JP2001089569A - Production of granular polyarylene sulfide resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To bring it a subject to provide a method for producing a granular arylene sulfide resin having high purity in a short time required for polymerization processing. SOLUTION: In the method for producing a polyarylene sulfide by reacting a polyhalogenated aromatic compound with a thioetherification agent in an polar organic solvent in at least two processes described below, process 1: a process for reacting the polyhalogenated aromatic compound with the thioetherification agent at 245-290 deg. C and process 2: a process for cooling the reaction product obtained by the process 1, the cooling speed is characterized to be controlled in the range of 0.2 deg. C/min. to 1.3 deg.C/min. to obtain the granular polyarylene sulfide resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a highly pure granular polyarylene sulfide resin in a high yield in a short 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. It is described in Japanese Patent Publication No. 52-12240, for example, that this resin is obtained by reacting a dihalogenated aromatic compound with an alkali metal sulfide in an organic polar solvent. According to this method, generally, after the polymerization system in a high temperature state is taken out by flashing into a container under normal pressure or reduced pressure,
To recover the resin through solvent recovery, washing and drying,
Finally, a powdery resin having a particle diameter of several microns to 50 microns is obtained. This powdery resin becomes dusty when dry and easily scatters, has a low bulk density, is bulky, and is difficult to handle.Also, at the time of melt extrusion, since the amount of discharge is reduced due to entrainment of air, pelletization is necessary. There is a problem that extrusion productivity is inferior.

On the other hand, a method of recovering a granular resin having a relatively large bulk density by cooling the reaction system after the polymerization reaction is disclosed in
JP-A-9-1536 and JP-A-60-235838 disclose special conditions such as addition of a precipitant to precipitate polyarylene sulfide in a molten state at the time of particle formation, that is, at a cooling stage. Alternatively, the particulate resin can be recovered by controlling the temperature.

[0004] As a result of our recent research, the molar ratio of the polyhalogenated aromatic compound to the organic polar solvent in the polymerization reaction stage and the cooling rate after the polymerization reaction are reduced in the particle formation and finally obtained polymer particles. It has been found that this affects the amount of by-products remaining. When the molar ratio between the polyhalogenated aromatic compound and the organic polar solvent in the polymerization reaction system is changed, the method disclosed in the above publication has revealed a problem that granular resin may not be obtained in some cases. . The above publication does not disclose any influence on the production of granular polyarylene sulfide by the molar ratio of the polyhalogenated aromatic compound in the polymerization reaction system and the organic polar solvent and the cooling rate after the polymerization.

In addition, the granular resin obtained when the temperature is inappropriately controlled contains a large amount of by-products of polymerization in the particles, which indicates that the finally obtained polyarylene sulfide resin is volatile during heating. There is a problem in that the quality of the composition is reduced, such as an increase in components, thermal deterioration and coloring. Further, in powder and particulate polyarylene sulfide,
Reduction of resin yield also poses a problem. Accordingly, there is a strong need for an improved method of obtaining granular polyarylene sulfide resin with high purity and high yield.

[0006]

SUMMARY OF THE INVENTION The object of the present invention is to improve the disadvantages of the prior art and to provide a process for producing a highly pure granular polyarylene sulfide resin in a short polymerization process time. I do.

[0007]

