JPH03285955A - Polyphenylene sulfide composition - Google Patents

Abstract

PURPOSE:To obtain a composition having excellent impact strength of molded article and reduced in surface spitting of melted extrusion product by blending a composition consisting of polyphenylene sulfide and a specific olefin based copolymer with specific organic phosphite based compound. CONSTITUTION:The aimed polyphenylene sulfide composition obtained by blending 100 pts.wt. composition obtained by adding (B) an olefin based copolymer consisting essentially of 60-90wt.% alpha-olefin (preferably ethylene) and 1-40wt.% glycidyl ester (glycidyl methacrylate) of alpha,beta-unsaturated acid to (A) polyphenylene sulfide, preferably having 100-10000 poise melt viscosity and preferably subjected to acid treatment, hot water treatment or cleaning treatment by an organic solvent with (C) 0.05-10 pts.wt. organophosphite based compound expressed by the formula (R1 and R2 are 6-30C aromatic, aliphatic or alicyclic hydrocarbon group).

Description

Detailed Description of the Invention <Industrial Application Field> The present invention can provide molded products with good impact properties and flexibility, and can also be used particularly when melt-extruding tubes, sheets, etc. The present invention relates to a polyphenylene sulfide composition that does not cause generation and has excellent moldability.

<Prior art> As a polyphenylene sulfide with improved impact resistance, Japanese Patent Application Laid-Open No. 154757/1983 discloses an olefin consisting of an α-olefin and a glycidyl ester of an α,β-unsaturated acid as an olefin polymer containing an epoxy group. A composition comprising a copolymer is also disclosed in Japanese Patent Application Laid-open No. 62-15
3343, JP-A-62-153344, and JP-A-62-153345, α-olefin and α, β are added to polyphenylene sulfide subjected to specific treatments.
- A composition comprising an olefinic copolymer comprising a glycidyl ester of an unsaturated acid is disclosed.

<Problems to be Solved by the Invention> However, although the impact properties of the above-mentioned conventional compositions are greatly improved by incorporating an olefin copolymer containing an epoxy group, it is difficult to melt-extrude them into tubes, sheets, etc. When molded, gelation occurs due to excessive polymer intermolecular reaction and undesirable side reactions, causing problems such as spots on the surface of the molded product and loss of mechanical properties.

Therefore, the present invention provides polyphenylene sulfide which can provide molded products with good impact properties and flexibility, and which also has excellent molding processability and does not generate lumps, especially when melt-extruding tubes and sheets. The objective is to obtain a composition.

Means for Solving the Problem> That is, the present invention provides polyphenylene sulfide with α-
The following structural formula (I ) is a polyphenylene sulfide composition containing 0.05 to 10 parts by weight of an organic phosphite compound represented by:

(In the formula, R1 and R2 are aromatic, aliphatic or alicyclic hydrocarbon groups having 6 to 3 carbon atoms, and these may be the same or different groups.) Polyphenylene used in the present invention Sulfide (hereinafter referred to as PP)
(referred to as S) is a polymer containing the structural formula % or more, more preferably 90 mol % or more, and if the content of the repeating unit is less than 70 mol %, heat resistance will be impaired, so it is not preferable.

PPS is generally a polymer with a relatively small molecular weight obtained by the production method typified by Japanese Patent Publication No. 45-3368, and an essentially linear polymer obtained by the production method typified by Japanese Patent Publication No. 52-12240. In the case of the polymer obtained by the method described in the above-mentioned Japanese Patent Publication No. 45-3368, it is possible to obtain the polymer by heating in an oxygen atmosphere after polymerization or by adding a crosslinking agent such as a peroxide. It is also possible to increase the degree of polymerization and use it by adding and heating PPS, and in the present invention, it is possible to use PPS obtained by any method, but the effects of the present invention are outstanding. And because PPS itself has excellent toughness, an essentially linear polymer having a relatively high molecular weight obtained by the production method typified by the above-mentioned Japanese Patent Publication No. 52-12240 is more preferably used.

Furthermore, less than 30 mol% of the repeating units of PPS can be composed of repeating units having the following structural formula.

The melt viscosity of the PPS used in the present invention is not particularly limited as long as it is possible to obtain a molded product, but the PPS itself should have a toughness of 100 poise or more, and a moldability of 10. Those having OOO poise or less are more preferably used.

The PPS used in the present invention is preferably produced through the above polymerization step and then subjected to acid treatment, hot water treatment, or washing with an organic solvent.

In the case of carrying out acid treatment, the following is the case.9 In the present invention, PPS
The acid used for the acid treatment is not particularly limited as long as it does not have the effect of decomposing PPS, and examples include acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, carbonic acid, and propylic acid, among which acetic acid and hydrochloric acid are used. is more preferably used, but those that decompose and deteriorate PPS, such as nitric acid, are not preferred.

