JPH04103660A - Polyphenylene sulfide resin composition - Google Patents

Abstract

PURPOSE:To obtain the title resin composition having improved impact resistance and flexibility without damaging excellent characteristics of the resin by blending a polyphenylene sulfide resin with a specific polyalkylene glycol and an olefin-based copolymer. CONSTITUTION:100 pts.wt. total amounts of (A) 70-99.5wt.% polyphenylene sulfide resin and (B) 30-0.5wt.% polyalkylene glycol shown by formula I and/or formula II (R is X when n=1 and R is 2-6C organic group when N>=2; R1 is C2-6 alkylene; R2 is 1--24C organic group; X is C1-10 organic group containing at least one of epoxy group, acid anhydride group, COOH and vinyl or H; (m) is 5-25,000; (n) is 1-10; (p) is 2-100) are blended with (C) 0.5-40 pts.wt. copolymer (preferably ethylene/glycidyl methacrylate copolymer) comprising an alpha-olefin and an alpha,beta-unsaturated glycidyl ester to give the objective compound.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a resin composition in which the impact resistance of polyphenylene sulfide is improved.

[Prior Art] Polyphenylene sulfide (hereinafter abbreviated as PPS) is attracting attention as a material for electric/electronic equipment and automobile equipment due to its excellent heat resistance and chemical resistance. Furthermore, it can be molded into various molded parts, films, sheets, fibers, etc. by injection molding, extrusion molding, etc., and is widely used in fields where heat resistance and chemical resistance are required.

However, PPS has significant disadvantages of poor ductility and brittleness.

Conventionally, fillers such as glass fibers have been added to improve the impact resistance of PPS, but this improvement has not yet been sufficient for applications that require flexibility.

Polymer blends with modified polyolefin copolymers have also been attempted, for example, in JP-A-58-154757, JP-A-59-152953, and JP-A-59-1999.
189166 and the like. However, when blending these modified polyolefin copolymers with PPS,
Good PPS molded products have not been obtained due to increased viscosity and short shots during injection molding.

On the other hand, a polymer alloy with polyalkylene glycol was previously studied by the present applicant and was found to improve the tensile elongation and moldability of PPS. However, with these alloy products, PPS molded products with excellent impact resistance have not yet been obtained.

[Issues to be solved by the invention Ifi 1 The present invention has been made to solve the above-mentioned conventional technical problems, and improves moldability, impact resistance, and flexibility without impairing the characteristics of PPS. An object of the present invention is to provide a PPS resin composition.

[Means for Solving the Problems] That is, the present invention provides (a) polyphenylene sulfide resin 7
0 to 99.5% by weight, (b) 30 to 0.5% by weight of polyalkylene glycol represented by general formula (1) and/or (II) R-++0-
R, →-0-XE (1)m
n X-0fR+ O←THR2-+O-R+→-r→-
, O-X (II) (wherein R is X when n-1,
When n≧2, it is an organic group having 2 to 6 carbon atoms, R3 is an alkylene group having 2 to 6 carbon atoms, R2 is an organic group having 1 to 24 carbon atoms, and X is an epoxy group, an acid anhydride group, or a carboxyl group. , an organic group having 1 to 10 carbon atoms containing at least one vinyl group, or hydrogen, m is 5 to 25,000, and n is 1 to 10
%p represents an integer from 2 to 100) total of 10
The present invention relates to a polyphenylene sulfide resin composition in which 0.5 to 40 parts by weight of an olefin copolymer consisting of an α-olefin and a glycidyl ester of an α,β-unsaturated acid is added to 0 parts by weight.

The details will be explained below.

The pps used in the present invention is a polymer containing 70 mol% or more, more preferably 90 mol% or more of repeating units represented by the following bonding unit, and less than 30 mol% of the repeating units have the following structure. It may also be a copolymer containing a repeating unit having the following.