Means for Solving the Problems To achieve the above object, the granular polyarylene sulfide resin of the present invention is obtained by the following method. That is, the present invention
(1) The reaction of a polyhalogenated aromatic compound and a sulfidizing agent in an organic polar solvent is performed in at least the following two steps: Step 1: A polyhalogenated aromatic compound and a sulfidizing agent are reacted in a temperature range of 245 ° C. to 290 ° C. Reacting step 2: cooling the reactant reacted in step 1 in the method for producing polyarylene sulfide, wherein the cooling rate is 0.2 ° C. in the temperature range of at least one part of step 2. / Minute to 1.3 ° C./minute, a method for producing a granular polyarylene sulfide resin, (2) a reaction of a polyhalogenated aromatic compound and a sulfidizing agent in an organic polar solvent. At least two successive steps: Step 1: a polyhalogenated aromatic compound and a sulfide in a temperature range of 245 ° C. to 290 ° C. Step of reacting the agent Step 2: In the method for producing polyarylene sulfide, which is carried out in a step including a step of cooling the reactant reacted in Step 1, the polyhalogenated aromatic introduced into the polymerization system in Step 1 The molar ratio of the compound and the organic polar solvent present in the reaction system at the end of Step 1 is M, and in Step 2, 2
In the temperature range of 45 ° C. or less, first, the cooling rate S1 (0.2
≦ S1 (° C./min)≦1.3), cooling at least to a temperature T1 (° C.) defined by the following (Equation 1), and then at a cooling rate S2 (1.3 <S2 (° C./min)) A method for producing a granular polyarylene sulfide resin characterized by multi-stage cooling for cooling, and T1 = −0.33 × (100 × S1 + 20 × M−760) +20 (Equation 1) (where 150 ≦ T1 ≦ 245) 0.2 ≦ S1 ≦ 1.3 0.5 ≦ M ≦ 10 M represents the polyhalogenated aromatic compound (Mh) introduced into the polymerization system and the organic polarity present in the reaction system at the end of step 1. The molar ratio of the solvent (Ms) (M = Ms / M
h). (3) Step 1 is carried out using an organic carboxylate, water, an alkali metal chloride, an organic sulfonate, an alkali metal sulfate, an alkaline earth metal oxide, an alkali metal phosphate,
The process for producing a granular polyarylene sulfide resin according to the above (1) or (2), wherein the process is carried out in the presence of at least one polymerization aid selected from alkaline earth metal phosphates.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The polyarylene sulfide in the present invention is a homopolymer or a copolymer having a repeating unit of the formula-(Ar-S)-as a main constituent unit.
Examples of Ar include units represented by the following formulas (A) to (K), among which (A) is particularly preferred.

[0009]

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(R1 and R2 are substituents selected from hydrogen, an alkyl group, an alkoxy group, and a halogen group, and R1 and R2 may be the same or different.) It may contain a small amount of a branching unit or a crosslinking unit represented by the following formulas (L) to (N). The copolymerization amount of these branching units or crosslinking units is preferably in the range of 0 to 1 mol% with respect to 1 mol of-(Ar-S) -unit.

[0011]

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The polyarylene sulfide in the present invention may be a random copolymer, a block copolymer or a mixture thereof containing the above repeating unit.

Further, the molecular weight of each of the various polyarylene sulfides is not particularly limited.
5,000 Pa · s (310 ° C., shear rate 1,000 /
Seconds) can be exemplified as a preferable range.

As typical examples thereof, polyphenylene sulfide, polyphenylene sulfide sulfone,
Examples thereof include polyphenylene sulfide ketone, random copolymers thereof, block copolymers, and mixtures thereof. Particularly preferred polyarylene sulfides include p-phenylene units as main constituent units of the polymer.

[0015]

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, Polyphenylene sulfide, polyphenylene sulfide sulfone, and polyphenylene sulfide ketone containing 90 mol% or more.

The sulfidizing agent used in the present invention includes alkali metal sulfides and alkali metal hydrosulfides. Specific examples of the alkali metal sulfide include, for example, sodium sulfide, potassium sulfide, lithium sulfide, rubidium sulfide, cesium sulfide, and the like. Of these, sodium sulfide is preferably used. These alkali metal sulfides can be used as hydrates or aqueous mixtures or in anhydrous form.

Specific examples of the alkali metal hydrosulfide include:
For example, sodium bisulfide, potassium bisulfide, lithium bisulfide, rubidium bisulfide, cesium bisulfide and the like can be mentioned, among which sodium bisulfide is preferably used.
These alkali metal hydrosulfides can be used as hydrates or aqueous mixtures or in anhydrous form.

It is also possible to use an alkali metal hydroxide and / or an alkaline earth metal hydroxide together with the sulfidizing agent. Specific examples of the alkali metal hydroxide, for example, sodium hydroxide, potassium hydroxide,
Lithium hydroxide, rubidium hydroxide, cesium hydroxide and the like, as specific examples of the alkaline earth metal hydroxide, for example, calcium hydroxide, strontium hydroxide, barium hydroxide and the like, among which sodium hydroxide is It is preferably used.

