JPH07122019B2 - Polyphenylene sulfide composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention can provide a molded article having good impact resistance and flexibility, and further, particularly when melt extruding a tube or sheet, The present invention relates to a polyphenylene sulfide composition which does not generate and has excellent moldability.

<Prior Art> As a polyphenylene sulfide with improved impact resistance, an olefin composed of an α-olefin and an α, β-unsaturated glycidyl ester as an epoxy group-containing olefin polymer is disclosed in JP-A-58-154757. A composition obtained by blending a system copolymer is also a polyphenylene sulfide which has been subjected to a specific treatment in JP-A-62-153343, JP-A-62-153344 and JP-A-62-153345. A composition comprising an olefin-based copolymer composed of an α-olefin and a glycidyl ester of an α, β-unsaturated acid is disclosed.

<Problems to be Solved by the Invention> However, although the impact resistance of the above-mentioned conventional composition is significantly improved by blending the epoxy group-containing olefin-based copolymer, it is melt-extruded into a tube, sheet or the like. In this case, there is a problem in that gels are formed due to excessive polymer intermolecular reaction or unfavorable side reaction, resulting in scratches on the surface of the molded product or deterioration of mechanical properties.

Therefore, the present invention can provide a molded article having good impact properties and flexibility, and further, particularly when melt extruding a tube, a sheet, or the like, there is no generation of lumps, and polyphenylene sulfide having excellent molding processability. The subject is the acquisition of a composition.

<Means for Solving the Problem> That is, the present invention provides polyphenylene sulfide with α-
Based on 100 parts by weight of a composition containing an olefin copolymer having 60 to 90% by weight of an olefin and 1 to 40% by weight of a glycidyl ester of an α, β-unsaturated acid as essential components, the following formula (I) The present invention provides a polyphenylene sulfide composition comprising 0.05 to 5 parts by weight of a hindered phenol compound containing at least one structural unit in the molecule.

(In the formula, R ₁ and R ₂ are hydrocarbon groups having 1 to 6 carbon atoms, and these may be the same or different groups.) Polyphenylene sulfide (hereinafter referred to as PPS) used in the present invention.
Is referred to as) 70 mol% or more of the repeating unit represented by, more preferably
A polymer containing 90 mol% or more, wherein the repeating unit is 70
If it is less than mol%, heat resistance is impaired, which is not preferable.

PPS is generally a polymer having a relatively small molecular weight obtained by the production method represented by JP-B-45-3368, and an essentially linear polymer obtained by the production method represented by JP-B-52-12240. In the polymer obtained by the method described in JP-B-45-3368, a polymer having a relatively high molecular weight and a crosslinking agent such as a peroxide can be obtained by heating in an oxygen atmosphere after the polymerization. It is also possible to use by increasing the degree of polymerization by adding and heating, it is possible to use PPS obtained by any method in the present invention, the effect of the present invention is remarkable Because of the excellent toughness of PPS itself, an essentially linear polymer having a relatively high molecular weight, which is obtained by the production method typified by JP-B-52-12240, is more preferably used.

Further, PPS can comprise less than 30 mol% of its repeating unit with a repeating unit having the following structural formula.

The melt viscosity of PPS used in the present invention is not particularly limited as long as it is possible to obtain a molded article, but 320 ° C., shear rate 1
The melt viscosity when measured under the condition of 000 seconds ^-1 is 100 poise or more in terms of toughness of PPS itself, but 1 in terms of moldability.
The one having a poise of not more than 0,000 is more preferably used.

The PPS used in the present invention is preferably one which has been subjected to the acid treatment, hot water treatment or washing with an organic solvent after being produced through the above-mentioned polymerization step.

The case of performing acid treatment is as follows. The acid used for the acid treatment of PPS in the present invention is not particularly limited as long as it has no action of decomposing PPS, and examples thereof include acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, carbonic acid and propyl acid. However, acetic acid and hydrochloric acid are more preferably used, but those which decompose and deteriorate PPS such as nitric acid are not preferable.

The acid treatment method includes a method of immersing PPS in an acid or an aqueous solution of an acid, and it is also possible to appropriately stir or heat if necessary. For example, when using acetic acid, pH
Dip the PPS powder in the aqueous solution of 4 heated to 80-90 ℃,
A sufficient effect can be obtained by stirring for 30 minutes. The acid-treated PPS needs to be washed several times with water or warm water to physically remove residual acid or salt.

Water used for washing is preferably distilled water or deionized water in the sense that the effect of preferable chemical modification of PPS by acid treatment is not impaired.

When performing hot water treatment, it is as follows.

