JP3097249B2 - Polyarylene sulfide and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyarylene sulfide, and more particularly to a polyarylene sulfide having a short-chain branch.

[0002] Polyarylene sulfide has attracted attention as a member for electric and electronic equipment and a member for automobile equipment by utilizing its excellent heat resistance and chemical resistance.

[0003] In addition, it can be formed into various molded parts, films, sheets, fibers, etc. by injection molding, extrusion molding, etc.
Widely used in fields requiring heat resistance and chemical resistance.

[0004]

2. Description of the Related Art A typical polyarylene sulfide is
JP-B-45-3368, JP-B-52-12240
No., for example.

However, polyarylene sulfide obtained by a method of reacting a dihalo aromatic compound with an alkali metal sulfide in an organic amide solvent disclosed in Japanese Patent Publication No. 45-3368 is low in air due to its low molecular weight. And the high molecular weight polymer obtained by this oxidative curing was inferior in extrudability due to high degree of crosslinking and branching, and was difficult to apply to films and fibers. In addition, mechanical properties, particularly toughness, were poor.

On the other hand, the polyarylene sulfide obtained by the polymerization reaction disclosed in Japanese Patent Publication No. 52-12240 is slightly improved in mechanical properties as compared with the previously obtained polymer, but is still insufficient. is not. Moreover, since the obtained polymer was substantially linear, the dependence of the melt viscosity on the shear rate was low and the processability was poor.

[0007]

SUMMARY OF THE INVENTION The present invention provides a polyarylene sulfide having improved toughness, which is a disadvantage of polyarylene sulfide, without impairing workability.

[0008]

That is, according to the present invention, the component (I) is 90 to 99.95 mol%, the component (II) is 10 to 0.05 mol%, and the weight average molecular weight is 100%.
Compounds represented by the general formula (III), the compound represented by the general formula (IV) and the compound represented by the following general formula (V) in a polyarylene sulfide having an average molecular weight of from 500 to 500,000, : (I
V) = 90: 10-99.5: 0.05, ((III)
+ (IV)) / (V) = 0.90 to 1.45 molar ratio and reacting at 180 to 280 ° C. is a method for producing polyarylene sulfide.

The details will be described below.

The polyarylene sulfide of the present invention is obtained, for example, by reacting an alkali metal sulfide represented by the general formula (V) with a polyhalo aromatic compound represented by the general formulas (III) and (IV) in an organic polar solvent. It can be obtained by:

As the alkali metal sulfide used in the present invention, any one may be used as long as it satisfies the structural formula (V).
Examples thereof include sodium sulfide, potassium sulfide, cesium sulfide, rubidium sulfide and hydrates thereof. These alkali metal sulfides may be used alone or in combination.

These alkali metal sulfides may be used by adding water suitable for use if they are anhydrous, or dehydrated to a water content suitable for use if they are hydrates. Is also good.

As the polyhalo aromatic compound used in the present invention, any compounds represented by the general formulas (III) and (IV) can be used.

Among them, the dihalo aromatic compound satisfying the general formula (III) is preferably 1,4-dichlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dibromobenzene. , 1,2-dibromobenzene, 1,3-dibromobenzene, 1,4-
Difluorobenzene, 1,2-difluorobenzene,
1,3-difluorobenzene, 1,4-diiodobenzene, 1,2-diiodobenzene, 1,3-diiodobenzene, 4,4′-dichlorobiphenyl, 4,4′-dibromobiphenyl, 4,4 '-Difluorobiphenyl,
4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone, 4,4'-difluorobenzophenone, 4,4'-dichlorodiphenylsulfone, 4,4 '
-Dibromodiphenylsulfone, 4,4'-difluorodiphenylsulfone, and the like. Among them, 1,4-dichlorobenzene, 1,4-dibromobenzene, 4,4'-dichlorobiphenyl, 4,4 '-Dibromobiphenyl, 4,4'-dichlorobenzophenone,
4,4'-Dichlorodiphenylsulfone is preferred. These dihaloaromatic compounds can be used alone or in combination of one or more.

The dihalo aromatic compound satisfying the general formula (IV) is preferably 2,5-dichlorodiphenyl sulfide, 2,5-dichlorophenyl-4-biphenylthioether, 2,5-dichlorobiphenyl,
It is possible to mention 5-dichlorodiphenylsulfone, 2,5-dichlorodiphenylether, 2,5-dichlorobenzophenone and mixtures thereof. Particularly preferably, 2,5-dichlorodiphenyl sulfide,
5-dichlorophenyl-4-biphenylthioether is exemplified.