When an alkali metal hydrosulfide is used as the sulfidizing agent, it is particularly preferable to use an alkali metal hydroxide at the same time. .20 mol, preferably 1.00 to 1.15 mol, more preferably 1.
The range of 005 to 1.100 mol can be exemplified. The sulfidizing agent can be introduced into the system in any of the following pre-steps, between the pre-step and step 1 and in step 1, but is preferably introduced in the pre-step.

The polyhalogenated aromatic compound used in the present invention has two or more halogen atoms in one molecule,
And a compound 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, 1,2,2
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, 4,4 '
And polyhalogenated aromatic compounds such as -dichlorodiphenylketone, and preferably p-dichlorobenzene, 4,4'-dichlorodiphenylsulfone, and 4,4 '.
-Dichlorodiphenyl ketone, more preferably p-dichlorobenzene. It is also 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.

The amount of the polyhalogenated aromatic compound used is
From the viewpoint of obtaining a polyarylene sulfide having a viscosity suitable for processing, 0.9 to 2.0 mol, preferably 0.95 to 1.5 mol, more preferably 1.005 to 1.2 mol per mol of the sulfidizing agent. The range of the mole can be exemplified. The polyhalogenated aromatic compound can be introduced into the system at any stage of the pre-process shown below, between the pre-process and the process 1 and at any stage of the process 1, but preferably between the pre-process and the process 1 And / or introduced in step 1.

In the present invention, an organic polar solvent is used as a polymerization solvent. Specific examples 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 can be mentioned, 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 (polymerization system) is 0.5 to 10 mol, preferably 2 to 8 mol, more preferably 3 to 7 mol per mol of the sulfidizing agent. Moles, more preferably in the range of 3.8 to 6 moles. If the amount is too small, an undesirable reaction tends to occur. If the amount is too large, the degree of polymerization tends to hardly 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 any of the following pre-process steps, between the pre-process step and step 1, and in step 1.

In the present invention, a polymerization aid is used if necessary. Here, the polymerization aid refers to a substance having an action of increasing the viscosity of the obtained polymer. Specific examples of such a polymerization aid include, for example, organic carboxylate, water, alkali metal chloride, organic sulfonate, alkali metal sulfate,
Alkaline earth metal oxides, alkali metal phosphates, alkaline earth metal phosphates and the like can be mentioned. These may be used alone or in combination of two or more. Among them, organic carboxylate and / or water are preferably used.

The organic carboxylate is represented by the general formula R (COO
M), 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. A metal). Specific examples include lithium acetate, sodium acetate, potassium acetate, sodium propionate, lithium benzoate, sodium benzoate, sodium phenylacetate, sodium p-toluate, and the like. The organic carboxylate is prepared by subjecting the organic carboxylic acid to one or more compounds selected from the group consisting of alkali metal hydroxides, alkali metal carbonates, and alkali metal bicarbonates in an organic polar solvent in substantially equivalent stoichiometric amounts. It may be formed by adding and reacting. 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 an organic metal carboxylate hydrate or aqueous solution, an alkali metal sulfide hydrate or an aqueous solution, or an alkali metal hydrosulfide aqueous solution, or added directly into the reaction system. Either one or both may be used.

There is no particular limitation on the time when the polymerization aid is introduced into the system, and it is possible to introduce the polymerization aid into the system at any of the following pre-process steps, between the pre-process step and step 1, and at any stage of step 1. .

In the present invention, the reaction of the polyhalogenated aromatic compound and the sulfidizing agent in an organic polar solvent is carried out in at least two steps, Step 1 and Step 2. An auxiliary step may be added before or after these steps.

Step 1 Step 1 is a step of reacting a polyhalogenated aromatic compound with a sulfidizing agent in an organic polar solvent at a temperature range of at least 245 ° C. to 290 ° C.

