JPS62185716A - Production of polyarylene sulfide - Google Patents

Abstract

PURPOSE:To produce a high-MW polyarylene sulfide excellent in heat resistance, by bringing a dihaloaromatic compound, an alkali metal sulfide and a halogenated triazine into contact with each other at a low temperature and reacting them at a high temperature. CONSTITUTION:A dihaloaromatic compound (A) (e.g., p-dichlorobenzene), an alkali metal sulfide (B) (e.g., Na2S), a halotriazine (C) (e.g., cyanuric chloride), a polar solvent (D) (e.g., N-methylpyrrolidone) and, optionally, an alkali metal halide (E) (e.g., LiBr) are mixed together so that the molar ratio A/B may be 0.75-2.0, the molar ratio D/B may be 1-15, the molar ratio E/B may be 2.0 - or below and component C may be present in an amount of 0.005-2.0mol%, based on component B, and brought into contact with each other for 0.2-4hr at 120-155 deg.C and a pressure of from an autogenous pressure to 50kg/cm<2> (abs.) to react component C with component B, and the reaction mixture is further reacted at 180-330 deg.C within 20hr.

Description

[Detailed Description of the Invention] [Field of Industrial Interest 71J] The present invention relates to a method for producing polyarylene sulfide. The present invention relates to a method for producing polyarylene sulfide by which arylene sulfide can be easily obtained.

[Prior art and its problems] Polyarylene sulfide such as polyphenylene sulfide is a thermoplastic resin that has heat-curing properties, and has excellent chemical resistance, good mechanical properties in a wide temperature range,
It has excellent properties as an engineering plastic, such as heat resistance and rigidity.

It is known that the polyarylene sulfide of the polyphenylene sulfide rod is usually obtained by polymerizing a dihalogen aromatic compound and an alkali metal sulfide in a polar solvent.

It is usually carried out by polymerizing p-dichlorobenzene and sodium sulfide in a polar solvent (see IVJ52-12240, etc.).

However, since the molecule 6 of ordinary polyarylene sulfide 2 is small, in order to obtain a high molecular weight final product, it is necessary to harden the low molecular weight polyarylene sulfide by heat treatment, which is a complicated operation.

Conventionally, as a method for producing polymer-attached branched polyarylene sulfide, a method in which a polyhalogen aromatic compound is present in the reaction system (Japanese Patent Application Laid-open No. 197430/1989), etc. is known. Addition of a halogen aromatic compound has the disadvantage that the heat resistance of the resulting polymer decreases. That is, according to this method, the produced polymer tends to gel, has a large melt flow value, and has a low melting point. There were some problems with the quality of the product. Additionally, it is conceptually described that polymerization can be carried out at 180 to 300°C with the presence of a polyhalogen heterocyclic compound in the reaction system, but at this temperature a decomposition reaction occurs and the quality of the resulting polymer becomes unstable. There was a problem.

[Object of the Invention] This invention has been made in accordance with the above-mentioned 1.

That is, the purpose of the present invention is to solve the above problems, and 1)
It has excellent heat resistance and moldability into films, fibers, etc., and can easily produce polyarylene sulfide of stable quality and high molecular weight. The objective is to provide a new manufacturing method.

+ Qj [In order to achieve the first objective, this inventor conducted intensive research and found that in the presence of a halogenated triazine,
The inventors have arrived at this invention by discovering that item 1 above can be easily achieved by a 2t) reaction method in which the main components of the reaction system are brought into contact at a low temperature and then a polymerization reaction is carried out at a high temperature.

[Efforts to achieve the above objective] i! of this invention to achieve the above objectives. iThe point is.

Dihalogen aromatic compounds, alkali metal sulfides and halogenated triazines were heated at 120-155°C in a polar solvent.
This is a method for producing polyarylene sulfide, which is characterized by contacting at a temperature of 180 to 330°C and reacting by heating.