The acid treatment may be carried out by immersing PPS in an acid or an aqueous solution of the acid, and stirring or heating may be carried out as necessary.

For example, when using acetic acid, a pH 4 aqueous solution is
A sufficient effect can be obtained by immersing the PPS powder in a solution heated to 90° C. and stirring for 30 minutes. The acid-treated PPS needs to be washed several times with water or hot water to physically remove residual acids or salts.

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

When performing hot water treatment, the procedure is as follows.

When treating the PPS used in the present invention with hot water, the temperature of the hot water is 100°C or higher, preferably 120°C.
As mentioned above, it is important that the temperature is more preferably 150°C or higher, particularly preferably 170°C or higher; a temperature lower than 100°C is not preferred because the preferred chemical modification effect of PPS is small.

In order to achieve the desired effect of chemical modification of PPS by hot water washing of the present invention, the water used is preferably distilled water or deionized water. The ratio of PPS to water, which is carried out by charging a predetermined amount of PPS and heating and stirring it in a pressure vessel, is preferably as much water as possible, but usually,
A bath ratio of PP3200r or less is selected.

In addition, since the decomposition of the terminal groups is undesirable, the treatment atmosphere is preferably an inert atmosphere to avoid this.Furthermore, the PPS that has undergone this hydrothermal treatment is
It is preferable to wash with warm water several times to physically remove any remaining components.

When washing with an organic solvent, the procedure is as follows.

The organic solvent used for cleaning PPS in the present invention is not particularly limited as long as it does not have the effect of decomposing PPS, and examples include N-methylpyrrolidone, dimethylformamide, dimethylacetamide, and 1,3-dimethylimidazolidinone. , hexamethylphosphorus amide, nitrogen-containing polar solvents such as piperazinone, sulfoxide/sulfone solvents such as dimethyl sulfoxide, dimethyl sulfone, sulfolane, ketone solvents such as acetone, methyl ethyl ketone, diethyl getone, acetophenone, dimethyl ether, dipropyl ether, Ether solvents such as dioxane, tetrahydrofuran, chloroform, methylene chloride, trichloroethylene, ethylene dichloride, perchlorethylene, monochloroethane, dichloroethane,
Halogenated solvents such as tetrachloroethane, perchloroethane, chlorobenzene, methanol, ethanol, propatool, butanol, pentanol, ethylene glycol, propylene glycol, phenol, cresol, polyethylene glycol. Examples include alcohol/phenol solvents such as polypropylene glycol, and aromatic hydrocarbon solvents such as benzene, toluene, and xylene. Among these organic solvents, use of N-methylpyrrolidone, acetone, dimethylformamide, chloroform, etc. is particularly preferred, and these organic solvents may be used singly or in combination of two or more.

As a method of cleaning with an organic solvent, PP is added in an organic solvent.
There are methods such as immersing S, and it is also possible to stir or heat as necessary.

There is no particular restriction on the washing temperature when washing PPS with an organic solvent, and any temperature from room temperature to about 300°C can be selected. Although there is a tendency that the higher the cleaning temperature, the higher the cleaning efficiency, a sufficient effect can usually be obtained at a cleaning temperature of room temperature to 150°C.

It is also possible to wash under pressure in a pressure vessel at a temperature above the boiling point of the organic solvent. Further, there is no particular restriction on the cleaning time, and although it depends on the cleaning conditions, in the case of batch cleaning, a sufficient effect can usually be obtained by cleaning for 5 minutes or more.

It is also possible to wash continuously.

It is sufficient to simply wash the PPS that is not produced by polymerization with an organic solvent, but in order to further exhibit the effects of the present invention, it is preferable to combine washing with water or hot water. When a high-boiling water-soluble organic solvent is used, it is preferable to wash with water or hot water after washing the organic solvent, as the residual organic solvent can be easily removed.The water used for these washings is distilled water or deionized water. Preferably it is water.

In addition, the PPS used in the present invention may contain ordinary additives such as lubricants, crystal nucleating agents, ultraviolet inhibitors, and colorants, as well as small amounts of other polymers, as long as they do not impair the effects of the present invention. Furthermore, for the purpose of controlling the degree of crosslinking of PPS, a crosslinking accelerator such as a common peroxidant and a thiophosphinic acid metal salt described in JP-A-59-131650 or JP-A-58-204045 is used. It is also possible to incorporate crosslinking inhibitors such as dialkyltin dicarboxylate and aminotriazole, which are described in Japanese Patent Publication No. 58-20406.

