JPH026773B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing polyarylene sulfide, and more specifically, the present invention relates to a method for producing polyarylene sulfide, which is characterized by reacting a halogenated aromatic compound and an alkali metal sulfide in the presence of an alkali metal iodide. The present invention relates to a method for manufacturing fluid. In a method for producing polyarylene sulfides, a method in which a corresponding halogen-containing aromatic compound and an alkali metal sulfide or an alkaline earth metal sulfide are reacted in a polar solvent is already known (U.S. Pat. No. 3,354,129 and Special Publication No. 45-3368),
In addition, various catalysts have been disclosed for a solvent-free method or a method using a catalyst if necessary. That is,
Combinations of alkali metal carboxylates and alkali metal carbonates (U.S. Pat. No. 4,038,259), alkali metal sulfates (U.S. Pat. No. 4,038,260), lithium carboxylates, or lithium chloride (U.S. Pat.
4038261), lithium halide (U.S. Patent No.
4038263), lithium carbonate (US Pat. No. 4039518)
), lithium acetate (U.S. Patent No. 4046114), trialkali phosphate salt (Japanese Patent Publication No. 56-20030), dialkali phosphionate salt (Japanese Patent Publication No. 56-20031), etc.
It is listed as a catalyst for the production of high molecular weight polyarylene sulfide. It is also known that in the process for producing polyarylene sulfides, amides are used as solvents and inorganic bases are used to activate the sulfur donor. As a result of various studies and studies on new catalysts to replace the above-mentioned various catalysts, the present inventor discovered that in the production of polyarylene sulfide, a halogenated aromatic compound and an alkali metal sulfide are reacted in a polar solvent. By reacting in the presence of an alkali metal iodide as a catalyst during the reaction, a polyarylene sulfide having a higher melt viscosity than a polyarylene sulfide obtained by a similar reaction without using an alkali metal iodide at all. It was discovered that the id can be obtained. That is, the present invention provides (a) General formula [] Para-dihalobenzene represented by The total number of carbon atoms in at least 50 mol% of the paradihalobenzene used is
6 with the condition that each R must be hydrogen.
~24 pieces. ), and (b) 0 to 3.0 mol % based on the paradihalobenzene content of the general formula [ ] Ar group or heterocyclic group, X is the same as above, and n≧3
It is. ) A method for producing a polyarylene sulfide by reacting a polyhaloaromatic compound represented by (c) with an alkali metal sulfide in a (d) polar solvent, comprising: (e) 1 mol of an alkali metal sulfide. Per, 0.01~
In the presence of 2.0 moles of alkali metal iodide (a)
The molar ratio of (c) to (c) is 0.85:1 to 1.15:1, and the molar ratio of (c) to (d) is 1:2 to 1:15,
The present invention provides a method for producing polyarylene sulfide, which is characterized by carrying out a polymerization reaction at a temperature of 160 to 295°C for a maximum of 60 hours. Therefore, a preferred embodiment of such a polymerization reaction is a reaction time of 0.2 to 8 hours and a reaction temperature of 190 to 275 hours.
℃, and the alkali metal iodide is sodium iodide, potassium iodide, or a mixture thereof. The paradihalobenzenes of the general formula [] that can be used according to the present invention include, for example, P-dichlorobenzene, P-dibromobenzene, P-diiodobenzene, 1-chloro-4-bromobenzene, 1-chlorobenzene, -4-iodobenzene, 1-bromo-4-iodobenzene, 2,5-dichlorotoluene, 2,5-dichloro-paraxylene, 1-ethyl-2,5-dichlorobenzene, 1-ethyl-
2,5-dibromobenzene, 1-ethyl-2-bromo-5-chlorobenzene, 1,2,4,5-tetramethyl-3,6-dichlorobenzene, 1-cyclohexyl-2,5-dichlorobenzene, 1-
Phenyl-2,5-dichlorobenzene, 1-benzyl-2,5-dichlorobenzene, 1-phenyl-2,5-dibromobenzene, 1-benzyl-
2,5-dibromobenzene, 1-phenyl-2-
Bromo-5-chlorobenzene, 1-P-tolyl-
2,5-dichlorobenzene, 1-P-tolyl-
2,5-dibromobenzene, 1-hexyl-2,
Mention may be made of 5-dichlorobenzene and the like or mixtures. Next, examples of the polyhaloaromatic compound of the general formula [] include 1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene, 1,3,
5-trichlorobenzene, 1,2,4-tribromobenzene, 1,2,4-triiodobenzene,
1,3,5-trichloro-2,4,6-trimethylbenzene, 1,2,3-trichloronaphthalene, 1,2,4-trichloronaphthalene, 1,
2,6-trichloronaphthalene, 2,3,4-trichlorotoluene, 2,4,6-trichlorotoluene, 1,2,3,4-tetrachloronaphthalene, 1,2,4,5-tetrachlorobenzene,
2,2',4,4'-tetrachlorobiphenyl is mentioned. Therefore, the polyhaloaromatic compound of the general formula [] has a content of 0 to 0 with respect to the content of paradihalobenzene.
