JPS62153345A - Polyphenylene sulfide resin composition - Google Patents

Abstract

PURPOSE:To contrive improvement in impact properties, by blending a polyphenylene sulfide resin having a sodium content of a specified value or below with a specified olefin copolymer. CONSTITUTION:A polyphenylene sulfide resin (hereinafter referred to as PPS) having a sodium content of 900 ppm or below is blended with an olefin copolymer composed of 60-99.5 wt. % alpha-olefin and 0.5-40 wt. % glycidyl ester of an alpha, beta-unsaturated acid as essential ingredients. The sodium content of PPS can be lowered to 900 ppm or below by an acid treatment or hot water treatment. A preferred example of the alpha-olefin in the olefin copolymer is ethylene. A preferred example of the glycidyl ester of an alpha, beta-unsaturated acid is glycidyl methacrylate. The preferred blending ratio of the ingredients of the compsn. is such that PPS is 70-97 wt. % and the olefin copolymer is 30-3 wt. %.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention is directed to ! ? This relates to a polyphenylene sulfite resin composition with improved r properties, and 11th article relates to a polyphenylene sulfite resin composition with improved impact properties by incorporating an olefin copolymer into a specific polyphenylene sulfite resin. Necessary for something that is covered by something.

<Prior art> Conventionally, as polyphenylene sulfite resin compositions with improved sand impact properties,
No. 757 discloses a composition comprising an oleic copolymer comprising an α-olefin and a glycidyl ester of an α,β-unsaturated acid.

The problem that the invention seeks to solve> ``However,
Even in the composition described in the above-mentioned publication, the effect of improving 17I bacterial attack is insufficient. As is known in the past, the molecular chain of ordinary polyphenylene sulfite resin is poor in reaction meters, so it is difficult to react with epoxy molecules such as the oleic copolymer described in the above-mentioned publication. Even if the rubber component is blended, the interface with polyphenylene sulfite is insufficient, so it is difficult to improve the impact properties at present. Therefore, the present inventors conducted intensive investigations with the aim of improving the impact properties of rubber components, such as polyphenylene sulfite (polyphenylene sulfite) or 1 fat composition. It has been discovered that this objective can be achieved by blending a specific rubber with 1<5 trefoil, and the present invention has been achieved.

Means for Solving the Problems> That is, the present invention provides a polyphenylene sulfide resin having a sodium content of 900 ppm or less, and 60 to 99.5% by weight of α-olefin and α-olefin.

Glycidyl ester of β-unsaturated acid 0.5-40% by weight
The present invention provides a polyphenylene sulfide resin composition containing an oleic copolymer having as an essential component.

Polyphenylene sulfide (hereinafter referred to as PP) used in the present invention
(referred to as S) is a polymer containing 70 mol% or more, more preferably 90 mol% or more of repeating units represented by the structural formula ←CΣS+, and if the repeating unit is less than 70 mol%, heat resistance will be impaired. Therefore, it is undesirable.

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

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

The melt viscosity of PPS used in the present invention is not particularly limited as long as it is possible to obtain molded products, but in terms of the toughness of PPS itself, it is 100 poise or more, but in terms of moldability, it is 10,000 poise. The following are more preferably used.

The PPS used in the present invention has a sodium content of 900
pI)m or less, more preferably 70099m or less, most preferably 5001)I)
m or less, particularly preferably 300 ppII or less. It is not preferable to use PPS with a sodium content of more than 9001)t)m because the significant effect of improving impact properties by the olefin copolymer is not achieved.

1) PS obtained according to a known method is 1000-15
Contains 00 ppm or more of sodium.

As an effective means for reducing the sodium content of such PPS to 9009 pm or less, treatments such as acid treatment or heat treatment can be used. These methods include, for example, immersing PPS in an acid such as acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, carbonic acid, propylic acid, etc. or an aqueous solution thereof, and heating or accompanying the PPS as necessary, or heating it in a pressure vessel. Examples include water treatment methods and methods that combine these methods.

When these treatments are performed, it is preferable to wash with warm water several times in order to remove residual acids, salts, etc. These treatments must ensure that the concentration falls below 900 pI)m.

In addition, 'PPS used in the present invention may contain ordinary additives such as antioxidants, heat stabilizers, lubricants, crystal nucleating agents, ultraviolet inhibitors, colorants, etc., and a small amount of additives, as long as they do not impair the effects of the present invention. Various types of polymers can be added, and in addition, for the purpose of controlling the crosslinking decay of PPS, crosslinking agents such as ordinary peroxidants and thiophosphinic acid metal salts described in Japanese Patent Publication No. 59-131650 can be added. Accelerator or JP-A-58-2
It is also possible to incorporate crosslinking inhibitors such as dialkyltin dicarboxylate and aminotriazole described in JP-A No. 04045, JP-A-58-204046, and the like.