The above-mentioned method for producing PPS includes a method in which a halogen-substituted aromatic compound, such as p-dichlorobenzene, is polymerized in the presence of sulfur and sodium carbonate, a method in which a halogen-substituted aromatic compound, such as p-dichlorobenzene, is polymerized in the presence of sulfur and sodium carbonate, a method in which sodium sulfide, sodium hydrogen sulfide and sodium hydroxide, or sulfurized A method of polymerizing p-dichlorobenzene using hydrogen and sodium hydroxide, preferably in the presence of sodium aminoalkanoate or an alkali metal salt of an organic carboxylic acid as a polymerization aid, a method of self-polycondensing p-chlorothiophenol, etc. However, a method in which sodium sulfide and p-dichlorobenzene are reacted in an amide solvent such as N-methylpyrrolidone or dimethylacetamide or a sulfonic solvent such as dimethylsulfoxide or sulfolane is particularly preferred.

These manufacturing methods are already known, and US Patent No. 25131
Publication No. 88, Special Publication No. 44-27671, Special Publication No. 4
Publication No. 5-3368, Japanese Patent Publication No. 52-12240,
JP-A-61-225217, U.S. Patent No. 32741
No. 65, U.S. Patent No. 1160660, Special Publication No. 4
This method is disclosed in Japanese Patent No. 6-27255, Belgian Patent No. 29437, and the like.

Further, PPS may be linear or branched, or may be a mixture of these structures.

In addition, the melt viscosity of these is 10 poise to 100 as measured at 300°C using a Koka type flow tester (Dice: inner diameter 0.5 mm, length 2.0 mm, load: 10 kg).
000 po i s-e, preferably 50 po i s
It is in the range of e to 50,000 poise.

Further, in order to improve the compatibility with the polyalkylene glycol and olefin copolymer used in the present invention, highly reactive functional groups may be introduced into PPS. The functional groups to be introduced include thiol groups, amino groups, carboxyl groups, hydroxyl groups, and acid anhydride groups.

Epoxy groups and the like are preferred. Considering the reactivity with the olefin copolymer and polyalkylene glycol, amino groups and/or carboxyl groups are particularly preferred as the functional groups to be introduced into PPS.

Examples of methods for introducing it include a method of copolymerizing a halogen-containing aromatic compound containing these functional groups, and a method of introducing PPS by polymerizing a low molecular compound containing a functional group.

Furthermore, the above PPS is subjected to deionization treatment (acid cleaning, hot water cleaning, etc.)
The sodium ion content may be reduced by performing the following steps.

The polyalkylene glycol used in the present invention is a polyalkylene glycol represented by general formula (1) or (II). Preferred polyalkylene glycols used in the present invention include a formula in which R is an organic group having 1 to 9 carbon atoms having an epoxy group, a carboxyl group, or an acid anhydride group, and R3 is an alkylene group having 2 to 4 carbon atoms; R2
is an organic group having 1 to 15 carbon atoms, X is an 1 to 9 organic group having an epoxy group, a carboxyl group, or an acid anhydride group, m is 1
Examples include polyalkylene glycols in which n is 0 to 15,000, n is 1 to 5, and p is 3 to 50.

Here, R, R2, and X in the formula are expressed as organic groups, but this includes not only hydrocarbon groups but also heteroatom-containing functional groups such as ether, ketone, amide, and sulfone in RR2, However, it does mean that there is no problem. Further, m in the formula indicates the degree of polymerization of the polyalkylene glycol segment, and if m is smaller than 5, heat resistance will be poor and a large amount of gas will be generated during molding, which is not preferable. On the other hand, if m is larger than 25,000, the compatibility between polyalkylene glycol and PPS will decrease.

Some examples of the polyalkylene glycols include addition polymers of alkylene oxides and polyhydric alcohols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, glycerin, pentaerythritol, and sorbitol.

Further, an epoxy group or an acid anhydride group can be introduced into the polyalkylene glycol by utilizing the reactivity of the terminal hydroxyl group of the polyalkylene glycol. For example, epoxy-modified polyalkylene glycol can be obtained by reacting epichlorohydrin, and acid anhydride-modified polyalkylene glycol can be obtained by reacting trimellitic anhydride-containing chloride.