In the polyarylene sulfide of the present invention, the content of the component (II) is 10 mol% or less and 0.05% or less.
Mol% or more. Preferably, it is at most 5 mol% and at least 0.5 mol%. When the content is more than 10 mol%, the melting point of the obtained polymer is extremely low.

With regard to the molar ratio of the general formula (III) + (IV) and the general formula (V) used in the method of the present invention, ((III) + (IV)) / (V) = 0.
90-1.45, preferably 0.95-1.30
It is.

If the charge ratio is less than 0.90, the polymer may be decomposed. If the charge ratio exceeds 1.45, the molecular weight hardly increases, which is not preferable.

The polar organic solvent which is a polymerization solvent used in the present invention may be any solvent as long as it can be polymerized, and preferably, N-methylpyrrolidone, N-ethylpyrrolidone, N-cyclohexylpyrrolidone, N-methylcaprolactam, Mention may be made of tetramethylurea and mixtures thereof. In particular, from an economic point of view, N
-Methylpyrrolidone, N-cyclohexylpyrrolidone,
N-methylcaprolactam is preferred.

The polymerization temperature in the present invention is 18
0-280 ° C. Preferably it is 210-270 degreeC. If the temperature is lower than 180 ° C., the molecular weight hardly increases, while
If the temperature exceeds 0 ° C., decomposition of the polymer may occur, which is not preferable.

In the method of the present invention, a polymerization aid may be added to the polymerization system for the purpose of increasing the molecular weight of the polyarylene sulfide. As the polymerization aid, lithium chloride, n-decane, n-tetradecane, p-
Cimene, sodium acetate, potassium acetate, lithium acetate, water and the like can be mentioned.

As long as the effects of the present invention are not impaired,
Oxidative curing and addition of a branching agent with a tri- or higher functional polyhalo compound may be performed.

The weight average molecular weight of the polyarylene sulfide of the present invention is from 10,000 to 500,000.
Preferably, it is 15,000 or more and 100,000 or less.
When the weight average molecular weight is less than 10,000, the properties as a polymer are hardly exhibited. If it exceeds 500,000, the molecular weight is too high and the processability is poor, which is not preferable. The weight average molecular weight in the present invention is a value in terms of polystyrene measured by gel permeation chromatography (GPC).

The non-Newton index of the polyarylene sulfide of the present invention is 1.05 or more and 2.0 or less,
Further, depending on the structure and the like, it is 1.1 or more and 1.8 or less, which shows excellent workability.

The polyarylene sulfide obtained according to the present invention has excellent mechanical properties and workability, so that it can be very easily formed into tough films, sheets, fibers and the like.

Furthermore, this polyarylene sulfide can be processed into various molds by injection molding, extrusion molding, blow molding, rotational molding, etc., but it is difficult for cracks to enter even if it is thick. It will be.

Further, the polymer of the present invention is filled with a powdery filler such as carbon black, calcium carbonate, silica and titanium oxide, or a fibrous filler such as carbon fiber, glass fiber, asbestos fiber and polyaramid fiber. Can also be used.

The polymer obtained by the method of the present invention includes polycarbonate, polyphenylene oxide, polysulfone, polyacetal, polyimide, polyamide, polyester, polystyrene, polyolefin, A
One or more resins such as BS may be mixed and used.

[0029]

The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

The weight average molecular weight shown here is the value of the ultrahigh temperature GP.
In C, α-chloronaphthalene is used as a solvent and converted into polystyrene at 210 ° C.

The non-Newton index was measured by a capillograph (manufactured by Toyo Seiki) using a die having a length of 60 mm and a diameter of 1 mm.

Melting temperature (Tm), glass transition temperature (Tm)
g) was determined by DSC (manufactured by Seiko Denshi).
It was measured at ° C / min.

Reference Example 1 275 thiophenol was added to a 5-liter separable flask.
g, dimethylformamide 3 l, sodium hydroxide 10
An aqueous sodium hydroxide solution in which 2 g was dissolved in 200 ml of water and 300 ml of benzene were charged and the temperature was raised to 120 ° C.
Here, 296 ml of benzene, which is an azeotropic solvent, and 243 m of water
1 was distilled off.