In the hot water treatment of PPS used in the present invention,
It is important that the temperature of the hot water is 100 ° C. or higher, more preferably 120 ° C. or higher, even more preferably 150 ° C. or higher, particularly preferably 170 ° C. or higher. It is not preferable because it is small.

The water used is preferably distilled water or deionized water in order to exert the preferable chemical modification effect of PPS by the hot water washing of the present invention. The operation of hot water treatment is usually
A predetermined amount of PPS is added to a predetermined amount of water, and the mixture is heated and stirred in a pressure vessel. The ratio of PPS and water is preferably as much as possible, but usually 1 part of water is added to PP.
A bath ratio of S200g or less is selected.

In addition, since the decomposition of the terminal group is not preferable in the processing atmosphere, it is desirable to set it in an inert atmosphere in order to avoid this. Further, it is preferable to wash the PPS after the hot water treatment operation with hot water several times in order to physically remove the remaining components.

The following is the case of washing with an organic solvent.

The organic solvent used for washing PPS in the present invention is not particularly limited as long as it does not have an action of degrading PPS, and for example, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, 1,3-dimethylimidazolidinone. ,
Hexamethylphosphoramide, nitrogen-containing polar solvents such as piperazinones, sulfoxide / sulfone solvents such as dimethyl sulfoxide, dimethyl sulfone, and sulfolane, acetone, methyl ethyl ketone, diethyl ketone,
Ketone solvents such as acetophenone, dimethyl ether, dipropyl ether, dioxane, ether solvents such as tetrahydrofuran, chloroform, methylene chloride, trichlorethylene, ethylene dichloride, perchlorethylene, monochloroethane, dichloroethane, tetrachloroethane, perchlorethane, Halogen-based solvents such as chlorobenzene, methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, phenol, cresol,
Polyethylene glycol. Examples thereof include alcohol / phenolic solvents such as polypropylene glycol and aromatic hydrocarbon solvents such as benzene, toluene and xylene. Among these organic solvents, it is particularly preferable to use N-methylpyrrolidone, acetone, dimethylformamide, chloroform and the like, and these organic solvents are used alone or in a mixture of two or more kinds.

As a method of washing with an organic solvent, PPS in an organic solvent is used.
There is a method of immersing in, and if necessary, it is possible to appropriately stir or heat.

The washing temperature when washing PPS with an organic solvent is not particularly limited, and an arbitrary temperature from normal temperature to 300 ° C can be selected. The higher the cleaning temperature is, the higher the cleaning efficiency tends to be, but normally, the cleaning temperature of room temperature to 150 ° C. is sufficient to obtain the effect.

It is also possible to wash under pressure at a temperature above the boiling point of the organic solvent in a pressure vessel. Also, the washing time is not particularly limited. Although it depends on the washing conditions, in the case of batch type washing, a sufficient effect is usually obtained by washing for 5 minutes or more. It is also possible to wash in a continuous manner.

It is sufficient to wash the PPS produced by the polymerization with an organic solvent, but in order to further exert the effect of the present invention,
It is preferably combined with water washing or warm water washing. When a high-boiling-point water-soluble organic solvent such as N-methylpyrrolidone is used, it is preferable to wash the organic solvent and then wash with water or warm water to easily remove the residual organic solvent. Water used for these washings is preferably distilled water or deionized water.

Further, the PPS used in the present invention may be added with a usual additive such as a lubricant, a crystal nucleating agent, an anti-UV agent, and a coloring agent, and a small amount of another kind of polymer within a range that does not impair the effects of the present invention. Further, for the purpose of controlling the degree of crosslinking of PPS, conventional peroxides and crosslinking accelerators such as metal thiophosphinic acid salts described in JP-A-59-131650 or JP-A-58-204045. Crosslinking inhibitors such as dialkyltin dicarboxylates and aminotriazoles described in JP-A-58-20406 and JP-A-58-20406 can be added.

The olefin copolymer used in the present invention is a copolymer composed of an α-olefin and a glycidyl ester of an α, β-unsaturated acid, and the α-olefin here is ethylene, propylene and butene-. 1, but ethylene is preferably used. Further, the glycidyl ester of an α, β-unsaturated acid has the general formula (R represents a hydrogen atom or a lower alkyl group), and specific examples thereof include glycidyl acrylate, glycidyl methacrylate and glycidyl ethacrylic acid. Of these, glycidyl methacrylate is preferably used. . The copolymerization amount of the glycidyl ester of α, β-unsaturated acid in the olefin copolymer is 0.5 to 40% by weight, particularly preferably 3 to 30% by weight,
If it is less than 40% by weight, the impact property improving effect cannot be obtained.
If it exceeds the range, gelation occurs during melt-kneading with PPS, and extrusion stability, moldability, and mechanical properties deteriorate, which is not preferable.

