no particular limitation on the timing of introducing the polymerization aid into the system, and it is possible to introduce the polymerization aid into the system in any of the following pre-steps, between the pre-step and this step, and at any stage of this step. It is possible.

In the present invention, (a) a sulfidizing agent,
An example of a reaction step of (b) a polyhalogenated aromatic compound and (c) a metal compound in an organic polar solvent will be described below. That is, the method for producing a polyarylene sulfide resin of the present invention includes a pre-process and a post-process in addition to the present process described below, and it is particularly preferable to perform the process in the following processes including the pre-process. Further, auxiliary steps may be added before and after these steps.

First, dehydration is carried out in the presence of an organic polar solvent and (a) a sulfidizing agent, if necessary, an alkali metal hydroxide and a polymerization aid, preferably in an inert gas atmosphere, at a temperature in the range of room temperature to 250 ° C. The reaction is performed, and the amount of water in the reaction system is adjusted (pre-process).

The water content of the reaction system as referred to herein is a value obtained by subtracting the water content removed outside the reaction system from the water content introduced into the reaction system as an aqueous solution and hydrate at the time of charging the raw materials. There is no particular limitation on this amount, but in particular -0.5 to 2.5 per mol of the charged (a) sulfidizing agent.
Mol, more preferably in the range of 0 to 2.0 mol, from the viewpoint of polymerization rate and suppression of by-products.

Next, a predetermined amount of (b) a polyhalogenated aromatic compound and (c) a metal compound, and if necessary, an organic polar solvent and a polymerization aid are added to the obtained mixture, and at least 2 parts are added.
The polymerization reaction is performed at a temperature of 00 ° C. or higher, preferably 210 to 300 ° C. (this step).

It is also possible to add water or (b) a polyhalogenated aromatic compound or monohalogenated compound during the polymerization reaction or during the subsequent cooling step.

The granular polyarylene sulfide thus obtained is usually washed with an organic solvent and / or water and dried (post-treatment).

The organic solvent used for washing is not particularly limited as long as it does not have a function of decomposing the polyarylene sulfide resin.
Pyrrolidone, dimethylformamide, nitrogen-containing polar solvents such as dimethylacetamide, dimethylsulfoxide, sulfoxidesulfone solvents such as dimethylsulfone,
Ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone and acetophenone; ether solvents such as dimethyl ether, dipropyl ether and tetrahydrofuran; and halogen solvents such as chloroform, methylene chloride, trichloroethylene, ethylene dichloride, dichloroethane, tetrachloroethane and chlorobenzene. Solvent, methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol,
Examples include alcohol / phenol solvents such as phenol, cresol, and polyethylene glycol, and aromatic hydrocarbon solvents such as benzene, toluene, and xylene. Among these organic solvents, it is particularly preferable to use N-methyl-2-pyrrolidone, acetone, dimethylformamide, chloroform and the like. These organic solvents are used alone or in combination of two or more.

As a method of washing with an organic solvent, there is a method of immersing a polyarylene sulfide resin in an organic solvent, and it is also possible to agitate or heat as needed.

The washing temperature for washing the polyarylene sulfide resin with an organic solvent is not particularly limited.
Any temperature between normal temperature and about 300 ° C. can be selected. Although the cleaning efficiency tends to increase as the cleaning temperature increases, a sufficient effect can usually be obtained at a cleaning temperature of normal temperature to 150 ° C.

The ratio of the polyarylene sulfide resin to the organic solvent used for washing is preferably as large as possible, but a bath ratio of 300 g or less of the polyarylene sulfide resin to 1 liter of the organic solvent is usually selected.

It is preferable that the polyarylene sulfide resin washed with the organic solvent is further washed several times with water or warm water in order to remove the remaining organic solvent.

As a method for washing the polyarylene sulfide resin with water or hot water, there is a method of immersing the polyarylene sulfide resin in water or hot water, and it is also possible to agitate or heat as needed.

The washing temperature at the time of washing the polyarylene sulfide with water or hot water is preferably 20 ° C. to 220 ° C. in consideration of the removal of by-products and the safety of high pressure.
50 ° C to 200 ° C is more preferred.

The water or the water used for washing with warm water is preferably distilled water or deionized water, but if necessary, formic acid, acetic acid, propionic acid, butyric acid, chloroacetic acid, dichloroacetic acid, acrylic acid, crotonic acid. Organic acidic compounds such as benzoic acid, salicylic acid, oxalic acid, malonic acid, succinic acid, phthalic acid, fumaric acid and alkali metals thereof,
An aqueous solution containing an alkaline earth metal salt, an inorganic acidic compound such as sulfuric acid, phosphoric acid, hydrochloric acid, carbonic acid, and silicic acid, and an ammonium ion may be used.

The operation of the hot water treatment is usually carried out by charging a predetermined amount of polyarylene sulfide resin into a predetermined amount of water, and heating and stirring at normal pressure or in a pressure vessel. As for the ratio of the polyarylene sulfide resin and water, it is preferable that the amount of water is large.
A bath ratio of 200 g or less of the polyarylene sulfide resin is selected.