Examples of surface polar melts 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-methylcaprolactam, N-ethylcaprolactam, N-isopropylcaprolactam, N-inbutylcaprolactam, N-propylcaprolactam, N-butylcaprolactam, N
-Cyclohexylcaprolactam, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-isobutyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-butyl-2-
Pyrrolidone, N-cyclohexyl-2-pyrrolidone, N
-, methyl-3-methyl-2-pyrrolidone, N-sochlorohexyl-2-pyrrolidone, N-methyl-3-methyl-
2-pyrrolidone, N-methyl-3,4,5-trimethyl-2-pyrrolidone, N-methyl-2-piperidone, N-
Ethyl-2-piperidone, N-inpropyl-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-dimethylethyleneurine J, 1,3-dimethylpropyleneurea, l-methyl-1-oxosulfolane, 1-ethyl-1-oxosulfolane, l-7enyl-1-oxosulfolane, l-methyl-1-oxophos fan, l
-propyl-1-oxophos 777.1-7enyl
-Oxophosphan and the like. These solvents are
One type may be used alone, or two or more types may be used in combination.

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-dichlorobenzene, p-dichlorobenzene, p-
Dibromobenzene, m-dibromobenzene, p-shortbenzene, 1-10-4-bromobenzene, 1-chloro-4-iodobenzene natonodihalogen-substituted benzene; 2,5-dichlorotoluene, 2,5-dichloroxylene, 1-ethyl-2,5-dichlorobenzene, l-
Ethyl-2,5-dibromobenzene, 1-ethyl-2-
Bromo-5-chlorobenzene, 1,2,4.5-tetramethyl-3,6-dichlorobenzene, I-cyclohexyl-2,5-dichlorobenzene, l-phenyl-2,5
-dichlorobenzene, l-benzyl-2,5-dichlorobenzene, l-phenyl-2,5-dibromobenzene,
1-p-)Sail-2,5-dichlorobenzene, 1-p
-Dihalogen-substituted benzenes such as toluyl-2,5-dibromobenzene and 1-hexyl-2,5-dichlorobenzene, dihalogen-substituted biphenyls such as 4,4°-dichloropiphenyl, 1,4-dichloronaphthalene, l ,
dihalogeno-substituted naphthalenes such as e-dichloronaphthalene, 2.8-'; chloronaphthalene, and the like. Among these, preferred are dihalogen-substituted benzenes, and p-dichlorobenzene is particularly preferred.

Examples of the alkali metal sulfides include lithium oxide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide, and mixtures thereof. In the method of the present invention, it is also possible to use them as hydrates or aqueous mixtures. Preferred examples of the alkali metal sulfide include lithium Viride and sodium sulfide, with sodium sulfide being particularly preferred.

As the halogenated triazine, two or three 15J of the four IRJ atoms forming the triazine ring:
A halogen atom is bonded to the original F. Examples include dihalogen triazines and trihalogen triazines. Among these, trihalogen triazines are preferred.

Examples of the triazine ring include 1,2.4-) riazine ring, 1,3.5-)su7dine cJ, and the like. Among these, a 1,3.5-) riazine ring is preferred.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a chlorine atom and a bromine atom are preferred, and a chlorine atom is particularly preferred.

+fi The halogen atoms contained in the halogenated triazine may be of the same type or different types.

The group bonded to the remaining carbon atom that is not bonded to a halogen atom among the carbon atoms forming the triazine ring in the dihalogen triazines is a hydrogen atom,
Hydrocarbon groups such as alkyl groups, aryl groups, arylalkyl groups, and aryl groups, wood acid groups, alkoxy groups,
Examples include amide 7 group. Among these, a hydrogen atom, a methyl group, a methoxy group, and a hydroxyl group are preferred.