Add an amount of 3.0 mol%, preferably 0.1 to 3.0 mol%. The alkali metal sulfide is preferably sodium sulfide or potassium sulfide, and is usually used as a hydrate or a mixture with water. Alternatively, the alkali metal sulfide can be obtained from hydrogen sulfide or a stoichiometric amount of alkali metal hydroxide corresponding to the alkali metal bisulfide by neutralization in or outside the reaction solution. It is desirable to additionally use alkali metal hydroxide in order to neutralize alkali metal bisulfides, which are often present as impurities even when pure alkali metal sulfides are used. The amount of such alkali metal hydroxide can be selected depending on the amount of alkali metal bisulfide contained in the alkali metal sulfide used, and is generally based on 1 mole of alkali metal sulfide.
The maximum amount is 0.8 mol, but a larger amount can be selected if necessary. Alkali metal hydroxides that can be used are, for example, lithium hydroxide, sodium hydroxide and potassium hydroxide or mixtures thereof. Compounds which, when combined with water, regenerate the alkali metal hydroxide in the hydrolysis step may also be used for the same purpose. The molar ratio of dihalobenzene to alkali metal sulfide is 0.85:1 to 1.155:1, but it is better to be as close to 1:1 as possible, preferably 0.95:1 to 1.155:1.
The ratio is 1.05:1. Generally, the polar solvent may be any polar solvent as long as it sufficiently dissolves the organic and inorganic reactants under the reaction conditions, but lactams and amides are preferred, and N-alkyl lactams can be particularly preferably used. Examples of usable solvents include dimethylformamide, dimethylacetamide, caprolactam, N-methylcaprolactam, N-ethylcaprolactam, N-isopropylcaprolactam, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N- Isopropyl-2-pyrrolidone, N-methyl-3-methyl-2-pyrrolidone, N-methyl-5-methyl-2-pyrrolidone,
N-methyl-3,4,5-trimethyl-2-pyrrolidone, N-methyl-2-piperidone, N-ethyl-2-piperidone, N-methyl-6-methyl-
2-piperidone, N-methyl-3-ethyl-2-
Examples include piperidone, N-methyl-2-oxohexamethyleneimine, and N-ethyl-2-oxohexamethylene. One or more of these solvents may be selected and used as a mixed solvent. The method of the present invention is characterized in that the polymerization reaction is carried out in the presence of 0.01 to 2.0 mol, preferably 0.05 to 1.0 mol, of alkali metal iodide per mol of alkali metal sulfide. Sodium iodide or potassium iodide is preferred, and either one type or several different types may be used.
It can be used as an anhydride, a hydrate, or a mixture with water. It is also possible to neutralize the corresponding alkali metal hydroxide directly, if necessary as an aqueous mixture, in the reaction solution with the desired stoichiometric amount of hydroiodic acid. In the method according to the present invention, the general formula []
The paradihalobenzene, the polyhaloaromatic compound of the general formula [], the alkali metal sulfide, the alkali metal iodide, or the alkali metal hydroxide used as necessary may be mixed in any form in the polar solvent used. However, it is possible to cause a reaction. However, when alkali metal sulfides and alkali metal iodides are used in the form of hydrates or aqueous mixtures, it is preferable to remove most of the water present before addition of paradihalobenzene, e.g. This can be done by distilling off water from the solution. In such a reaction, the reaction procedure is as follows. That is, a polar solvent such as an N-alkyl lactam, an alkali metal sulfide and an alkali metal iodide, and optionally an alkali metal hydroxide are introduced into the reactor, and the water of hydration or water of the mixture is added to the reactor. Remove dehydration. If the alkali metal iodide is used in the form of a hydrate or an aqueous mixture, it is also possible to divide the dehydration into two stages. Thereafter, paradihalobenzene and, if necessary, the polyhaloaromatic compound of the general formula [] are added to initiate polymerization. When an anhydrous alkali metal iodide is used, it can be added together with paradihalobenzene after dehydration. The polyarylene sulfide produced by the polymerization reaction can be processed using a conventional procedure, such as passing through the reaction product to collect the polymer, followed by washing with water, or
Alternatively, it can be obtained by diluting the reaction product with water, then taking the polymer and washing it with water. Alternatively, the solvent may be distilled off from the reactor and the residue subsequently washed with water as described above. The melt viscosity of the polyarylene sulfide obtained by the present invention varies depending on the amount of alkali metal iodide used, but as a result of measurement using the melt viscosity measurement method described below, It exhibits a melt viscosity of 90 to 300 poise, which is higher than the melt viscosity of polyarylene sulfide, which is 38 poise, obtained by a method that does not use an alkali metal iodide. Therefore, a separate reinforcing step required for polyarylene sulfide obtained by other methods can be omitted, and direct molding such as ordinary extrusion molding, injection molding, extrusion blow molding, etc. is possible. For example, it can be used in mechanical parts, automobile parts, electronic parts, office equipment supplies, household goods, etc. Furthermore, it can be mixed with other polymers, fillers such as graphite, metal powders, inorganic powders, fibrous materials, glass fibers, or conventional stabilizers and pigments to form molded products. To measure the melt viscosity as an evaluation method for polyarylene sulfide, use a Koka type flow tester to measure the fluidity Q under the conditions of 290℃, 20Kg/cm ² , nozzle 0.5mmφ x 5mm, and use the following formula. Calculated by applying η=π・r ⁴ /8・L×P/Q η: Melt viscosity (poise) r: Nozzle radius (cm) L: Nozzle length (cm) P: Load (Kg/cm ² ) Q: Flow Degree (cm ³ /mm) Next, the present invention will be specifically explained using Examples, but the present invention is not limited to these Examples. Example 1 Sodium sulfide (Na ₂ S・XH ₂ O) 15.54 g
(0.12 mol/approx. 60% purity), sodium hydroxide 0.39
g (0.0098 mol), and anhydrous sodium iodide
17.99 g (0.12 mol) were added into 50 g of N-methyl-2-pyrrolidone. This mixture was heated slowly while flushing with nitrogen, and was dehydrated by increasing the temperature to 190° C. over 1.5 hours, and 6.5 ml of a distillate consisting mainly of water was distilled off. The reaction mixture was then cooled to 160 DEG C. and a solution containing 17.64 g (0.12 mol) of paradichlorobenzene in 20 g of N-methyl-2-pyrrolidone was added.