The granular polyarylene sulfide resin obtained through such a process has a low by-product content,
When used in fibers, films, resin compositions for molding, etc., it has little gel and gas and is excellent in moldability.

The polyarylene sulfide resin obtained by the production method of the present invention may be used alone or, if desired, an inorganic filler such as glass fiber, carbon fiber, titanium oxide, calcium carbonate, or the like. Inhibitors, heat stabilizers,
Additives such as ultraviolet absorbers and coloring agents can also be added, such as polyamide, polysulfone, polyphenylene,
Polyolefins having functional groups such as polycarbonate, polyether sulfone, polyethylene terephthalate, polybutylene terephthalate, polyethylene, polypropylene, polytetrafluoroethylene, epoxy groups, carboxyl groups, carboxylic acid ester groups, acid anhydride anhydride groups, etc. Resins such as a system elastomer, a polyetherester elastomer, a polyetheramide elastomer, a polyamideimide acetal, and a polyimide can also be used.

The polyarylene sulfide resin obtained by the production method of the present invention has excellent characteristics such as excellent heat resistance, chemical resistance, flame retardancy, electrical properties and mechanical properties, and particularly low content of impurities. It can be widely used not only for injection molding but also for extrusion molding of fibers, sheets, films and pipes by extrusion.

Specific uses of these molded articles include, for example, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable condenser cases, optical pickups, oscillators, various terminal boards, and transformers. , Plugs, printed circuit boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, electrical appliances such as computer-related parts・ Electronic components; VTR
Parts, TV parts, irons, hair dryers, rice cooker parts, microwave parts, audio parts, audio equipment parts such as audio / laser disks (registered trademark) / compact disks; lighting parts, refrigerator parts, air conditioner parts,
Home and office electrical product parts such as typewriter parts and word processor parts, office computer-related parts, telephone-related parts, facsimile-related parts, copier-related parts, cleaning jigs, motor parts, writers, typewriters, etc. Machinery-related parts represented by;
Optical equipment such as microscopes, binoculars, cameras, clocks, etc., precision machinery related parts; tap faucets, mixing faucets, pump parts, pipe joints, water flow control valves, relief valves, hot water temperature sensors, water flow sensors, water meters Plumbing parts such as housing; valve alternator terminal, alternator connector, IC regulator, potentiometer base for light deer, various valves such as exhaust gas valve, fuel related, exhaust system, intake system various pipes, air intake nozzle snorkel, intake Manifold, fuel pump, engine cooling water joint,
Carburetor main body, carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake pad wear sensor, thermostat base for air conditioner, heating hot air flow control valve, radiator Brush holder for motor, water pump impeller, turbine vane, wiper motor related parts,
Distributors, starter switches, starter relays, wire harnesses for transmissions, window washer nozzles, air conditioner panel switch boards, coils for fuel related electromagnetic valves, connectors for fuses, horn terminals, electrical component insulation plates, step motor rotors, lamp sockets, Lamp reflector,
Automotive / vehicle related parts such as a lamp housing, a brake piston, a solenoid bobbin, an engine oil filter, an ignition device case, a vehicle speed sensor, a cable liner; and other various applications.

[0054]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. In addition, the measuring method of a physical property is as follows. [Reaction rate of monomer (p-dichlorobenzene)] The unreacted monomer (p-dichlorobenzene) remaining in the polymerization system was quantified by gas chromatography analysis. The reaction rate was calculated based on the following equation.

Reaction rate (%) = (1- (XZ) / (Y-
Z)) × 100 X: Number of moles of remaining unreacted p-dichlorobenzene Y: Number of moles of p-dichlorobenzene at the time of charging Z: Number of moles of p-dichlorobenzene in excess with respect to the sulfur source at the time of charging Indicates that the reaction is easy to proceed. [Loss on heating] Dried polyphenylene sulfide (PP
S) About 10 g of the resin was weighed, and the weight loss when the resin was treated at 320 ° C. for 2 hours was determined.

The smaller the value, the better the amount of gas generated during heating. Example 1 In a 1 liter autoclave equipped with a stirrer, 118 g (1.00 mol) of 47% sodium hydrosulfide, 42.9 g (1.03 mol) of 96% sodium hydroxide, and 163 g of N-methyl-2-pyrrolidone (1.65
Mol), 27.0 g (0.33 mol) of sodium acetate and 150 g of ion-exchanged water, and gradually heated to 205 ° C. over about 3 hours while passing nitrogen at normal pressure to obtain water 2
After distilling out 05 g and N-methyl-2-pyrrolidone 4 g, the reaction vessel was cooled to 160 ° C., and 147 g (1.00 mol) of p-dichlorobenzene, [1,2-bis (diphenylphosphino) ethane] 5.76 g (0.01 mol) of dichloropalladium (II) and N-methyl-
131 g (1.31 mol) of 2-pyrrolidone were added.