Thereafter, 567.6 g of 1-bromo-2,5-dichlorobenzene was added, the temperature was raised to 150 ° C., and the temperature was maintained for 3 hours to complete the reaction. After cooling to room temperature, the reaction product was taken out and dimethylformamide was distilled off at 120 ° C. under 2 mmHg. The residue was washed with water to elute the by-product salt, dissolved in methanol, cooled to -78 ° C and recrystallized,
523 g of 5-dichlorodiphenyl sulfide (yield 82
%).

Reference Example 2 17.9 g of 2,5-dichlorothiophenol and 150 parts of dimethylformamide were placed in a 300-ml separate flask.
Then, 20 ml of benzene and 20 ml of an aqueous solution of sodium hydroxide in which 4.08 g of sodium hydroxide was dissolved in 10 ml of water were charged, and the temperature was raised to 120 ° C. Here, 19 ml of benzene as an azeotropic solvent and 11.2 ml of water were distilled off.

Thereafter, 4-bromobiphenyl 23.42
g was added, and the temperature was raised to 150 ° C. and maintained for 3 hours to complete the reaction. After cooling to room temperature, the reaction product was taken out and 2 mmH
Dimethylformamide was distilled off at 120 ° C. under 120 g. The residue was washed with water to elute the by-product salt, and then dissolved in ethanol.
After cooling to −30 ° C. for recrystallization, 16.5 g of 2,5-dichlorophenyl-4-biphenylthioether (yield 4)
9.8%).

Example 1 A 15-liter autoclave was charged with N-methylpyrrolidone (NM
P) 7 l were charged and the temperature was raised to 120 ° C. Then 2.8
2692.7 g of sodium sulfide hydrochloride, lithium acetate 41
5.8 g was charged, and while distilling water out of the system, gradually add 2 g.
The temperature was raised to 04 ° C, and when the temperature reached 204 ° C, 600 g of water was distilled off. At this time, the molar ratio of water in the system to sodium sulfide was 1.20.

After the temperature was raised, the system was cooled to 140 ° C., and 3011 g of p-dichlorobenzene was synthesized.
52.8 g of dichlorodiphenyl sulfide was added and 2
The temperature was raised to 50 ° C., and polymerization was performed for 3 hours.

The weight average molecular weight of the obtained polymer was 43,000 as measured by ultra high temperature GPC.

The non-Newtonian index measured at 300 ° C. by a capillograph was 1.15, the Tg measured by DSC was 80.6 ° C., and the Tm was 279.0 ° C.

Next, the obtained polymer was melt-kneaded with a twin-screw kneading extruder and pelletized. The obtained pellet was formed into a test piece by an injection molding machine. The molding conditions were as follows: cylinder temperature 290 ° C., injection pressure 800 kg / c
m ² , and the mold temperature was 145 ° C.

[0042] The obtained test piece was A for tensile measurement.
STM-638 method, impact strength is ASTM-25
The measurement was performed according to each of the six methods. The results are shown in Table 1. As shown, the burr length was short, the workability was excellent, and the material had excellent mechanical properties.

Example 2 A 15-liter autoclave was charged with 7 L of NMP and heated to 120 ° C.
The temperature rose. Then 2.8 sodium sulfide hydrochloride 269
2.7 g and 415.8 g of lithium acetate were charged, and the temperature was gradually raised to 204 ° C. while distilling water out of the system. 204
When ℃ was reached, 596 g of water were distilled off. At this time, the molar ratio of water in the system to sodium sulfide was 1.21.

After the temperature was raised, the system was cooled to 140 ° C., and 2980.6 g of p-dichlorobenzene was synthesized.
105.5 g of 5-dichlorodiphenyl sulfide was added, the temperature was raised to 250 ° C., and polymerization was performed for 3 hours.

The weight average molecular weight of the obtained polymer was 42.
2,000, non-Newtonian index measured at 290 ° C.
5, Tg was 79.1 ° C and Tm was 274.5 ° C.

The test piece was molded in the same manner as in Example 1 except that the injection temperature was 280 ° C.

The measurement results of the mechanical properties of the obtained test piece are shown in Table 1. The test piece had a short burr length, was excellent in workability, and had excellent mechanical properties.