Examples of the halogenated triazine include 2,
4.8-trichloro-1,3,5-triazine (cyanuric chloride), 2,4.8-tribromo-1,3,5
-triazine (cyanuric bromide), 2,4.8-) ryodo 1.3.5-triazine, 2,4.8- triple oro 1.3.5-) riazine, 2,4-dichloro-6-bromo -1,3,5-) riazine, 2-chloro, 4,8-dibromo-1,3,5-triazine, 2.4
-dichloro-1,3,5-)su7dine, 2,4-dichloro-6-methyl-1,3,5-)riazine, 2-methoxy-4,6-dichloro-1,3,5-triazine , 2-
Examples include hydroxy-4,8-dichloro-1,3,5-triazine, 3,5.8-)dichloro-1,2,4-)riazine, and the like. Among these exemplified halogenated triazines, cyanuric chloride and cyanuric bromide are preferred, and cyanuric chloride is particularly preferred.

In addition, the halogenated triazines described in +Wi may be used alone or in combination of two or more.

In the method of this invention, the dihalogen aromatic compound (A
), the alkali metal sulfide (B) and the halogenated triazine (C) are brought into contact with each other in the polar solvent (D) at a temperature in a specific range for an appropriate time (this step is carried out in step t).
(referred to as the B stage), and then heated to a specific range of temperature to cause a reaction (hereinafter this stage is referred to as the second stage).
Polyarylene sulfide can be produced.

In the method of the present invention, the blending ratio of each component is preferably as follows.

That is, the molar ratio of (A) component/(B) JA component is 0.7
5 to 2.0, preferably 0.90 to 1.2. This dihalogen aromatic compound (A) and alkali metal sulfide (
Since the reaction with B) is a T molar reaction, it is usually within the above range.

The above ((:) J & minute is 0.0 for the above (B) component.
005 to 2.0 mol%, preferably 0.01 to 1
．． It is 5 mol%. Said (C) lji, minute is 0.00
If it is less than 5 mol%, it may be difficult to produce the polyarylene sulfide of polymer-h), and if it is more than 2.0 mol%, gelation may occur in some cases. .

The molar ratio of component (El)/component (B) is 1-15, preferably 2-1O. If this molar ratio is smaller than 1, the reaction may become non-uniform, and if the molar ratio is larger than 15, productivity may be reduced.

In addition, when producing this polyarylenonulfite,
Alkali metal halide (E) as a catalyst in the reaction system
It is preferable that the two coexist.

Examples of alkali metal halogen compounds include lithium fluoride, lithium chloride, and lithium bromide.

Examples include lithium iodide, sodium fluoride, potassium fluoride, rubidium fluoride, cesium fluoride, and mixtures thereof. In the method of the present invention, the various alkali metal halogen compounds exemplified above can be used as an anhydride, a hydrate, an aqueous mixture, or the like. Among these alkali metal halogen compounds, tl! Lithium chloride is preferred, and lithium chloride is particularly preferred.

The molar ratio of component (E)/component (B) is 1, usually 2.0 or less, preferably 0.01-1.5. If this molar ratio is small, the Eastai reaction rate may be low, the molecular weight of polyarylene sulfide may not be sufficiently high, or the combination of salts such as common salt remaining in the polymer may not be sufficiently low. There is. On the other hand, when it is larger than 2.0, the salt used as a catalyst in the produced polymer has a high e
It may remain in lf.

In addition, when producing this polyarylene sulfide,
It may be preferable to coexist an alkali hydroxide (F), a metal carboxylic acid salt known as a catalyst (G), an aromatic sulfone Iv salt, and a reducing agent in the reaction system.

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

Examples of the carboxylic acid metal salt include lithium acetate, lithium propionate, lithium 2-methylpropionate, lithium acetate, 3-methyl lithium acetate, lithium quartzate, lithium hexanoate, lithium heptanoate, lithium benzoate, Among these, lithium carboxylate is preferable, and lithium acetate is particularly preferable. good.

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

As the reducing agent, for example, hydrazine.

Examples include hydrides, alkali formates, etc., and preferred ones include:
Hydrides, especially borohydrides (NaBH4), potassium borohydride J, and calcium hydride (C21H7).

The molar ratio of component (G)/(B) ff1 is 2.0 or less, preferably 0.01 to 1.5. If this molar ratio is greater than 2.0, the resulting polymer may not have a small melting length.