Specific examples of polyalkylene glycols preferably used in the present invention include polyethylene glycol and polytetramethylene glycol, which have a molecular weight of 300 to 10oooooo and whose terminal functional group is a hydroxyl group, epoxy U, carboxyl group, or acid anhydride group. .

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 examples of the α-olefin herein include ethylene, propylene, butene-1, etc. are mentioned, but ethylene is preferably used. Examples of glycidyl esters of α,β-unsaturated acids include glycidyl acrylate, glycidyl methacrylate, and glycidyl ethacrylate, with glycidyl methacrylate being particularly preferably used. The amount of copolymerized glycidyl ester of a, β-unsaturated acid in the olefin copolymer is 1
It is preferably 3 to 30% by weight to 50% by weight. If it is less than 1% by weight, the toughness will not be improved, and if it exceeds 50% by weight, the effect will not change and the cost will increase.

In addition, the olefin copolymer may be further copolymerized with other unsaturated monomers, such as vinyl ether, vinyl acetate, vinyl propionate, and acrylic, as long as the amount is 40% by weight or less and does not impede the purpose of the present invention. Methyl acid, methyl methacrylate, acrylonitrile, styrene, etc. may be copolymerized.

In the present invention, if the PPS content is less than 70% by weight, the heat resistance and chemical resistance of PPS will decrease, and if the polyalkylene glycol content is less than 0.5% by weight, the alloy will have an increased viscosity. cannot be suppressed, and moldability deteriorates. Also, a total of 100% of PPS and polyalkylene glycol
The content of olefin copolymer is 0.5f based on the heavy duplex weight.
If it is less than 1 part by weight, the impact resistance of the blend will not be improved, and if it exceeds 40 parts by weight, the flame retardance will decrease.

Furthermore, by adding a small amount of other polymers to the resin composition of the present invention,
It is also possible to impart other physical properties. Examples of the polymer to be added include olefins.

Styrene-based, urethane-based, ester-based, fluorine-based.

Thermoplastic elastomers such as amide and acrylic, polybutadiene, polyisoprene, polychloroprene, polybutene, styrene butadiene rubber and its hydrogenated products, acrylonitrile butadiene rubber, ethylene propylene copolymer, ethylene propylene ethylidene norbornene copolymer, etc. Rubber components: nylon 6, nylon 66, nylon 610, nylon 12. Nylon 11. nylon 4
Polyamide resins such as 6, polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyarylate, polystyrene, polyα-methylstyrene, polyvinyl acetate, polyvinyl chloride, polyacrylic ester, polymethacrylic ester, polyacrylonitrile , polyolefin, polyurethane, polyacetal, polyphenylene oxide, polycarbonate, polysulfone, polyether sulfone, polyallyl sulfone, polyphenylene sulfide sulfone, polyether ketone, polyether ether ketone, polyphenylene sulfide ketone, polyamideimide, silicone resin, phenoxy resin Examples include homopolymers such as fluororesins and melt-processable resins that form an anisotropic melt phase, random or block copolymers, graft copolymers, and mixtures or modified products thereof.

Furthermore, if necessary, reinforcing fillers such as glass fibers, carbon fibers, ceramic fibers such as alumina fibers, aramid fibers, wholly aromatic polyester fibers, metal fibers, potassium titanate whiskers, calcium carbonate, mica, talc, silica, etc. Barium sulfate, calcium sulfate, kaolin, clay, pyroferrite, bentonite, sericite, zeolite, nephelinsinite, attapulgite, wollastonite, ferrite, calcium silicate, magnesium carbonate, dolomite, antimony trioxide, zinc oxide, oxide Titanium, magnesium oxide, iron oxide, molybdenum disulfide, graphite, gypsum, glass beads, glass powder
Inorganic fillers such as glass balloons, quartz, quartz glass, and organic or 81H-free materials can also be blended.

