JPH0797451A - Polyarylene sulfide copolymer and its production - Google Patents

Abstract

PURPOSE:To produce a polyarylene sulfide copolymer which has excellent mechanical characteristics and in which a functional polyarylene sulfide and a functional reactive polyolefin are dispersed well in each other and further functional groups of these two polymer are reacted with each other at a high conversion rate. CONSTITUTION:99-70wt.% functional polyarylene sulfide is reacted with 1-30wt.% functional reactive polyolefin to give a polyarylene sulfide copolymer in which at least 7% of the functional groups of the functional polyarylene sulfide are reacted with functional groups of the functional reactive polyolefin.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polyarylene sulfide copolymer and a method for producing the same. More specifically, the present invention relates to a polyarylene sulfide copolymer that can be suitably used in various electric and electronic fields and fields that require highly rigid materials, and a method for producing the same.

[0002]

2. Description of the Related Art Techniques called polymer blends and polymer alloys have been used in order to improve the properties of polymers, and research thereof has been actively conducted in recent years. The production of polymer blends and polymer alloys is generally carried out by kneading the polymers using an extruder. Regarding the polyarylene sulfide resin, many melt blends of the polyarylene sulfide resin and various other polymers have been published for the purpose of improving various properties. Among them, a method in which a polyarylene sulfide having an amino group and various reactive polymers are simply melted and kneaded is disclosed in, for example, JP-A-4-153262.

[0003]

However, in this case, since the polymers are incompatible with each other, the amino group of the polyarylene sulfide does not sufficiently react with the reactive polymer, and the dispersion of the polymers is insufficient. Therefore, there is a problem in that it is impossible to achieve satisfactory improvement in mechanical properties. The present invention has been made in view of the above problems, the dispersibility of the polymers is good,
An object of the present invention is to provide a polyarylene sulfide copolymer having excellent mechanical properties, and further to provide a method for producing a polyarylene sulfide copolymer having a high reaction efficiency of functional groups.

[0004]

[Means for Solving the Problems] In order to achieve the above object, as a result of intensive studies, a polyarylene sulfide (A) having a functional group and a polyolefin (B) having a functional group are mixed at a predetermined mixing ratio during the reaction. And, (A)
By reacting a predetermined amount of the functional group of (B) with the functional group of (B), a target polyarylene sulfide copolymer can be obtained, and further, a predetermined mixing ratio of (A) and (B) The inventors have found that the target method for producing a polyarylene sulfide copolymer can be obtained by dissolving (A) and (B) in a solution in a polar solvent and reacting them in a solution state, and completed the present invention.

That is, according to the present invention, in the polyarylene sulfide copolymer obtained by reacting the polyarylene sulfide (A) having a functional group and the reactive polyolefin (B) having a functional group, the above-mentioned (A )
And the blending ratio (% by weight) at the time of the reaction of (B) is (A):
(B) = 99 to 70: 1 to 30 and (A)
There is provided a polyarylene sulfide copolymer, which is obtained by reacting 7% or more of the functional group (1) with the functional group (B).

Also provided is a polyarylene sulfide resin composition comprising 100 parts by weight of the polyarylene sulfide copolymer and 5 to 500 parts by weight of a fibrous and / or powdery filler (C). It

Further, in the method for producing a polyarylene sulfide copolymer in which a polyarylene sulfide (A) having a functional group and a reactive polyolefin (B) having a functional group are reacted, the above (A) and (B) are replaced by
(A): (B) = 99 to 70: a polyarylene sulfide characterized by being dissolved in a polar solvent at a compounding ratio (% by weight) of 1 to 30 and reacting (A) and (B) in a solution state. A method of making a copolymer is provided.

Further, the reaction temperature in the step of reacting the above (A) and (B) in a solution state is 220 to 300 ° C.
A method for producing a polyarylene sulfide copolymer is provided.

Furthermore, the above-mentioned reaction in solution state of (A) and (B) is to react 7% or more of the functional group of (A) with the functional group of (B). A method for producing a sulfide copolymer is provided.

The present invention will be described in detail below. The polyarylene sulfide copolymer of the present invention has a functional group-containing polyarylene sulfide (A) of 99 to 70% by weight,
And reactive polyolefins (B) 1 to 3 having a functional group
0% by weight is obtained by reacting. In this case, it is necessary to react 7% or more of the functional group of (A) with the functional group of (B).

1. Polyarylene sulfide (A) having a functional group (1) The functional group of the functional group (A) is not particularly limited, and examples thereof include an amino group, an amide group, a carboxyl group, a hydroxyl group, an acid chloride group and an isocyanate group. Can be mentioned. Of these, an amino group and an amide group are preferable.