Prior to step 1, in the presence of an organic polar solvent and a sulfidizing agent, if necessary, an alkali substance, a polyhalogenated aromatic compound and a polymerization aid, preferably under an inert gas atmosphere, from room temperature to 250 ° C. May be performed to adjust the amount of water in the reaction system (previous step).

Here, the amount of water in the reaction system is an amount obtained by subtracting the amount of water removed outside the reaction system from the amount of water introduced into the reaction system as an aqueous solution and hydrate at the time of charging the raw materials. The amount is not particularly limited, but is preferably in the range of -0.5 to 2.5 mol, more preferably 0 to 2.0 mol, per mol of the charged sulfidizing agent.
It is preferable in terms of polymerization rate and suppression of by-products. If the water content in the system is too large, prior to step 1, the mixture containing at least the organic polar solvent and the sulfidizing agent is heated from 150 ° C. to about 250 ° C., preferably in an inert gas atmosphere. It is preferred to remove the amount of water out of the system.

Further, the reaction may be carried out in a temperature range of less than 245 ° C. before the step 1, and then the temperature may be raised from 245 ° C. to 290 ° C. to further carry out the polymerization reaction. Step 1 temperature is 2
If the temperature is lower than 45 ° C., the polymerization rate becomes slow, and if it exceeds 290 ° C., the produced polyarylene sulfide and the organic polar solvent are liable to be decomposed.

Step 2 In the step 2, ie, the step of cooling the reactant reacted in the step 1, the cooling rate is controlled within the range of 0.2 ° C./min to 1.3 ° C./min in at least one temperature range. I do.

In the step 2, the molar ratio of the polyhalogenated aromatic compound introduced into the polymerization system in the step 1 to the organic polar solvent present in the reaction system at the end of the step 1 is defined as M. In the temperature range of 245 ° C. or lower, first, the cooling rate S1 (0.2 ≦ S1 (° C./min)≦1.3)
And at least a temperature T1 defined by the following (Equation 1)
It is preferable to cool to (° C.).

However, of the time required from 245 ° C. to T1, the cooling time exceeding 1.3 ° C./min is 10 minutes.
%, There is no problem unless the object of the present invention is essentially impaired. Further, the cooling rate in the temperature range exceeding 245 ° C. is not particularly limited, but is preferably in the same rate range as in S1.

In order to obtain high-purity polymer particles, it is preferable to cool the reaction system at a relatively low speed (S1) to stably generate polymer particles. However, if the cooling is performed at the speed S1 in all the temperature ranges, the total polymerization time becomes longer, and the productivity is deteriorated.

Therefore, we examined in detail the behavior of forming polymer particles in the cooling process, and found that the cooling rate and the amount of solvent used strongly affected the formation of polymer particles. Then, those relationships were arranged and an empirical formula (Formula 1) was obtained. That is, if at least the region up to the temperature T1 shown in (Equation 1) is cooled at a relatively low speed (S1), high-purity polymer particles can be obtained even after cooling at a higher speed (S2). The present inventors have found something and have led to the present invention. T1 = −0.33 × (100 × S1 + 20 × M−760) +20 (Expression 1) However, 150 ≦ T1 ≦ 245 0.2 ≦ S1 ≦ 1.3 0.5 ≦ M ≦ 10 M is before polymerization. Is the molar ratio of the polyhalogenated aromatic compound (Mh) to the molar amount (Ms) of the organic polar solvent present in the reaction system at the end of the step 1 (M = Ms /
Mh).

The range of S1 is preferably 0.6 ≦ S1 ≦ 1.2, more preferably 0.8 ≦ S1 ≦ 1.2. If S1 is too small, the time required for step 2 will be extremely long and the productivity will decrease, and if S1 is too large, the yield and quality of granular polyarylene sulfide will be reduced, and neither is preferred.

The cooling rate S1 may be varied as long as the object of the present invention is not substantially impaired.
Does not hinder the average cooling rate. However, 245
Of the time required from C to T1, the cooling rate is 1.3
Even if the time exceeding ℃ / min is less than about 10%, there is no problem unless the object of the present invention is essentially impaired.
When the cooling rate exceeds 1.3 ° C./min in the above range,
Not taken into account when averaging the cooling rates.