The reaction mixture was heated for about 30 minutes in a nitrogen atmosphere with an initial pressure of 5 kg/ ^cm2 .
The mixture was heated to 250°C for 5 minutes and reacted at that temperature for 5 hours. After the reaction was completed, the reaction mixture was cooled to room temperature and then added to a large amount of water to separate the product.
By washing with water several times, finally washing with acetone, and drying, 11.81g of polyphenylene sulfide was obtained.
(yield 91%). The melt viscosity η of the obtained polyphenylene sulfide was 205 poise. Examples 2 to 4 The reaction was carried out in the same manner as in Example 1, except that the amount of anhydrous sodium iodide used in Example 1 was changed. The results are shown in Table 1. Comparative Example A reaction was carried out in the same manner as in Example 1 except that anhydrous sodium iodide was not used. The result is the first
Shown in the table.

[Table] Example 5 Example 1 except that anhydrous iodide was used together with paradichlorobenzene after dehydration in Example 1.
The reaction was carried out in the same manner. As a result, 11.87 g (yield 91%) of polyphenylene sulfide was obtained.
Its melt viscosity η was 149 poise. Example 6 The reaction was carried out in the same manner as in Example 3 except that potassium iodide was used instead of sodium iodide. As a result, polyphenylene sulfide 12.41
g (yield 96%), and the melt viscosity η was 91 poise. Example 7 In Example 3, 0.218 g of 1,2,4-trichlorobenzene (0.0012 mol: 1 mol % based on the number of moles of paradichlorobenzene) was used as a branching component together with paradichlorobenzene, and the amount of paradichlorobenzene was increased accordingly. 17.64g to 17.38g
The reaction was carried out in the same manner as in Example 3 except that the amount was reduced to (0.1182 mol). As a result, 12.28 g (yield 95%) of polyphenylene sulfide was obtained, and its melt viscosity η was 1087 poise.

Claims (1)

[Claims] 1 (a) Paradihalobenzene represented by the general formula [ ], and (However, each X is chlorine, bromine, or iodine,
Each R is hydrogen, an alkyl group, a cycloalkyl group,
or aryl groups, which may be combined, and the total number of carbon atoms in each molecule is from 6 to 24, provided that each R must be hydrogen in at least 50 mol% of the paradihalobenzene used. It is. ) (b) 0 to 3.0 mol % of the polyhalo aromatic compound represented by the general formula [ ] based on the paradihalobenzene content, Ar is an aromatic or heterocyclic group having carbon atoms, X is the same as above, and n
≧3. ) (c) together with an alkali metal sulfide; (d) in a method for producing polyarylene sulfide, which is reacted in a polar solvent, (e) from 0.01 to 1 mole of alkali metal sulfide;
In the presence of 2.0 moles of alkali metal iodide (a)
and (c) in a molar ratio of 0.85:1 to 1.15:1, and
(c) to (d) molar ratio of 1:2 to 1:15, 160
A method for producing polyarylene sulfide, which comprises carrying out a polymerization reaction at a temperature of ℃ to 295℃ for a maximum of 60 hours. 2. The method according to claim 1, wherein the condensation polymerization reaction time is 0.2 to 8 hours. 3. The method according to claim 1, wherein the polycondensation reaction temperature is 190 to 275°C. 4 Reaction is 0.05 per mole of alkali metal sulfide
2. The method of claim 1 carried out in the presence of ~1.0 moles of alkali metal iodide. 5. The method according to claim 1, wherein the reaction is carried out in the presence of sodium iodide, potassium iodide or a mixture thereof. 6. Claim 1 in which the alkali metal sulfides and alkali metal iodides are used in the form of their hydrates or in aqueous mixtures, and one or more stages of dehydration are carried out before the addition of paradihalobenzene.
The method described in section. 7. The method according to claim 1, wherein the polar solvent is N-methyl-2-pyrrolidone. 8. The method according to claim 1, wherein X in the general formula [] is chlorine, bromine or iodine.