Example 3 7 liters of NMP was charged into a 15 liter autoclave at 120 ° C.
The temperature rose. Then 2.8 sodium sulfide hydrochloride 269
2.7 g and 415.8 g of lithium acetate were charged, and the temperature was gradually raised to 204 ° C. while distilling water out of the system. 204
When ℃ was reached, 597 g of water were distilled off. At this time, the molar ratio of water in the system to sodium sulfide was 1.21.

After the temperature was raised, the system was cooled to 140 ° C., and 2889.4 g of p-dichlorobenzene was synthesized.
263.8 g of 5-dichlorodiphenylesulphide was charged, the temperature was raised to 250 ° C., and polymerization was carried out for 3 hours.

The weight average molecular weight of the obtained polymer was 48.
The non-Newtonian index measured at 2,000 and 280 ° C. is 1.4.
9, Tg was 70.7 ° C and Tm was 259.6 ° C.

The test piece was molded in the same manner as in Example 1 except that the injection temperature was set at 270 ° C.

The measurement results of the mechanical properties of the obtained test piece are shown in Table 1. The test piece had a short burr length, was excellent in workability, and had excellent mechanical properties.

Example 4 250 ml of NMP in a 500 ml autoclave;
96.17 g of sodium octahydrate sulfide, lithium acetate 1
4.85 g was charged, and 204
The temperature was raised to ° C. When the temperature reached 204 ° C., 20.75 g of water were distilled off. At this time, the molar ratio of water in the system to sodium sulfide was 1.25.

After the temperature was raised, the system was cooled to 140 ° C., and 105.45 g of p-dichlorobenzene was synthesized.
4.85 g of 5-dichlorophenyl-4-biphenylthioether was added, the temperature was raised to 250 ° C., and polymerization was performed for 3 hours.

The weight average molecular weight of the obtained polymer was 41.
2,000, non-Newtonian index measured at 290 ° C.
7, Tg was 78.2 ° C and Tm was 272.6 ° C.

Comparative Example 1 A 15-liter autoclave was charged with 7 L of NMP and heated at 120 ° C.
And 2682.7 g of 2.8 sodium salt sodium sulfide,
415.8 g of lithium acetate was charged, and the temperature was gradually raised to 204 ° C. while distilling water. When the temperature reached 204 ° C., 592 g of water were distilled off. At this time, the molar ratio of water to sodium sulfide was 1.22.

After the temperature was raised, the system was cooled to 140 ° C., 3041 g of p-dichlorobenzene was added, the temperature was raised to 250 ° C., and polymerization was carried out for 3 hours.

The weight average molecular weight of the obtained polymer was 46.
The non-Newtonian index measured at 000 and 300 ° C. is 1.0
0, Tg was 90.8 ° C, and Tm was 282.9 ° C.

Further, the molding of the test piece was performed in the same manner as in Example 1.
Performed according to the method described in The measurement results of the mechanical properties of the obtained test piece are shown in Table 1. As a result, the burr length was long, the workability was poor, and the mechanical properties were also poor.

[0060]

[Table 1]

[0061]

As described above, the polyarylene sulfide of the present invention is excellent in toughness and workability.

Claims (2)

(57) [Claims] (1) The following component (I) is 90 to 99.
95 mol%, component (II) is 10 to 0.05 mol%
And a polyarylene sulfide having a weight average molecular weight of 10,000 to 500,000. Embedded image (X represents CO or SO ₂ , and p and n each represent 0 or 1.) (Y represents S, CO, SO ₂ or O, Z represents CO, SO ₂ or O, and q, r, and m represent 0 or 1, respectively) 2. A compound represented by the following general formula (III), a compound represented by the following general formula (IV) and a compound represented by the general formula (V) in an organic amide solvent,
I): (IV) = 90: 10 to 99.5: 0.05,
((III) + (IV)) / (V) = 0.90-1.4
5. A method for producing polyarylene sulfide, comprising charging at a molar ratio of 5 and reacting at 180 to 280 ° C. Embedded image (A and B are Cl, Br, F or I, respectively, X is CO or S
O ₂ , p, and n represent 0 or 1.) (C and D are Cl, Br, F or I, respectively, Y is S, CO,
SO ₂ or O, Z represents CO, SO ₂ or O, q, r, and m represent 0 or 1, respectively. (E represents an alkali metal, a represents 0 to 9)