Since the alkali hydroxide is used to make the reaction system alkaline, there is no particular restriction on its addition 7I).

In the method of the present invention, in addition to the above-mentioned various components, active hydrogen-containing aromatic compounds such as dichloroaniline, dichloronitrobenzene, etc. By adding a halogen aromatic nitro compound such as "("), the molecular weight of the polyarylene sulfide can be further increased, the melt flow can be decreased, and the residual salt content can be lowered.

This -j? l! In method 1, each of the above components is
They may be contacted all at the same time or separately, and there are no particularly strong restrictions on the amount of ingredients to be used.

The temperature of the first stage in this generation IjI is 120~
The temperature is 155°C, preferably 130-145°C. If this temperature is less than 120°C, the heat resistance of the obtained polyarylene sulfide may decrease;
If the temperature is 55°C or higher, the component (C) will be easily decomposed and the branching reaction will not proceed for 1-minute d1, resulting in the formation of polymer molecules. 11
may become unstable.

+nfn Additional writing stage contact time is 1 usually, 0.2 to 4:1
ii1. Preferably, it is between 0.5 and 2 verses. This #d
If the contact time is shorter than 0.2 hours, the heat resistance of the polyarylene sulfide subjected to 1'J may not be sufficiently improved.
Quality may become unstable. On the other hand, even if the contact time is made longer than 4 hours, the corresponding effect is small and the process may become disadvantageous.

In addition, in the first step, the reaction mainly occurs between the component (C) and the component (B) J&, and a portion of the component (B)
It is estimated that a reaction between the components and component (A) occurs. One of the reasons why the first stage is set to the above operating conditions is to efficiently carry out the reaction between component (C) and component (B) prior to the polymerization reaction.

The reaction temperature in the second stage is 180-330°C, preferably 220-300°C. If the reactor temperature is lower than 180°C, the rate of the attraction reaction is insufficient, while if it is higher than 330°C, the reaction temperature is This may induce a reaction or reduce the productivity of polyarylene sulfide.

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

In addition, after the completion of the first stage, the temperature of the reaction system may be raised in the same reactor and the reaction stage may be taken over, or the reaction may be carried out by transferring to another reactor.

There is no particular restriction on the reaction method as long as the above conditions are met.

The pressure of the reaction system in the first stage, second stage, and intermediate stages is not particularly limited;
50 K g/crn' (absolute pressure), preferably the autogenous pressure of the reaction system is 10 K g/crn' (absolute pressure).

The first stage, the second stage, and intermediate stages thereof may be performed in an atmosphere f of an inert gas such as nitrogen, carbon dioxide, or water vapor.

After the second step, the polyarylene sulfide is
It can be obtained by fractionation directly from the reaction solution by standard techniques, such as by filtration or telescopic separation, or by fractionation from one reaction vessel, for example after addition of wood and/or diluted acid.

Filtration is generally followed by washing with water to remove any inorganic components that may adhere to the aggregate, such as alkali metal sulfides and alkali hydroxides. In addition to or after this washing step, washing with other washing solutions such as methanol or extraction may also be carried out.6 The solvent may be distilled off from the reaction vessel, followed by washing as described in 1. By doing so, it is also possible to recover the aggregates.

If necessary, in addition to or after the washing step, one of various desalting treatments may be performed to remove salt, etc. in the resin.
! It is also possible to further reduce the degree of e.

When the polyarylene sulfide produced by the method of 1.1 is molded into various products, other heptapolymer, pigments and fillers such as graphite, metal powder, glass powder, quartz powder or glass fiber, Alternatively, it can be mixed with additives customary for polyarylene sulfides, such as customary stabilizers or N1 release agents.

Polyarylene sulfide such as polyphenylene sulfide obtained by the method of Section 11 has high heat resistance,
It is a polymer polyarylene sulfide with stable quality, and in addition, it is manufactured as a polymer resin with low Fs1 such as salt in the polymer, excellent moisture resistance and electrical insulation, and small melt flow. Because you can
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 suitably used for mechanical parts as well as electrical and electronic parts. It is an excellent engineering plastic.