The 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, and the α-olefin herein refers to ethylene, propylene, butene-1, etc. Ethylene is preferably used. 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. Olefin-based compound [Kokareru α,
The glycidyl ester of β-unsaturated acid has a weight content of 0.5
-40 width loss%, especially 3-30 small G1% is preferable, and 0.
If the amount is less than 5ffl%, the desired effect cannot be obtained;
If it exceeds ω% by weight, gelation will occur during melt-kneading with PPS, and extrusion stability, moldability, and mechanical properties will deteriorate, which is not preferable.

In addition, the olefin copolymer may contain other copolymerizable unsaturated monomers, such as vinyl needles, vinyl acetate, vinyl propionate, within a maximum amount of 40% or less and within a range that does not impair the purpose of the present invention. Methyl acrylate, methyl methacrylate, acrylonitrile, styrene, etc. may be copolymerized.

There is no particular limit to the ratio of blending PPS and olefin copolymer, but if the olefin copolymer is less than 3% by weight, it is difficult to obtain the desired effect, and if it exceeds 30% by weight, the strength of PPS Not only is there a risk of loss of rigidity and heat resistance, but also gelation occurs during melt-kneading, which tends to impair extrusion stability and moldability.
97% by weight, preferably 30 to 3% by weight of the olefin copolymer, more preferably PP375 to 95mono37
5-9, olefin copolymer 25-5% by weight, especially P
Olefin copolymer 2 for P380-90% by weight
A range of 0 to 10% by weight can be preferably selected.

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. It is possible to improve strength, rigidity, heat resistance, dimensional stability, etc. by blending in the range of 10 to 1300 parts by weight.

Examples of such fibrous reinforcing agents include inorganic fibers such as glass fibers, glass fibers, alumina fibers, silicon carbide fibers, ceramic fibers, asbestos fibers, stone wax fibers, and metal fibers, and carbon fibers.

Granular reinforcing agents 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, sulfates such as calcium sulfate and barium sulfate, glass beads, boron nitride, silicon carbide, Saroyan, silica, etc.
These may be hollow. Two or more of these reinforcing agents can be used in combination, and if necessary, the reinforcing agent can be pretreated with a coupling agent such as a silane type or a 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-knead PPS, an olefin copolymer, and a reinforcing agent in an extruder at a temperature higher than the melting point of PPS, and then pelletize the mixture.

In addition, the melt-kneading temperature is preferably 280 to 340°C,
If the temperature is lower than 280'C, the melting of PPS may become insufficient, and if the temperature exceeds 340'C, the olefin copolymer may undergo thermal deterioration and gelation, so care must be taken.

The present invention will be described in more detail with reference to Examples above.

<Example> Reference example 1 (PPS chassis) O 1 ~ Crepe sulfide 1 ~ Lium 3.26Ky (2
5 mol, containing 40% water of crystallization>, sodium hydroxide 43
, sodium acetate trihydrate 1.36 to 3 (approximately 10 mol)
iJ3 and N-methyl-2-pyrrolidone (hereinafter referred to as NMP)
) on 7.9! J was charged, the stomach was gradually warmed to 205°C while stirring, and 1.59 ml of distilled fishing rod containing 1°36 KFl of water was removed. 3.75 Kg (25.5 mol) of 1,4-dichlorobenzene and N M
P 2 K'J was added and heated at 265°C for 404 minutes. The reaction product was washed 5 times with warm water at 70'C and heated to 80'C.
Dry under reduced pressure for 24 hours at C to obtain powdered PP with a melt viscosity of about 2500 poise (320'C, shear rate 1000 sec-]).
Approximately 2 kg.

The total sodium content in this PPS powder is 1°130t
)l)m.

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

Example 1 Approximately 2 to 3 q of the PPS powder obtained in Reference Example 1 was poured into a PL+4 acid-resistant aqueous solution 20.1) heated to 90'C, and the mixture was stirred with the valve open for approximately 30 minutes, and then filtered. , washed with deionized water at about 90'C until the pH of the filtrate was 7, '12
It was dried under reduced pressure at 0'C for 24 hours to obtain '1C) powder.

The total sodium content in this PPS was 273DDm.