Further, the olefin-based copolymer is 40% by weight or less, and within a range that does not impair the object of the present invention, other copolymerizable unsaturated monomers such as vinyl ether, vinyl acetate, vinyl prionate, and acrylic acid. Methyl, methyl methacrylate, acrylonitrile, styrene and the like may be copolymerized.

The mixing ratio of PPS and olefin-based copolymer is not particularly limited, but if the olefin-based copolymer is less than 3% by weight, it is difficult to obtain the effect of impact properties, and if it exceeds 50% by weight, PPS
Not only the strength, rigidity and heat resistance of PPS may be impaired, but also gelation occurs during melt-kneading, which tends to impair extrusion stability and moldability. Combined 50 to 3% by weight, especially PPS 60 to 9
The range of 40 to 5% by weight of the olefin-based copolymer can be preferably selected with respect to 5% by weight.

Further, in the present invention, an ethylene / propylene copolymer, an ethylene / butene copolymer, a copolymer of ethylene / (meth) acrylic acid and its derivative and styrene /
An elastomer component such as a hydrogenated product of a butadiene / styrene block copolymer can also be used in combination with the above olefin copolymer.

The hindered phenolic compound used in the present invention is a compound containing at least one structural unit represented by the following formula (I) in the molecule.

(In the formula, R ₁ and R ₂ are hydrocarbon groups having 1 to 6 carbon atoms, and these may be the same or different groups.) Specific examples of the hindered phenolic compound that can be used in the present invention As triethylene glycol-bis [3-tert-butyl-5-methyl-4-hydroxyphenyl)
Propionate], 1,6-hexanediol-bis [3
-(3,5-ditertiarybutyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-ditertiarybutylanilino) -1, 3,5-triazine, pentaerythrityl-tetrakis [3- (3,5-diterthaributyl-4
-Hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-ditertiarybutyl-
4-hydroxyphenyl) propionate], octadecyl-3- (3,5-ditertiarybutyl-4-hydroxyphenyl) propionate, 2,2-thiobis (4-methyl-6-tert-butylphenol), N, N'- Hexamethylene bis (3,5-ditertiarybutyl-4-hydroxy-hydrocinnamamide), 3,5-ditertiarybutyl-4-hydroxybenzylphosphonate diethyl ester, 1,3,5-trimethyl-2, 4,6-tris (3,
5-ditertiarybutyl-4-hydroxybenzyl) benzene, bis (3,5-ditertiarybutyl-4-hydroxybenzylphosphonate ethyl) calcium and N,
Examples thereof include N'-bis [3- (3,5-ditertiarybutyl-4-hydroxyphenyl) propionyl] hydrazine, and these can be used alone or in the form of a mixture of two or more kinds.

The amount of the hindered phenol compound to be compounded is appropriately 0.05 to 5 parts by weight, preferably 0.1 to 4 parts by weight, relative to 100 parts by weight of the PPS composition containing the olefin copolymer. If it is less than 0.05 parts by weight, the desired effect of improving the seeds will not be obtained, and if it is 5 parts by weight or more, the impact strength of the composition will decrease, which is not preferable.

In the present invention, the fibrous and / or granular reinforcing agent is not an essential component, but if necessary, it may be blended in a range not exceeding 300 parts by weight with respect to 100 parts by weight of the total of PPS and the olefin copolymer. It is possible to improve the strength, rigidity, heat resistance, dimensional stability, etc. by adding the compounding agent in an amount of usually 10 to 200 parts by weight.

Such fibrous reinforcing materials include glass fibers, alumina fibers, silicon carbide fibers, ceramic fibers, asbestos fibers,
Inorganic fibers such as gypsum fibers, metal fibers, and carbon fibers are included.

Further, as a granular reinforcing material, silicates such as wollastonite, sericite, kaolin, mica, clay, bentonite, asbestos, talc, and alumina silicate, metals such as alumina, silicon chloride, magnesium oxide, zirconium oxide, and titanium oxide. Examples include oxides, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, glass beads, boron nitride, silicon carbide and silica, which may be hollow. These reinforcing materials can be used in combination of two or more kinds, and if necessary, they can be used after being pretreated with a coupling agent such as a silane-based or titanium-based coupling agent.

The method for preparing the composition of the present invention is not particularly limited, but PPS,
A typical method is to melt-knead an olefin polymer and a hindered phenol compound and optionally a reinforcing material at a temperature equal to or higher than the melting point of PPS in an extruder, and then pelletize.