For example, the glass fiber has a fiber length of 1.5 to 12 am.
, chopped strands with a fiber diameter of 3 to 24 μm, milled fibers with a fiber diameter of 3 to 8 μm, glass flakes and glass powder of 325 mesh or less.

In addition, plasticizers and mold release agents such as aromatic hydroxy derivatives,
Add silane-based and titanate-based coupling agents, lubricants, heat-resistant stabilizers, weather-resistant stabilizers, crystal nucleating agents, foaming agents, rust preventive agents, ion trapping agents, flame retardants, flame retardant aids, etc. as necessary. You may.

The method of producing the PPS resin silk compound acid of the present invention includes 1) a method of mixing each component in a mixer etc., and then melt-kneading using an extruder and then pelletizing; 2) a pellet obtained by method 1); Examples include a method in which other components are added to the mixture and melt-kneaded again to form pellets. 3) A method in which each component is dissolved in a solvent and stirred under heating.

Furthermore, it is also possible to use known equipment such as a Banbury, a kneader, and an odocrape in each of the above methods, either singly or in combination.

The PPS resin molded product of the present invention can be produced by injection molding, sheet molding,
It can be processed into various molded products by vacuum forming, irregular shaping, foam molding, etc. and used.

[Examples] The present invention will be specifically described below with reference to Examples, but the present invention is not limited only to these Examples.

In addition, the melt viscosity of PPS and the composition after alloying was measured using a Koka type flow tester (Dice: inner diameter 0.5 mm, length 2
．． 0mm; load: 10 kg) at 300°C.

Reference example 1: N in an autoclave with an internal volume of 151) equipped with a stirrer.
-Methyl-2-pyrrolidone (hereinafter abbreviated as NMP) 5
000g and sodium sulfide (Na2Sφ2.9H20
) 1898g (14.8 mol) was added, the temperature was raised to 205°C, and 420g of water and 5g of NMP were distilled off. Next, 2132 g (14.5 mol) of p-dichlorobenzene
was added, and the reaction was carried out at 250°C for 3 hours. After the reaction is complete,
The reaction was cooled to room temperature and the polymer was isolated by centrifugation. The conversion rate of dichlorobenzene was 98.5%. Wash the polymer repeatedly with warm water and heat at 100°C under reduced pressure.
By drying it all day and night, the melt viscosity was reduced to 300poi.
I got pps of se. Furthermore, by curing this PPS in air at 250°C for 5 hours, the melt viscosity was increased to 200.
Got 0poise pps. The PPS obtained in this manner is designated as PP5-I.

Reference Example 2 p-dichlorobenzene (14.35 mol) was used instead of p-dichlorobenzene (14.5 mol) in Reference Example 1; 3.
The same operation as in Reference Example 1 was performed except that 5-dichloroaniline (0.15 mol) was used. The conversion rate of the polymer is 9
4%, and the melt viscosity before and after curing is 28
0poise.

It was 2800 points. The pps thus obtained is designated as PP5-II.

Reference example 3 3,5-dichloroaniline of reference example 2 (0.15 mol)
2,4-dichlorobenzoic acid (0.15 mol) instead
The same operation as in Reference Example 2 was performed except that . The conversion rate of the polymer was 96%, and the melt viscosity before and after curing was 280 po and 2600 po, respectively.
It was ise. The PPS obtained in this way is p
ps-m.

Reference example 4 3,5-dichloroaniline of reference example 2 (0.15 mol)
3,5-diaminochlorobenzene (0,15
The same operation as in Reference Example 2 was performed except that mol) was used.

The conversion rate of the polymer was 95%, and the melt viscosity before and after curing was 110 poise and 2800 poise, respectively.
It was ois e.

The PPS thus obtained is designated as PP5-IV.