The next olefin copolymer used in the present invention is a copolymer consisting of an α-olefin and a glycidyl ester of an α, β-unsaturated acid. 1, among others, ethylene is preferably used. In addition, glycidyl esters of α,β-unsaturated acids are compounds represented by the general formula (R represents a hydrogen atom or a lower alkyl group), and specifically include glycidyl acrylate, glycidyl methacrylate, and ethacrylic acid. Among them, glycidyl methacrylate is preferably used. α in olefin copolymers
.

The amount of copolymerization of glycidyl ester of β-unsaturated acid is 0.5
-40% by weight, especially 3-30% by weight is preferred, 0.5% by weight
f! If it is less than 40% by weight, no impact property improvement effect can be obtained, and if it exceeds 40% by weight, gelation will occur during melt-kneading with PPS.
This is not preferred because extrusion stability, moldability, and mechanical properties deteriorate.

In addition, the olefin copolymer may contain other copolymerizable unsaturated monomers, such as vinyl ether, vinyl acetate, vinyl glypionate, acrylic acid, in an amount of 40% by weight or less and within a range that does not impair the purpose of the present invention. Methyl, methyl methacrylate, acrylonitrile, styrene, etc. may be copolymerized.

There is no particular restriction on the blending ratio of PPS and olefin copolymer, but if the olefin copolymer content is less than 3% by weight, it is difficult to obtain impact properties, and if it exceeds 50% by weight, the strength and toughness of PPS will decrease. PP850~
50-3f of olefin polymer compared to 97% by weight! Amount%, especially PP560-95f! Olefin copolymerization #40-5f based on the amount%! The range of the amount % can be preferably selected.

In addition, in the present invention, ethylene/propylene copolymers, ethylene/butene copolymers, ethylene/(meth)acrylic acid and derivatives thereof copolymers, hydrogenated products of styrene/butadiene/styrene block copolymers, etc. An elastomer component can also be used in combination with the above olefin copolymer.

The organic phosphite compound used in the present invention is a compound represented by the following structural formula (I).

(In the formula, R1 and R2 are aromatic, aliphatic or alicyclic hydrocarbon groups having 6 to 30 carbon atoms, and these may be the same or different groups.) In the above structural formula, carbon The aromatic hydrocarbon group having numbers 6 to 30 is a monovalent group containing at least one aromatic ring, such as phenyl group, tolyl group, xylyl group, t-
Butylphenyl group, 2.4- or 2.6-di-t-butyl-4-methylphenyl group, 2,6-di-t-butyl-4-methylphenyl group, ethylphenyl group, 2,6-di-t-butyl-4- Ethylphenyl group, propylphenyl group, n-
Nuclear substituted phenyl groups such as butylphenyl group, pentylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, decylphenyl group, lauryl phenyl group, valmitylphenyl group, stearyl phenyl group, oleylphenyl group , benzyl group, naphthyl group, etc. The aliphatic hydrocarbon group is an alkyl group, alkenyl group, or alkynyl group having 6 to 30 carbon atoms, such as a hexyl group, heptyl group, octyl group, nonyl group, decyl group, lauryl group, palmityl group, or stearyl group. , oleyl group, etc. Furthermore, examples of alicyclic hydrocarbon groups having 6 to 30 carbon atoms include cyclohexyl group, methylcyclohexyl group,
Examples include t-butylcyclohexyl group and cyclohexylmethyl group.

Among these, specific examples of organic phosphite compounds that can be suitably used in the present invention include bis(2,4-di-t
-butylphenyl)pentaerythritol-di-phosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol-di-phosphite, bis(octylphenyl)pentaerythritol-di-phosphite, and Surat Examples include urirubentaerythritol-di-phosphite and bis-stearyl-pentaerythritol-di-phosphite, each of which can be used alone or as a mixture of two or more.

The amount of the organic phosphite compound is in the range of 0.05 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the pps@compound containing the olefin copolymer. It is. If it is less than 0.05 parts by weight, the intended effect of improving the appearance of bumps cannot be obtained, and if it is more than 10 parts by weight, 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 an amount not exceeding 300 parts by weight based on a total of 100 parts by weight of PPS and olefin copolymer. is possible, usually 10~
Strength, rigidity,
It is possible to improve heat resistance, dimensional stability, etc.

Such fibrous reinforcement materials include glass fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber,
Examples include inorganic fibers such as gypsum fibers and metal fibers, and carbon fibers.