This powder and ethylene-glycidyl methacrylate (88
/12 weight ratio> copolymer (hereinafter abbreviated as olefin copolymer) was triblended at a weight h1 ratio of 80:20, melt-mixed using a screw extruder set at 290 to 310'C, and pelletized. . Next, Peret]～29
It is fed to a screw in-line injection molding machine set at 0 to 300'C, and the strip is heated to a mold temperature of 140 to 150'C.
1 to form a test piece for mechanical property evaluation @A' type.

Izot impact strength (AS-MD-256>, heat distortion temperature (△STM D
-648> is as shown in Table 1, and the impact strength was extremely high, and the decrease in heat distortion temperature was smaller than that of the sample not containing the olefin copolymer.

Philippine-Chinese Cross 1 Row 1-2 Reference Example 1 PPS' cauterized end as it is (Comparison! 9
11 > And U; 1 Using acetic acid treatment, washing, and drying in the same manner as in Example 1 (Comparative Example 2), pelletizing and extrusion molding were performed without blending the olefin copolymer. For test j1, the impact strength and heat distortion temperature of 111 Ti were as shown in Table 1.

Comparative Example 3 Instead of using the PPS powder prepared in Reference Example 1 after treating it with acetic acid, PPS powder 2 prepared in Reference Example 1 was used.
) powder was used as it was; Izot impact strength and thermal deformation were evaluated on test pieces that were melt-mixed with an olefin copolymer, pelletized, and injection molded in exactly the same manner as in Example 1. Temperatures were as listed in Table 1.

Examples 2 to 5, Comparative Example 4 PPS powder 2 prepared by 1q in Reference Example 1 KFI and 1ON of deionized water were charged into an autoclave, and the autoclave was sealed at normal pressure. The mixture was back-warmed to a temperature of 100.degree. C., kept warm (hot water treatment) for about 36 minutes while stirring, and then cooled. Take out the contents, filter, and further heat at 70°.
After repeating 5 times of soaking and stirring in deionized Honsuri 10.1) of C, 2411 at 120'C.
．． It was dried under reduced pressure for a period of time and then used as a final method. each P P
The total sodium content in the S powder was as shown in Table 1.

Hereinafter, the olefin copolymer was melt-mixed, pelletized, and index molded in exactly the same manner as in Example 1. It was as described.

Example 6 Example 1 Ethylene-glycidyl methacrylate (88/
Instead of using a copolymer with a copolymerization ratio of 94
A test piece was obtained by performing exactly the same operation as in Example 1, except that a copolymer of /6 (weight ratio) was used. The characteristic values evaluated for the obtained test pieces were as shown in Table 1.

Example 7 The same operation as in Example 1 was carried out except that the blending ratio of the olefin copolymer was limited to 10% by weight instead of 20% by weight. The characteristic values evaluated for the 1q test piece were determined as shown in Table 1.

Examples 8-9 PPS powder treated with acid in the same manner as in Example 1,
The olefin copolymer and glass fiber were melt-mixed, pelletized, and injection molded in exactly the same manner as in Example 1 using the V [as shown in Table 1]. was rare as shown in Table 1.

Comparative Examples 5-6 PPS and glass fiber obtained in Reference Example 1 (Comparative Example 5),
The PPS obtained in Reference Example 1, the olefin copolymer, and the glass fiber (Comparative Example 6) were melt-mixed, pelletized, and injected in exactly the same manner as in Example 1 in the proportions listed in Table 1. The test pieces evaluated after molding were as shown in Table 1.

Example 10 PPS powder treated with acid in the same manner as in Example 1,
The olefin copolymer and polyethylene were triblended at a weight ratio of 80:10:10, and then melt-mixed, pelletized, and injection molded in exactly the same manner as in Example 1 to obtain a test piece. The cut and notched Izot impact strength evaluated for the obtained test piece was 37 kg cm /
cm/notch, heat distortion temperature (high load) is 103℃
It is.

Example 11 Instead of using polyethylene in Example IQ, a polyethylene-polypropylene copolymer grafted with maleic anhydride ("N-Tafmer" M manufactured by Sanj1 Petrochemical Industry Co., Ltd.) was used.
Example 10 except that P-0610'') was used.
A test piece was obtained in exactly the same manner. The cut and notched Izo impact strength evaluated for the 1q test piece was 41.3 cm / cm notch, and the heat distortion temperature (high load) was 104 °C.

<Effects of the Invention> According to the present invention, a polyphenylene sulfide resin composition having extremely excellent impact resistance can now be produced.

Claims (1)

[Claims] Polyphenylene sulfide resin with sodium content of 900 ppm or less, α-olefin 60 to 99.5
Weight % and glycidyl esters of α,β-unsaturated acids 0
．． A polyphenylene sulfide resin composition containing 5 to 40% by weight of an olefin copolymer as an essential component.