Reference example 5 Internal volume equipped with a stirrer 15. N to Q autoclave
NP5000g, sodium sulfide (Na2S・2.9H
20) 1898g (1,4,8 mol), 180'Og of sodium benzoate and 48g of sodium hydroxide were added, and the temperature was raised to 205°C, and 418g of water and 5g of NMP were distilled off. Next, 2109 g of p-dichlorobenzene (
14,35 mol) and 3,5-diaminochlorobenzene (
0,1,5 mol) at 220°C for 2 hours, then 2 hours.
The reaction was carried out at 50°C for 3 hours. After the reaction was completed, the reaction product was cooled to room temperature and the polymer was isolated using a centrifuge.

The conversion rate of dichlorobenzene was 96.0%.

The polymer was repeatedly washed with hot water and dried under reduced pressure at 100° C. for a day and night to obtain PPS with a melt viscosity of 3400 poise. The PPS obtained in this way is pps-
Let it be v.

Reference example 6 α,ω-diglycidyl polyethylene glycol (Epolite 400E, manufactured by Kyoeisha Yushi, average molecular weight 400) 2
00g and 107g of bisphenol A were heated and stirred for 200.2 hours using a separable flask under a nitrogen stream. After cooling to room temperature, it was added dropwise to a large amount of diethyl ether to remove excess bisphenol A, and then dried under reduced pressure at room temperature for a day and night to obtain a terminal epoxy group-containing PEG [general formula (II) Tybuco] with an average molecular weight of 1200. Obtained. This is abbreviated as PEG-V.

Examples 1-6. Comparative Examples 1-2 PPs obtained in Reference Examples 1-5 and commercially available polyethylene glycol (average molecular weight 400. Abbreviated as PEG-1), α, ω
- diglycidyl polyethylene glycol [general formula (1)
Type] (Evolite 1゜OE, manufactured by Kyoeisha Yushi, average molecular weight 100. Abbreviated as PEG-n, Evolite 400E
, manufactured by Kyoeisha Yushi.

Average molecular weight 400. Abbreviated as PEG-III, Bunacol EX-861, manufactured by Nagase Kasei, average molecular m 1000,
Acetone solutions of PEG-IV (abbreviated as PEG-IV) or PEG-V were mixed, dried at 100"C, and then mixed with a commercially available olefin copolymer (Bond First; manufactured by Sumima Kagaku Co., Ltd.) and PEG-V.
A homogeneous tri-blend was carried out at the composition ratio shown in the table. After pelletizing the sample at 300°C using a lab blast mill (manufactured by Toyo Seiki), the cylinder temperature was increased to 29°C using an in-line screw injection molding machine (manufactured by Toshiba, l5-50EP).
A molded article was obtained at 0°C and a mold temperature of 140°C. The Izot impact test of the molded article was determined in accordance with ASTM D256. The test results are shown in Table 1.

[Effects of the Invention] As detailed above, the present invention provides a PPS resin composition with improved impact resistance and flexibility without reducing other physical properties of PPS, and its industrial value is expensive.

Claims (1)

[Claims] (1) (a) Polyphenylene sulfide resin 70-99
．． (b) Polyalkylene glycol represented by general formula (I) and/or (II) 30-0.5% by weight ▲Mathematical formulas, chemical formulas, tables, etc. are available▼(I) ▲Mathematical formulas, chemical formulas, tables, etc. etc.▼(II) (In the formula, R is X when n=1, an organic group having 2 to 6 carbon atoms when n≧2, R_1 is an alkylene group having 2 to 6 carbon atoms,
R_2 is an organic group having 1 to 24 carbon atoms, X is an organic group having 1 to 10 carbon atoms containing at least one of an epoxy group, an acid anhydride group, a carboxyl group, and a vinyl group, or hydrogen;
is an integer of 5 to 25,000, n is an integer of 1 to 10, and p is an integer of 2 to 100), α-
A polyphenylene sulfide resin composition prepared by adding 0.5 to 40 parts by weight of an olefin copolymer consisting of an olefin and a glycidyl ester of an α,β-unsaturated acid.