The range of M is preferably 2 ≦ M ≦ 8, more preferably 3 ≦ M ≦ 7, and still more preferably 3.8 ≦ M ≦ 6. If M is too small, undesired by-products are likely to be included in the finally obtained granular polyarylene sulfide, and if it is too large, the time for forming the granular polyarylene sulfide becomes extremely long, and the productivity is lowered. Is also not preferred.

In the present invention, it is essential to cool at least to the temperature T1 at the cooling rate S1, but it is more preferable to cool to at least (T1-20) ° C. at the cooling rate S1.

In step 2, the cooling rate S1 and the temperature T1
After cooling to below, the cooling rate S2 (1.3 <S2 (° C
/ Min)), and further cooling is carried out. The cooling rate is not particularly limited as long as it is a rate exceeding 1.3 ° C./min, but is preferably in the range of 1.3 to 10 ° C./min, more preferably 1.3 to 8 ° C./min. The speed may be constant, or the speed may be changed. If the speed is too low, the time required for step 2 becomes long, and the productivity is undesirably reduced.

In this cooling step, an organic polar solvent and / or a known organic solvent may be added or extracted as needed.

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. For example, nitrogen-containing organic solvents such as N-methyl-2-pyrrolidone, dimethylformamide and dimethylacetamide are used. Polar solvents, sulphoxide / sulfone solvents such as dimethyl sulfoxide and dimethyl sulfone, ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone and acetophenone, ether solvents such as dimethyl ether, dipropyl ether and tetrahydrofuran, chloroform, methylene chloride, trichloroethylene, Halogen solvents such as ethylene dichloride, dichloroethane, tetrachloroethane, chlorobenzene, methanol, ethanol, propanol, butanol, pentanol, ethylene glycol Lumpur, propylene glycol, phenol, cresol, alcohol phenol based solvents such as polyethylene glycol, benzene, toluene,
Examples include aromatic hydrocarbon solvents such as xylene. Among these organic solvents, use of N-methyl-2-pyrrolidone, acetone, dimethylformamide, chloroform or the like is preferred. In addition, these organic solvents include 1
It is used in a kind or a mixture of two or more kinds.

As a method of washing with an organic solvent, there is a method of immersing polyarylene sulfide in an organic solvent, and the like, and if necessary, stirring or heating can also be performed.

The washing temperature for washing the polyarylene sulfide with an organic solvent is not particularly limited, and is from room temperature to normal temperature.
Any temperature of 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 to the organic solvent is preferably higher in the amount of the organic solvent.
A bath ratio of less than or equal to g is selected.

The PPS resin that has been washed with an organic solvent is preferably washed several times with water or warm water in order to remove the remaining organic solvent.

As a method of washing the polyarylene sulfide with water or hot water, there is a method of immersing the polyarylene sulfide in water or hot water.
If necessary, stirring or heating can be appropriately performed.

The washing temperature for washing the polyarylene sulfide with water or hot water is preferably from 20 ° C. to 220 ° C., more preferably from 50 ° C. to 200 ° C. If the temperature is lower than 20 ° C., it is difficult to remove by-products.

Water or water used for washing with warm water is preferably distilled water or deionized water. 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 inorganic acidic compounds such as alkali metal, alkaline earth metal salts, sulfuric acid, phosphoric acid, hydrochloric acid, carbonic acid, and silicic acid And an aqueous solution containing ammonium ions and the like.

The operation of the hot water treatment is usually carried out by adding a predetermined amount of polyarylene sulfide to a predetermined amount of water, and heating and stirring at normal pressure or in a pressure vessel.
The proportion of polyarylene sulfide to water is preferably as high as possible, but a bath ratio of 200 g or less of polyarylene sulfide to 1 liter of water is usually selected.

The obtained granular polyarylene sulfide has a low content of by-products and, when used in fibers, films, resin compositions for molding and the like, has little gel and gas and is excellent in moldability.