Next, the reaction vessel was sealed under nitrogen gas,
The temperature was raised to 20 ° C. and maintained for 120 minutes. Then 50 ° C
Cooling was carried out.

Thereafter, the contents were taken out, sufficiently washed with warm water, and filtered with a glass filter. This is 1
It dried under reduced pressure at 20 degreeC.

As a result, the conversion of the monomer (p-dichlorobenzene) was 71%. Comparative Example 1 [1,2-Bis (diphenylphosphino) ethane] The same operation as in Example 1 was performed except that dichloropalladium (II) was not added.

In this case, the conversion of the monomer (p-dichlorobenzene) was inferior to 41%. Example 2 (c) Instead of [1,2-bis (diphenylphosphino) ethane] dichloropalladium (II) as the metal compound, bis [bis (1,2-diphenylphosphino) ethane] palladium (0 ) 9.03 g
The same operation as in Example 1 was performed except that (0.01 mol) was used.

As a result, the conversion of the monomer (p-dichlorobenzene) was 65%. Example 3 (c) As a metal compound, instead of [1,2-bis (diphenylphosphino) ethane] dichloropalladium (II), 4.75 g (0.009 mol) of bis (triphenylphosphine) dichlorocobalt was used. ) Was performed in the same manner as in Example 1 except that the above was used.

As a result, the conversion of the monomer (p-dichlorobenzene) was 62%.

As is clear from the results of Examples 1 to 3 and Comparative Example 1, the polyarylene sulfide resin obtained through the polymerization system of the present invention is different from Comparative Example 1 in which (c) the metal compound was not added. The reaction rate was higher than that. Example 4 In a 1 liter autoclave equipped with a stirrer, 118 g (1.00 mol) of 47% sodium hydrosulfide, 42.9 g (1.03 mol) of 96% sodium hydroxide, and 163 g of N-methyl-2-pyrrolidone (1.65
Mol), 27.0 g (0.33 mol) of sodium acetate and 150 g of ion-exchanged water, and gradually heated to 205 ° C. over about 3 hours while passing nitrogen at normal pressure to obtain water 2
After distilling out 05 g and N-methyl-2-pyrrolidone 4 g, the reaction vessel was cooled to 160 ° C., and 147 g (1.00 mol) of p-dichlorobenzene, [1,2-bis (diphenylphosphino) ethane] 5.76 g (0.01 mol) of dichloropalladium (II) and N-methyl-
131 g (1.31 mol) of 2-pyrrolidone were added.

Next, the reaction vessel was sealed under nitrogen gas,
The temperature was raised to 20 ° C. and maintained for 360 minutes. Then 50 ° C
Cooling was carried out.

Thereafter, the contents were taken out, washed sufficiently with warm water, and filtered through a glass filter.
It dried under reduced pressure at ° C.

As a result, the conversion of the monomer (p-dichlorobenzene) was almost 100%.

The obtained polyphenylene sulfide resin had a weight loss upon heating (weight loss upon heating) of 0.9% by weight. Comparative Example 2 The same operation as in Example 4 was performed except that [1,2-bis (diphenylphosphino) ethane] dichloropalladium (II) was not added.

As a result, the conversion of the monomer (p-dichlorobenzene) was almost 100%.

The weight loss of the obtained polyphenylene sulfide resin upon heating was 1.4% by weight.

As is evident from the results of Example 4 and Comparative Example 2, the polyarylene sulfide resin obtained by the method of the present invention is (c) Comparative Example 2 containing no metal compound.
As compared with the sample, the amount of gas generated during heating was small, and the sample was higher in purity.

[0071]

As described above, according to the production method of the present invention, a high-purity polyarylene sulfide resin can be efficiently produced in a short polymerization process time.

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Claims (4)

[Claims] (1) An alkali metal sulfide and / or an alkali metal hydrosulfide, (b) a polyhalogenated aromatic compound, and (c) a metal compound containing a metal of Group VIII of the periodic table. A method for producing a polyarylene sulfide resin, wherein the reaction is carried out in an organic polar solvent. 2. The metal compound containing a metal of Group VIII of the periodic table (c) is selected from a complex of a metal of Group VIII of the periodic table and / or a salt of a metal of Group VIII of the periodic table with a halogen. The method for producing a polyarylene sulfide resin according to claim 1, wherein the method is at least one. 3. The molar ratio of (a) an alkali metal sulfide and / or an alkali metal hydrosulfide to (c) a metal compound containing a metal belonging to Group VIII of the periodic table is 1: 0.00001.
The method for producing a polyarylene sulfide resin according to claim 1 or 2, wherein the ratio is in the range of -1 to 0.1. 4. The amount of the organic polar solvent in the reaction system is in the range of 0.5 to 10 mol per mol of the alkali metal sulfide and / or alkali metal hydrosulfide (a). A method for producing the polyarylene sulfide resin according to claim 1.