The melt-kneading temperature is sufficient to melt the composition,
Generally, 280 ° C or higher, usually 340 ° C or lower, that is, 280 ° C or higher from the viewpoint of preventing thermal deterioration and gelation of the olefin-based copolymer.
~ 340 ° C is preferred.

Hereinafter, the present invention will be described in more detail with reference to examples.

<Example> Reference example 1 (Polymerization of PPS) 3.26 kg (25 mol, water of crystallization) of sodium sulfide was added to an autoclave.
(Including 40%), 4 g of sodium hydroxide, 1.36 kg (about 10 mol) of sodium acetate trihydrate and 7.9 kg of N-methyl-2-pyrrolidone (hereinafter referred to as NMP), and gradually stirred at 205 ° C. Distilled water 1.5 including water 1.36kg
Was removed, and the residual mixture was added to 1,4-dichlorobenzene 3.75k.
g (25.5 mol) and NMP2kg were added, and it heated at 265 degreeC for 4 hours. The reaction product was washed 5 times with hot water at 70 ° C and then washed at 80 ° C for 24 hours.
After vacuum drying for about 2 hours, about 2 kg of powdered PPS having a melt viscosity of about 2,500 poise (320 ° C., shear rate of 1,000 sec ⁻¹ ) was obtained.

The same operation was repeated and used in the examples described below.

Examples 1 to 3 About 2 kg of the PPS powder obtained in Reference Example 1 was heated to 90 ° C.
Put it in the acetic acid aqueous solution 20 of 4 and continue stirring for about 30 minutes, then pass, wash with deionized water at about 90 ° C until the pH of the solution becomes 7, and dry under reduced pressure at 120 ° C for 24 hours. It was made into powder.

This PPS powder and ethylene-glycidyl methacrylate (88 /
(12 weight ratio) Copolymer, hindered phenol compound and, if necessary, elastomer were dry blended with the composition shown in Table 1, and then fed to a 40 mmφ single screw extruder set at 290 to 320 ° C. and melt-kneaded. To obtain PPS composition pellets.

Cylinder temperature 300-320 ℃, mold temperature 15
The test piece was molded by supplying it to an injection molding machine set at 0 ° C. In addition, the above pellets are a 30 mmφ single screw extruder equipped with a tape die with a width of 20 mm and a thickness of 1 mm t (temperature: 290 to 320 ° C).
And the tape was molded.

Next, the Izod impact strength of the above composition and the presence or absence of spots on the tape surface were visually evaluated, and the results are shown in Table 1.

As is clear from Table 1, the PPS composition of the present invention has very few tape spots on the tape surface and excellent Izod impact strength, and is a material suitable for sheet and tube applications of extremely high practical value. It has been found.

Example 4 The same procedure as in Example 1 was carried out except that the powder of PPS was "Ryton" PR-06 (polyphenylene sulfide manufactured by Philips Petroleum Co., Ltd.).

Comparative Example 1 Example 1 was repeated except that the hindered phenol compound was not added, and the results are shown in Table 1. The Izod impact strength was high, but there were many spots on the sheet surface.

Comparative Example 2 The procedure of Example 1 was repeated except that 8 parts by weight of the same hindered phenolic compound as in Example 1 was blended.

Although the spots on the seat surface were eliminated, the Izod impact strength decreased significantly.

<Effects of the Invention> According to the PPS composition of the present invention, the impact strength of the molded product is excellent, and the surface spots of the melt extruded product can be remarkably reduced. Therefore, the practical value as a sheet and tube material is extremely high. large.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP 58-204047 (JP, A) JP 55-129445 (JP, A) JP 64-26670 (JP, A) JP 59- 152953 (JP, A) JP 58-154757 (JP, A) JP 59-191761 (JP, A) JP 62-153343 (JP, A) JP 62-153344 (JP, A) JP 62-153345 (JP, A)

Claims (2)

[Claims] 1. A composition comprising a polyphenylene sulfide and an olefin copolymer having 60 to 90% by weight of an α-olefin and 1 to 40% by weight of a glycidyl ester of an α, β-unsaturated acid as essential components. A polyphenylene sulfide composition comprising 0.05 to 5 parts by weight of a hindered phenolic compound containing at least one structural unit of the following formula (I) in the molecule, relative to 100 parts by weight. (In the formula, R ₁ and R ₂ are hydrocarbon groups having 1 to 6 carbon atoms, and these may be the same or different groups.) 2. The polyphenylene sulfide composition according to claim 1, wherein the polyphenylene sulfide has been subjected to acid treatment, hot water treatment or washing treatment with an organic solvent.