The polyarylene sulfide obtained in the present invention may be used alone, or, if desired, an inorganic filler such as glass fiber, carbon fiber, titanium oxide and calcium carbonate, an antioxidant, and Stabilizers, UV absorbers,
It is also possible to add a coloring agent and the like, polyamide, polysulfone, polyphenylene, polycarbonate, polyethersulfone, polyethylene terephthalate, polybutylene terephthalate, polyethylene, polypropylene,
Polytetrafluoroethylene, olefin copolymer having functional groups such as epoxy group, carboxyl group, carboxylic ester group, acid anhydride group, polyolefin elastomer, polyether ester elastomer, polyether amide elastomer, polyamide imide, polyacetal, polyimide Resins such as these can also be blended.

The polyarylene sulfide resin obtained according to the present invention is excellent in heat resistance, chemical resistance, flame retardancy, electrical properties and mechanical properties, and is particularly excellent in that the content of impurities is small. Not only for injection molding,
By extrusion, it can be widely used as extruded products of fibers, sheets, films and pipes.

Further, the use thereof is, for example, a sensor,
LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable condenser cases, optical pickups, oscillators, various terminal boards, transformers, plugs, printed circuit boards, tuners, speakers, microphones, headphones, small motors , Magnetic head base, power module, semiconductor, liquid crystal, F
Electric and electronic parts such as DD carriages, FDD chassis, motor brush holders, parabolic antennas, and computer-related parts; VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio equipment Laser disc ・
Home and office electrical product parts represented by audio equipment parts such as compact discs, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, etc .; office computer related parts, telephone related parts, facsimile related parts, copying Machine-related parts such as machine-related parts, cleaning jigs, motor parts, lighters, typewriters, etc .: Optical equipment such as microscopes, binoculars, cameras, clocks, etc., precision machine-related parts; Water taps, pump parts, pipe joints, water flow control valves, relief valves, hot water temperature sensors, water flow sensors, water supply parts such as water meter housings; valve alternator terminals, alternator connectors, IC regulators, potentiometer bases for light drier , Exhaust gas valve Various valves, 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,
Brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, distributor, starter switch, starter relay, transmission wire harness, window washer nozzle, air conditioner panel switch board, fuel related electromagnetic valve coil, fuse Automotive / vehicle-related components such as connectors, horn terminals, electrical component insulation boards, step motor rotors, lamp sockets, lamp reflectors, lamp housings, brake pistons, solenoid bobbins, engine oil filters, ignition device cases, vehicle speed sensors, cable liners, etc. And various other uses.

[0059]

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.

<Yield of granular polyarylene sulfide>
The yield of the particulate polyphenylene sulfide was defined as a ratio of the yield of the particulate polyarylene sulfide to the weight (theoretical amount) assuming that all the sulfidizing agent containing one equivalent of sulfur after the dehydration step was converted to polyarylene sulfide.

<Amount of Gas Generated when Heating Granular Polyarylene Sulfide> The obtained granular polyarylene sulfide is heated at 320 ° C. for 2 hours under vacuum conditions to collect the generated gas component, and the weight fraction of the gas component is determined. Was.

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 N-methyl-2
-163 g (1.65 mol) of pyrrolidone, 27.0 g (0.33 mol) of sodium acetate, 150 g of ion-exchanged water
, And gradually heated to 205 ° C. over about 3 hours while passing nitrogen through at normal pressure. After distilling out 205 g of water and 4 g of NMP, the reaction vessel was cooled to 160 ° C. and 147 g of p-dichlorobenzene (1.00 g) was added. Mol), N-methyl-
131 g (1.31 mol) of 2-pyrrolidone was added (therefore, the molar ratio (M) of N-methyl-2-pyrrolidone at the end of step 1 to p-dichlorobenzene before polymerization was 2.93).

Next, the reaction vessel was sealed under nitrogen gas,
The temperature was raised to 0 ° C. and maintained for 70 minutes. Thereafter, cooling was performed at an average cooling rate of 1 ° C./min (S1). Since T1 is 218 ° C. according to (Equation 1), it is cooled to 198 ° C. while keeping the average cooling rate at 1 ° C./min, and then cooled at a cooling rate of 2 ° C./min.
Cooled to 0 ° C.