Granular reinforcement materials include wollastenite, sericite, kaolin, mica, clay, bentonite, asbestos, talc, silicates such as alumina silicate, and metal oxides such as alumina, silicon chloride, magnesium oxide, zirconium oxide, and titanium oxide. carbonates such as calcium carbonate, magnesium carbonate, dolomite, [6 salts such as calcium sulfate, barium sulfate, glass beads, boron nitride, silicon carbide, graphite and silica, etc., even if they are hollow. It is possible to use two or more of these reinforcing materials in combination, and if necessary, they can be pretreated with a coupling agent such as a silane type or titanium type before use.

The means for preparing the composition of the present invention is not particularly limited, but PPS
A typical method is to melt and mix an olefin polymer, an organic phosphite compound, and, if necessary, a reinforcing material in an extruder at a temperature higher than the melting point of PPS, and then pelletize the mixture.

Note that the melting and kneading temperature is set to sufficiently melt the composition.
Generally, the temperature is preferably 280°C or higher, and 340°C or lower, ie, 280 to 340°C, from the viewpoint of preventing thermal deterioration and gelation of the olefin copolymer.

The present invention will be explained in more detail with reference to Examples below.

<Example> Reference Example 1 (Polymerization of PPS) 3.26 kt (25 kt) of sodium sulfide was placed in an autoclave.
mol, containing 40% water of crystallization), sodium hydroxide 4",
Sodium acetate trihydrate 1.36kIr (approximately 10 moles)
and N-methyl-2-pyrrolidone (hereinafter referred to as NMP)7. Add Oqr and gradually heat to 205℃ while stirring.
After removing 1.51 ml of distilled water containing 1.36 ml of water, 3.75 m of 14-dichlorobenzene was added to the remaining mixture.
(25° 5 mol) and 2 kg of NMP were added and heated to 265°C.
The reaction product heated for 4 hours at
．． 500 poise (320°C, shear rate i, ooo sec-1
) of powdered pps of approximately 2 to 1 r was obtained.

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

Examples 1 to 3 Approximately 20% of the PPS powder obtained in Reference Example 1 was put into 20 μl of a pH 4 acetic acid aqueous solution heated to 90°C, and after stirring for about 30 minutes, it was filtered and the R liquid was separated. Wash with deionized water at about 90°C until the pH becomes 7, and dry under reduced pressure at 120°C for 24 hours to form a powder.

This PPS powder and ethylene-glycidyl methacrylate (
After tri-blending the copolymer (88/12 weight ratio) with an organic phosphite compound and, if necessary, an elastomer in the composition shown in Table 1, it was supplied to a 4oIIllIφ single-screw extruder set at 290 to 320°C, Melt and knead P
A PS composition pellet was obtained.

This pellet was supplied to an injection molding machine set at a cylinder temperature of 300 to 320°C and a mold temperature of 150°C to mold a test piece. Also, the above bellet @i 20 r
30m with tape die of am x thickness 1 wn t
It was supplied to a wφ single-screw extruder (temperature 290 to 320°C) to form a tape.

Next, the above composition was visually evaluated for its Izot impact strength and the presence or absence of stickiness on the tape surface, and the results are shown in Table 1.

As is clear from Table 1, the PPS composition of the present invention has extremely little bumpiness on the tape surface and has excellent Izot impact strength, making it a material suitable for sheet and tube applications with extremely high practical value. It turns out that.

Example 4 The same procedure as in Example 1 was conducted except that "Rydon" PR-06 (polyphenylene sulfide manufactured by Phillips Vetroleum) was used as the PPS powder, and the results are also shown in Table 1.

Comparative Example 1 The same machine as in Example 1 was used except that no organic phosphite compound was added, and the results are shown in Table 1. Although the Izotsu impact strength was high, there were many spots on the sheet surface.

Comparative Example 2 The same procedure as in Example 1 was carried out except that 15 parts by weight of the same organic phosphite compound as in Example 1 was blended.

Although the bumps on the sheet surface were resolved, the Izotsu impact strength was significantly reduced.

<Effects of the Invention> The PPS composition of the present invention has excellent impact strength for molded products and can significantly reduce surface bumps in melt-extruded products, so it has extremely practical value as a material for sheets and tubes. big.

Patent application Daitoshi Co., Ltd.

Claims (2)

[Claims] (1) Polyphenylene sulfide, α-olefin 6
For 100 parts by weight of a composition containing an olefin copolymer whose essential components are 0 to 90% by weight and 1 to 40% by weight of glycidyl ester of an α,β-unsaturated acid,
A polyphenylene sulfide composition containing 0.05 to 10 parts by weight of an organic phosphite compound represented by the following structural formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(I) (In the formula, R_1 and R_2 are aromatic, aliphatic, or alicyclic hydrocarbon groups having 6 to 30 carbon atoms, and these are mutually exclusive. (They 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 cleaning treatment with an organic solvent.