(2) Method for producing polyarylene sulfide (A) having a functional group The method for producing (A) used in the present invention is not particularly limited, and a known method can be used. For example,
The method described in JP-A-2-294331 can be mentioned. Specifically, in a polar solvent, (a) at least one metal sulfide selected from the group consisting of alkali metal sulfides and alkali metal hydrosulfides, (b) a dihalogen aromatic compound, and (c) It may be brought into contact with the functional group-containing compound. For example, when it is desired to introduce an amino group as a functional group, a polyhalogenamino aromatic compound may be used as (c). The molar ratio of the component (b) to the component (a) is preferably (a) / (b) = 1.03 to 1.25. The molar ratio of the component (b) to the component (c) is preferably (c) / (b) = 0.003 to 0.05. Its melt viscosity is 50-40,000.
It is preferably 0 poise. If it is less than 50, the strength is lowered and burrs are likely to occur during injection molding, resulting in insufficient moldability. If it exceeds 40,000, the viscosity at the time of melting becomes too high, resulting in decomposition or decomposition of the resin. Burrs are more likely to occur.

2. Reactive Polyolefin (B) Having a Functional Group The reactive polyolefin (B) having a functional group used in the present invention is not particularly limited, but examples thereof include the following. Ethylene 50-90% by weight
(Preferably 60 to 85% by weight), α, β-unsaturated carboxylic acid alkyl ester 5 to 49% by weight (preferably 7 to 4)
5% by weight) and a monomer containing 0.5 to 10% by weight (preferably 1 to 8% by weight) of a functional group-containing monomer. Where α, β
Examples of the unsaturated carboxylic acid alkyl ester include unsaturated carboxylic acids having 3 to 8 carbon atoms, such as alkyl esters of acrylic acid and methacrylic acid. Specifically, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate , N-butyl methacrylate, isobutyl methacrylate and the like. Above all, ethyl acrylate, acrylic acid n-
Butyl and ethyl methacrylate are preferred.

The functional group-containing monomer is not particularly limited. For example, a monomer containing an acid anhydride group, an epoxy group, an amino group, an amide group, a hydroxyl group, an acid chloride group, an isocyanate group, or the like, for example, , Maleic anhydride, glycidyl acrylate, acrylic acid, glycidyl methacrylate, methacrylic acid and the like. Of these, maleic anhydride and glycidyl methacrylate are preferable.

3. In the present invention, the mixing ratio in the reaction between (A) and (B) is such that the mixing ratio in the reaction between (A) and (B) is (%) by weight (A) :( B) = 99-7
It is necessary to set 0: 1 to 30. When (A) exceeds 99% by weight, the mechanical properties such as impact strength are not improved, and when it is less than 70% by weight, heat resistance and dimensional stability are significantly impaired. Particularly (A) :( B) = 97-80:
3-20 is preferable.

4. Reaction Rate of Functional Group of (A) In the present invention, as described above, it is necessary to react with 7% or more, preferably 10 to 100% of the functional group of (A), and the functional group of (B). If it is less than 7%, the mechanical properties of the resulting copolymer will be insufficient.

5. Reaction of (A) and (B) In the present invention, it is necessary to dissolve (A) and (B) in a polar solvent and to react them in a solution state. The solution state here means a state in which the polymer is dissolved in a polar solvent. Here, examples of the organic polar solvent used in the present invention include aprotic organic solvents such as amide compounds, lactam compounds, urea compounds, and cyclic organic phosphorus compounds. As the amide compound,
Formamides such as N, N-dimethylformamide,
Examples thereof include acetamides such as N, N-dimethylacetamide, N, N-diethylacetamide and N, N-dipropylacetamide, and aromatic carboxylic acid amides such as N, N-dimethylbenzoic acid amide. Examples of the lactam compound include caprolactam and N-methylcaprolactam, N-ethylcaprolactam, N-n-propylcaprolactam, N-propylcaprolactam, N-n-butylcaprolactam, N-isobutylcaprolactam, and N-cyclohexylcaprolactam. Caprolactams such as N-alkylcaprolactam; N-methyl-2-pyrrolidone, N-ethyl-
2-pyrrolidone, Nn-propyl-2-pyrrolidone,
N-isopropyl-2-pyrrolidone, N-n-butyl-
2-pyrrolidone, N-isobutyl-2-pyrrolidone, N
-Cyclohexyl-2-pyrrolidone, N-methyl-3-
Methyl-2-pyrrolidone, N-ethyl-3-methyl-pyrrolidone, N-methyl-3,4,5-trimethyl-2-
N-alkyl and other pyrrolidones such as pyrrolidone; N-
Methyl-2-piperidone, N-ethyl-2-piperidone, N-isopropyl-2-piperidone, N-methyl-
6,6-methyl-2-piperidone, N-methyl-3-ethyl-2-piperidone and the like can be mentioned. Further, as aprotic organic polar solvents other than the above, for example, urea compounds such as tetramethylurea, N, N′-dimethylethyleneurea, N, N′-dimethylpropyleneurea, 1-methyl-1-oxosulfolane, 1 -Ethyl-
1-oxosulfolane, 1-phenyl-1-oxosulfolane and other oxosulfolanes, 1-methyl-1-oxophosphorane, 1-n-propyl-1-oxophosphorane, 1-phenyl 1-oxophosphorane, etc. And oxophosphorane of the above. Among these solvents, amide compounds and lactam compounds can be mentioned as suitable examples, and N-alkyllactams and N-alkylpyrrolidones are preferable, and N-methylpyrrolidone is particularly preferable. These organic polar solvents may be used alone or in combination of two or more. Moreover, in this case, 220 to 300 ° C.
The reaction temperature is preferably 240 to 27
0 ° C. is more preferable. When it exceeds 300 ° C, decomposition and deterioration occur, and when it is less than 220 ° C, solid is precipitated.