Thereafter, the contents were taken out, diluted with 0.5 liter of N-methyl-2-pyrrolidone, and the solvent and solids were separated by filtration through a sieve (80 mesh).
It was washed several times with 1 liter of warm water and filtered to obtain polymer particles. This was dried at 120 ° C. under reduced pressure.

The yield of the obtained granular polyphenylene sulfide was 89%, and the gas component was 0.25% by weight.

Comparative 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 N-methyl-2
-163 g (1.65 mol) of pyrrolidone, 27.0 g (0.33 mol) of sodium acetate, 150 g of ion-exchanged water
, And gradually heated to 205 ° C. over about 3 hours while passing nitrogen through at normal pressure. After distilling out 205 g of water and 4 g of NMP, the reaction vessel was cooled to 160 ° C. and 147 g of p-dichlorobenzene (1.00 g) was added. Mol), N-methyl-
131 g (1.31 mol) of 2-pyrrolidone was added (therefore, the molar ratio (M) of N-methyl-2-pyrrolidone at the end of step 1 to p-dichlorobenzene before polymerization was 2.93).

Next, the reaction vessel was sealed under nitrogen gas,
The temperature was raised to 0 ° C. and maintained for 70 minutes. Then, after cooling to 200 ° C. at an average cooling rate of 4 ° C./min (S1), it was cooled to 50 ° C. at a cooling rate of 4.5 ° C./min.

Thereafter, the contents were taken out, diluted with 0.5 liter of N-methyl-2-pyrrolidone, and the solvent and solids were separated by filtration through a sieve (80 mesh).
It was washed several times with 1 liter of warm water and filtered to obtain polymer particles. This was dried at 120 ° C. under reduced pressure.

The yield of the obtained granular polyphenylene sulfide was 72%, and the gas component was 0.44% by weight.

Example 2 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 N-methyl-2
-163 g (1.65 mol) of pyrrolidone, 27.0 g (0.33 mol) of sodium acetate, 150 g of ion-exchanged water
, And gradually heated to 205 ° C. over about 3 hours while passing nitrogen through at normal pressure. After distilling out 205 g of water and 4 g of NMP, the reaction vessel was cooled to 160 ° C. and 147 g of p-dichlorobenzene (1.00 g) was added. Mol), N-methyl-
131 g (1.31 mol) of 2-pyrrolidone was added (therefore, the molar ratio (M) of N-methyl-2-pyrrolidone at the end of step 1 to p-dichlorobenzene before polymerization was 2.96).

Next, the reaction vessel was sealed under nitrogen gas,
The temperature was raised to 0 ° C. and maintained for 140 minutes. Thereafter, cooling was performed at an average cooling rate of 1.2 ° C./min (S1). Since T1 is 212 ° C. according to (Equation 1), the average cooling rate is 1.2 ° C. /
After cooling to 190 ° C, the cooling rate is 2 ° C
/ Min to 50 ° C.

Thereafter, the contents were taken out, diluted with 0.5 liter of N-methyl-2-pyrrolidone, and the solvent and solids were separated by filtration through a sieve (80 mesh).
It was washed several times with 1 liter of warm water and filtered to obtain polymer particles. This was dried at 120 ° C. under reduced pressure.

The yield of the obtained granular polyphenylene sulfide was 87%, and the gas component was 0.24% by weight.

Example 3 In a 1-liter autoclave equipped with a stirrer, 106 g (0.90 mol) of 47% sodium hydrosulfide, 38.7 g (0.93 mol) of 96% sodium hydroxide, N-methyl-2
-147 g (1.49 mol) of pyrrolidone, 24.4 g (0.30 mol) of sodium acetate, 135 g of ion-exchanged water
, And gradually heated to 205 ° C. over about 3 hours while passing nitrogen through at normal pressure to distill 181 g of water and 3 g of NMP. Then, the reaction vessel was cooled to 160 ° C., and 133 g of p-dichlorobenzene (0.90 Mol), N-methyl-
236 g (2.38 mol) of 2-pyrrolidone were added (therefore, the molar ratio (M) of N-methyl-2-pyrrolidone at the end of step 1 to p-dichlorobenzene before polymerization was 4.25).

