CN113039244B - Polyphenylene sulfide resin composition and molded article thereof - Google Patents
Polyphenylene sulfide resin composition and molded article thereof Download PDFInfo
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- CN113039244B CN113039244B CN201980075525.2A CN201980075525A CN113039244B CN 113039244 B CN113039244 B CN 113039244B CN 201980075525 A CN201980075525 A CN 201980075525A CN 113039244 B CN113039244 B CN 113039244B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/02—Polythioethers; Polythioether-ethers
Abstract
The present invention relates to a polyphenylene sulfide resin composition comprising 5 to 2000 parts by mass of an inorganic filler per 100 parts by mass of a polyphenylene sulfide-m-phenylene sulfide random copolymer. The invention has excellent wet heat resistance, can maintain high mechanical strength under the condition of long-term contact with water, and is especially suitable for being used for injection molding into cooling water, antifreeze circulation systems of automobiles and other products contacted with water and other liquids for a long time.
Description
Technical Field
The invention relates to the field of polymer materials, in particular to a polyphenylene sulfide resin composition and a molded product thereof.
Background
Polyphenylene Sulfide (PPS) has excellent fluidity, high temperature resistance, corrosion resistance, flame retardance, balanced physical and mechanical properties, excellent dimensional stability, excellent electrical properties, and the like, and is therefore widely used in the fields of electric, electronic parts, or automobile parts, and the like. In recent years, along with the wide application of polyphenylene sulfide resin materials in cooling water and antifreeze circulating systems for automobiles and the like, there is a further demand for excellent water resistance and moist heat resistance.
In contrast, patent document 1 (japanese laid-open patent publication No. 2018-141149) discloses a resin composition containing a polyphenylene sulfide and an inorganic filler, which improves the wet heat resistance by increasing the metal sodium atom content in the polyphenylene sulfide resin to 1000ppm or more, thereby improving the tensile strength retention after the wet heat treatment. However, an increase in the metal atom content causes a decrease in the tensile strength of the polyphenylene sulfide resin composition when untreated.
Patent document 2 (japanese laid-open patent publication No. 2018-123307) discloses a resin composition containing a poly-p-phenylene sulfide, an inorganic filler and an organic nucleating agent, wherein the melt cooling crystallization temperature (T mc ) And the crystal domain size of the polyphenylene sulfide resin is reduced and uniformized, thereby improving the water pressure resistance of the molded article. However, PEEK resin added as an organic nucleating agent is liable to be a foreign substance with respect to the main polyphenylene sulfide resin.
On the other hand, patent document 3 (japanese laid-open patent publication No. 2016-69650) discloses a poly-p-phenylene sulfide-m-phenylene sulfide copolymer in which m-phenylene sulfide units are copolymerized into a polyphenylene sulfide molecule to obtain a polymer having a lower crystallinity, thereby improving the bonding property between the formed film and the metal or resin surface. However, when the polymer is not mixed with a polyphenylene sulfide homopolymer, the film formation stability is poor, and at the same time, the strength of a film formed from the polyphenylene sulfide-m-phenylene sulfide copolymer is lower than that of the polyphenylene sulfide homopolymer, and the film is not suitable for molding into cooling water for automobiles and the like, antifreeze circulation systems and other molded articles having certain strength requirements in contact with liquid such as water for a long period of time.
Disclosure of Invention
The present inventors have conducted intensive studies to solve the above problems, and have found that although a poly (p-phenylene sulfide) -m-phenylene sulfide copolymer has low strength and poor wet heat resistance, when combined with an inorganic filler, the strength can be improved and the wet heat resistance can be improved more specifically, and the polyphenylene sulfide resin composition thus obtained can not only expand the use of the copolymer in a plastic molded article, but also further improve the wet heat resistance of the plastic molded article.
The invention also provides a molded product prepared from the polyphenylene sulfide resin composition. The heat and humidity resistant water-based paint has excellent heat and humidity resistance and is suitable for cooling water of automobiles and the like, antifreeze circulating systems and other parts contacted with water and other liquids for a long time.
Namely, the technical scheme of the invention is as follows:
1. a polyphenylene sulfide resin composition comprising:
(A) Poly-p-phenylene sulfide-m-phenylene sulfide random copolymer, and
(B) An inorganic filler, wherein the inorganic filler is a polymer,
the inorganic filler (B) is blended in an amount of 5 to 2000 parts by mass relative to 100 parts by mass of the (A) poly (p-phenylene sulfide) -m-phenylene sulfide random copolymer.