If only (A) and (B) are dry-blended and melt-kneaded, the proportion of the functional group of (A) reacting with (B) becomes low, and the copolymer having satisfactory mechanical properties can be obtained. You can't get coalesced.

6. Fibrous and / or powdery filler (C) In the polyarylene sulfide resin composition of the present invention, the above-mentioned polyarylene sulfide copolymer is blended with the fibrous and / or powdery filler (C ) Is blended.

The fibrous filler and / or the particulate filler (C) used in the present invention is not particularly limited, but an inorganic filler can be preferably used. Examples of the inorganic filler include carbonates such as calcium carbonate, magnesium carbonate and dolomite; sulfates such as calcium sulfate and magnesium sulfate; sulfites such as calcium sulfite; talc; clay; mica; titania; zirconia;
Ferrite; Asbestos; Glass fiber; Silicates such as calcium silicate, montmorillonite, bentonite, etc.
Metals such as iron, zinc, copper, aluminum and nickel; ceramics such as silicon carbide, silicon nitride, boron nitride and the like, whiskers such as potassium titanate and aluminum borate, carbon black, graphite, carbon fiber, etc. it can. These inorganic fillers may be used alone or in combination of two or more. Among these, usually, glass fiber, carbon fiber alone or a mixture thereof with a powdery or granular filler can be preferably used. As the fibrous filler and / or the granular filler (C), if necessary, instead of the inorganic filler or together with the inorganic filler, for example, wood powder, coconut shell powder, cork powder, An organic filler such as floc may be used.

There is no limitation on the average fiber diameter or particle diameter of the fibrous filler or powdery or granular filler (C), and one having an optimum diameter may be appropriately selected according to the purpose. The particle size is preferably 20 μm or less. If the average fiber diameter or particle diameter is larger than 20 μm, the dispersibility in the composition may decrease. The compounding ratio of the fibrous filler and / or the granular filler (C) to the polyarylene sulfide copolymer is 5 to 500 parts by weight, preferably 10 to 300 parts by weight with respect to 100 parts by weight of the polyarylene sulfide copolymer. It is a department. If the blending ratio is less than 5 parts by weight, the effect of blending the fibrous filler and / or the granular filler (C) will not be sufficiently exhibited, and if it exceeds 500 parts by weight, the kneadability and dispersion of the composition In some cases, the mechanical properties and even the mechanical strength may be reduced.

[0022]

EXAMPLES The present invention will be described more specifically below based on Examples and Comparative Examples. The reaction rate (%) of the amino group of the polyarylene sulfide (A) is based on the absorption spectrum of the amino group appearing at 3387 cm ⁻¹ in the IR spectrum ((amino group content before reaction−amino group after reaction) Content (mol%)) / amino group content before reaction (mol%) × 100.