Next, the reaction vessel was sealed under nitrogen gas,
After the temperature was raised to 0 ° C. and maintained for 70 minutes, 18 g of water (1
Mol). Thereafter, an average cooling rate of 1 ° C./min (S
Cooling was performed in 1). Since T1 is 210 ° C. according to (Equation 1), it was cooled to 185 ° C. with the average cooling rate kept at 1 ° C./min, and then cooled to 50 ° C. at a cooling rate of 2 ° C./min.

Thereafter, the contents were taken out, diluted with 0.5 liter of N-methyl-2-pyrrolidone, and the solvent and solids were separated by filtration through a sieve (80 mesh).
It was washed several times with 1 liter of warm water and filtered to obtain polymer particles. This was dried at 120 ° C. under reduced pressure.

The yield of the obtained granular polyphenylene sulfide was 88%, and the gas component was 0.20% by weight.

The molar ratio (M) of p-dichlorobenzene before the polymerization and N-methyl-2-pyrrolidone at the end of the step 1, the cooling rate S1 in the step 2, and the lower limit temperature T1 for maintaining the cooling rate S1 were determined according to the present invention. In the polyarylene sulfide resins obtained in Examples 1 to 3 having the values according to (Equation 1), the values of M, S1 and T1 are extremely high as compared with Comparative Example 1 in which the values do not comply with (Equation 1). It can be seen that the product has high yield and high purity.

[0079]

According to the production method of the present invention, granular polyarylene sulfide having high purity can be obtained in high yield.

Claims (3)

[Claims] 1. A reaction between a polyhalogenated aromatic compound and a sulfidizing agent in an organic polar solvent at least as follows:
Two steps, Step 1: a step of reacting the polyhalogenated aromatic compound with the sulfidizing agent in a temperature range of 245 ° C. to 290 ° C. Step 2: a step of cooling the reactant reacted in Step 1 The method for producing polyarylene sulfide, wherein the cooling rate is controlled within a range of 0.2 ° C./min to 1.3 ° C./min in at least a part of the temperature range in Step 2. Method of manufacturing resin. 2. The reaction of a polyhalogenated aromatic compound and a sulfidizing agent in an organic polar solvent in at least two consecutive steps as follows: Step 1: a polyhalogenated aromatic compound in a temperature range of 245 ° C. to 290 ° C. Step 2: a step of cooling the reactant reacted in Step 1 in the process for producing a polyarylene sulfide, wherein the polyhalogenation introduced into the polymerization system in Step 1 is performed. The molar ratio between the aromatic compound and the organic polar solvent present in the reaction system at the end of Step 1 is M, and in Step 2, 2
In the temperature range of 45 ° C. or less, first, the cooling rate S1 (0.2
≦ S1 (° C./min)≦1.3), cooling at least to a temperature T1 (° C.) defined by the following (Equation 1), and then at a cooling rate S2 (1.3 <S2 (° C./min)) A method for producing a granular polyarylene sulfide resin, characterized by multi-stage cooling for cooling. T1 = −0.33 × (100 × S1 + 20 × M−760) +20 (Equation 1) (where 150 ≦ T1 ≦ 245 0.2 ≦ S1 ≦ 1.3 0.5 ≦ M ≦ 10 M is polymerization The molar ratio of the polyhalogenated aromatic compound (Mh) introduced into the system to the organic polar solvent (Ms) present in the reaction system at the end of Step 1 (M = Ms / M
h). ) 3. The method according to claim 1, wherein the step 1 comprises an organic carboxylate, water, an alkali metal chloride, an organic sulfonate, an alkali metal sulfate,
The granular poly according to claim 1 or 2, wherein the polymerization is performed in the presence of at least one polymerization aid selected from an alkaline earth metal oxide, an alkali metal phosphate, and an alkaline earth metal phosphate. A method for producing an arylene sulfide resin.