2. The polyphenylene sulfide resin composition according to item 1 above, wherein the content of the m-phenylene sulfide unit in the (A) poly (p-phenylene sulfide) -m-phenylene sulfide random copolymer is 2 to 25% by weight relative to the total mass of the phenylene sulfide units in the random copolymer.
3. The polyphenylene sulfide resin composition according to item 1 above, wherein the melting point of the (A) poly (p-phenylene sulfide) -m-phenylene sulfide random copolymer is 210 to 280 ℃.
4. The polyphenylene sulfide resin composition according to item 1 above, wherein the inorganic filler (B) is blended in an amount of 26 to 2000 parts by mass based on 100 parts by mass of the (A) polyphenylene sulfide-m-phenylene sulfide random copolymer.
5. The polyphenylene sulfide resin composition according to item 1 above, further comprising (C) a polyphenylene sulfide homopolymer.
6. The polyphenylene sulfide resin composition according to item 5 above, wherein the blending amount of the (C) polyphenylene sulfide homopolymer is 10 to 2500 parts by mass per 100 parts by mass of the (A) polyphenylene sulfide-m-phenylene sulfide copolymer.
7. The polyphenylene sulfide resin composition according to the above 5, wherein the content of the m-phenylene sulfide unit in the (A) poly (p-phenylene sulfide) -m-phenylene sulfide random copolymer is 1 to 14% by weight relative to the total mass of the phenylene sulfide unit in the (A) poly (p-phenylene sulfide) -m-phenylene sulfide random copolymer and the (C) poly (p-phenylene sulfide) homopolymer.
8. The polyphenylene sulfide resin composition according to the above 5, wherein the inorganic filler (B) is blended in an amount of 5 to 150 parts by mass based on 100 parts by mass of the total mass of the (A) polyphenylene sulfide-m-phenylene sulfide random copolymer and the (C) polyphenylene sulfide homopolymer.
9. The polyphenylene sulfide resin composition according to the above 5, wherein the inorganic filler (B) is blended in an amount of 26 to 150 parts by mass based on 100 parts by mass of the total mass of the (A) polyphenylene sulfide-m-phenylene sulfide random copolymer and the (C) polyphenylene sulfide homopolymer.
10. The polyphenylene sulfide resin composition according to item 1 above, wherein the inorganic filler (B) is at least one selected from glass fibers, glass flakes, glass beads, carbon fibers, calcium carbonate, silica, talc and wollastonite.
11. The polyphenylene sulfide resin composition according to item 1 above, which further comprises (D) a silane compound.
12. The polyphenylene sulfide resin composition according to item 11 above, wherein the (D) silane compound is an alkoxysilane compound containing at least one of an epoxy group, an amino group, and an isocyanate group.
13. A molded article characterized in that: obtained by using the polyphenylene sulfide resin composition according to any one of the above 1 to 12.
14. The molded article according to the above 13, which is used in a cooling water/antifreeze circulation system.
Detailed Description
The following describes specific embodiments of the present invention:
1. (A) Poly (p-phenylene sulfide) -m-phenylene sulfide random copolymer:
the (A) poly (p-phenylene sulfide) -m-phenylene sulfide random copolymer used in the present invention is a random copolymer having repeating units represented by the following structural formula (I) and the following structural formula (II),
in the (A) poly (p-phenylene sulfide) -m-phenylene sulfide random copolymer used in the present invention, the content of the m-phenylene sulfide unit is preferably 2 to 25% by weight relative to the total mass of the phenylene sulfide units in the copolymer. When the content of the m-phenylene sulfide units is higher than 25wt%, the melting point and crystallinity of the poly-p-phenylene sulfide-m-phenylene sulfide random copolymer tend to decrease, and the heat resistance and the use temperature of the resin composition are greatly affected. The content thereof is more preferably 20wt% or less, and still more preferably 13wt% or less. When the content of the m-phenylene sulfide unit is less than 2% by weight relative to the total mass of the phenylene sulfide units in the copolymer, the effect of improving the moisture and heat resistance of the composition is limited, and the content is more preferably 3% by weight or more, and still more preferably 5% by weight or more.