Production Example Production of Polyarylene Sulfide Containing Amino Group In a reaction tank equipped with a stirrer, hydrous sodium sulfide (Na ₂ S
・ 5 hydrates) (833 mol) and N-methyl-2-pyrrolidone (NMP) (510 liters) were charged, and the pressure was reduced to 145 ° C.
Dehydration treatment was carried out for 1 hour while maintaining the above. Then, after cooling the reaction system to 45 ° C., p-dichlorobenzene 816
Mol and dichloroaniline (DCA) 43.0 mol were added, and the reaction was carried out at 240 ° C. for 5 hours. After that, the reaction tank was cooled, the contents were filtered off, and the cake was washed 3 times with hot water, then with NMP at 170 ° C. once, with water 3 times, and then with acetone once. And dried at 185 ° C. to obtain 77 kg of white, granular amino group-containing polyarylene sulfide (hereinafter abbreviated as DCA-PAS). This DCA-PAS has an amino group-containing unit content of 1.01 mol% and a melt viscosity of 202.
It was 0 poise.

Example 1 PAS950 having an amino group obtained by the production example
g, as a reactive polyolefin having a functional group, Bondyne AX8390 (copolymer obtained by radical polymerization of ethylene, ethyl acrylate and maleic anhydride) manufactured by Sumika Atchem Co., N-methylpyrrolidone 5000 m
l was put into a 10 liter autoclave, and the temperature was 260 ° C.
The reaction was carried out for 1 hour. After cooling to room temperature, the solid substance was separated, washed repeatedly with 5000 ml of pure water and acetone, and vacuum dried at 100 ° C. for 20 hours. The amino group reaction rate of PAS was 24%. Table 1 shows the reaction rate of amino groups of PAS and the physical properties of the obtained copolymer.

Example 2-3 A copolymer was prepared in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1 PAS950 having an amino group, obtained in Reference Example
g and 50 g of Bondine AX8390 were dry blended, and then melt-kneaded at 320 ° C. The amino group reaction rate of PAS was 5%. Table 1 shows the physical properties of the obtained copolymer.

Example 4 Graft copolymer obtained in Example 1 and chopped glass fiber (03MAFT1 manufactured by Asahi Fiber Glass Co., Ltd.)
No. 04, diameter 13 μm, length 3 mm) was dry-blended and then melt-kneaded at 320 ° C. Table 1 shows the amino group reaction rate of PAS and the physical properties of the obtained resin composition.

Comparative Example A comparative example was prepared by the same procedure except that 03MAFT104 was added. The results are shown in Table 1.

[Table 1] ──────────────────────────────────── Bondine 03MAFT104 Flexural strength Flexural modulus Impact strength Amino group reaction rate (wt%) (wt%) (MPa) (GPa) (kJ / m ² ) (%) ────────────────────── ─────────────── Reference Example 0 0 108 4.8 18.4 0 Example 1 5 0 128 128 4.0 28.9 24 Example 2 10 0 132 4.2 35 .9 46 Example 3 15 0 141 4.5 65.6 61 Comparative Example 1 5 0 100 4.4 4.4 19.6 5 Example 4 3 40 220 16.2 60 24 Comparative Example 2 3 40 224 15.5 51 5 ────────────────────────────────────

[0030]

As described above, according to the present invention, it is possible to obtain a polyarylene sulfide copolymer having excellent dispersibility between polymers and excellent mechanical properties. Further, a polyarylene sulfide resin composition having heat resistance, impact resistance, and dimensional stability can be obtained. Furthermore, it is possible to provide a method for producing a polyarylene sulfide copolymer having a high functional group reaction efficiency.

Claims (5)

[Claims] 1. A polyarylene sulfide copolymer obtained by reacting a polyarylene sulfide (A) having a functional group and a reactive polyolefin (B) having a functional group, wherein: Mixing ratio during reaction (wt%)
Is (A) :( B) = 99 to 70: 1 to 30 and is obtained by reacting 7% or more of the functional group of (A) with the functional group of (B). And a polyarylene sulfide copolymer. 2. A polyarylene sulfide resin composition comprising 100 parts by weight of the polyarylene sulfide copolymer according to claim 1 and 5 to 500 parts by weight of a fibrous and / or powdery filler (C). object. 3. A method for producing a polyarylene sulfide copolymer in which a polyarylene sulfide (A) having a functional group and a reactive polyolefin (B) having a functional group are reacted with each other, wherein (A) and (B) are: (A): (B) = 99-7
A method for producing a polyarylene sulfide copolymer, which comprises dissolving (A) and (B) in a solution in a polar solvent at a compounding ratio (wt%) of 0: 1 to 30 and reacting them in a solution state. 4. The method for producing a polyarylene sulfide copolymer according to claim 3, wherein the reaction temperature in the step of reacting the (A) and (B) in a solution state is 220 to 300 ° C. . 5. The solution-state reaction of (A) and (B) is to react 7% or more of the functional group of (A) with the functional group of (B). The method for producing the polyarylene sulfide copolymer according to any one of 3 to 5.