[Effects of the Invention] According to the present invention, the heat resistance is excellent, the quality is extremely stable, the melt flow is small, and the film, fiber, etc.
! lk! It is possible to easily produce polyphenylene sulfide of molecular weight which can be suitably molded into f. Also,
In the method of this invention, trichlorobenze/in the conventional υ: is used instead of in the reaction system.

Since a halogenated triazine such as cyanuric chloride is allowed to coexist and a subtraction reaction method is used, the use of the halogenated triazine li+ is replaced by the conventional method using trichlorobenzene (4). + about 7 r; minutes, and high quality polyarylene sulfide such as polyphenylene sulfide can be stably produced.

[Example] (Example 1) p-dichlorobenzene 81.5g (0.55mof
), cyanuric chloride 0.35 g (0,002 ml 0
) and anhydrous lithium sulfide 25.0 g (0,54
*O see) was put into an autoclave, and N-methyl-2
- Add 7306 ml (0.23 mall) of pyrrolid, and after flowing nitrogen for 10 minutes at room temperature, add 1
The temperature was raised to 20°C. Seal the autoclave and
After holding at ℃ for 1.5 hours, the temperature was raised to 265℃ and polymerization reaction was carried out over 2 hours.After the completion of the reaction, J! 2 under stirring 1
It was cooled to 90°C and then left until it reached room temperature.
The reaction mixture was placed in IQ water, filtered, washed with water, and washed with methanol. Melt flow value of the obtained polyphenylene sulfide (measurement conditions: 300°C, load 50K g/
Cm', nozzle length 10mm) is 0.04m, Q
The melting point measured by 0-mouth SC was 294℃/sec.
Met.

(Comparative example 1) In Example 1, after sealing the autoclave.

The same operation was performed except that the reaction was carried out at 285°C for 3 hours. The obtained polyphenylene sulfide had a melt flow value of 0.28 m/sec and a melting point of 234°C.

(Comparative Example 2) The same operation as in Example 1 was carried out using 0.45 g (0,0025 ◎ 9.) of trichlorobenzene instead of cyanuric chloride. The obtained polyphenylene sulfide had a melt flow value of 0.02 m/see and a melting point of 285°C.

(Example 2) Sodium sulfide nonahydrate 130.
4 g (0.54 layers on), lithium chloride 2
3 g (0,54 oJL) and N-methyl-2-
Add 370mJl of pyrrolidone and use 8B of water by azeotropic distillation.
ml was removed. Then p-dichlorobenzene81.
5 g (0.58 mall), cyanuric chloride 0.05
g (0,003moQ) and N-methyl-2
- Add 110 mJl of pyrrolidone, nitrogen atmosphere F, 1
After reacting at 35°C for 1 hour, the reaction was further carried out at 270°C for 2 hours.
After the completion of the polymerization reaction, which took a long time, cooling, filtration, washing with water, and washing with methanol were performed. The melt flow value of the obtained polyphenylene sulfide was 0.23 m/s
ec, melting point was 294°C.

(Comparative Example 3) The same operation as in Example 2 was performed except that one reaction was conducted at 270° C. for 3 hours. The resulting polyphenylene sulfide had a melt flow rate of 4 dt*0.52 m1/see and a melting point of 293°C.

Claims (3)

[Claims] (1) In a polar solvent, a dihalogen aromatic compound, an alkali metal sulfide, and a halogenated triazine are mixed at 120 to 1
A method for producing polyarylene sulfide, which comprises contacting at a temperature of 55°C and then heating to a temperature of 180 to 330°C to react. (2) The method for producing polyarylene sulfide according to claim 1, wherein the halogenated triazine is cyanuric chloride. (3) The method for producing polyarylene sulfide according to claim 1 or 2, wherein the dihalogen aromatic compound is p-dichlorobenzene.