The melting point of the (A) poly (p-phenylene sulfide) -m-phenylene sulfide random copolymer used in the present invention is preferably 210 to 280 ℃. When the melting point of the poly (p-phenylene sulfide) -m-phenylene sulfide random copolymer is higher than 280 ℃, the content of the intermediate phenylene sulfide units is too small, the effect of improving the moisture and heat resistance of the composition is limited, and the melting point is more preferably 270 ℃ or lower. When the melting point of the poly (p-phenylene sulfide) -m-phenylene sulfide random copolymer is lower than 210 ℃, the heat resistance thereof is greatly reduced, and the copolymer is unfavorable for use in a high-temperature environment, and the melting point thereof is more preferably 235 ℃ or higher, and still more preferably 250 ℃ or higher.
2. (B) Inorganic filler:
the composition formed of the (a) polyphenylene sulfide-m-phenylene sulfide random copolymer and the (B) inorganic filler has higher wet heat resistance than the composition formed of the (C) polyphenylene sulfide homopolymer and the (B) inorganic filler described later.
The inorganic filler according to the present invention refers to fillers known to be useful in resins. Such as glass fibers, carbon fibers, potassium titanate whiskers, zinc whisker oxide, aluminum borate whiskers, aramid fibers, aluminum oxide fibers, silicon carbide fibers, ceramic fibers, asbestos fibers, gypsum fibers, metal fibers, glass flakes, wollastonite, zeolite, sericite, kaolin, mica, talc, clay, pyrophyllite, bentonite, montmorillonite, hectorite, synthetic mica, asbestos, graphite, aluminosilicate, alumina, silica, magnesia, zirconia, titania, iron oxide, calcium carbonate, magnesium carbonate, dolomite, calcium sulfate, barium sulfate, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, glass microspheres, hollow glass microspheres, ceramic beads, boron nitride, silicon carbide, wollastonite, or the like. The inorganic filler may be a hollow inorganic filler in structure, and further, 2 or more kinds of the inorganic fillers may be selected for use. The average diameter of the inorganic filler is not particularly limited, and preferably 0.001 to 20. Mu.m, in this range, good fluidity and better appearance can be obtained.
In particular, in order to obtain a polyphenylene sulfide resin composition excellent in performance from the viewpoint of the combination of low molding shrinkage and flowability, the inorganic filler is preferably at least one of glass fiber or carbon fiber. The glass fiber is not particularly limited, and may be glass fiber used in the prior art. The glass fiber may be a fiber in the form of chopped strands, grit, milled fibers, or the like cut to length. In general, it is preferable to use glass fibers having an average diameter of 5 to 15. Mu.m. In the case of using chopped strands, the length is not particularly limited, and a fiber having a standard 3mm length suitable for extrusion kneading is preferably used. The cross-sectional shape of the fibrous filler is not particularly limited, and any one or more of round and flat fibers may be selected and used.
On the other hand, at least one of glass flakes, glass beads, hollow glass beads, calcium carbonate, silica, talc or wollastonite is preferable for obtaining a better product appearance.
3. The proportion of the component (B)
In the present invention, the content of the inorganic filler (B) is preferably 5 to 2000 parts by mass based on 100 parts by mass of the poly (p-phenylene sulfide) -m-phenylene sulfide random copolymer of the component (A). Within this addition range, the polyphenylene sulfide resin composition of the present invention can have good mechanical strength while maintaining good fluidity, processability and toughness. In the present invention, the amount of the component (B) to be added is preferably 26 parts by mass or more, more preferably 40 parts by mass or more, based on 100 parts by mass of the component (a). On the other hand, the amount of the inorganic filler (B) added is preferably 800 parts by mass or less, more preferably 300 parts by mass or less.
4. (C) Poly (p-phenylene sulfide) homopolymers
The (A) polyphenylene sulfide homopolymer used in the present invention is a polymer having a repeating unit represented by the following structural formula (I).
The structure of the polyphenylene sulfide homopolymer is not particularly limited, and a linear type polyphenylene sulfide may be used, or an oxidative crosslinking type polyphenylene sulfide or a branched type polyphenylene sulfide to which a tri-halogen functional reactant is added, preferably in an amount of less than 1wt%, may be used.
The polyphenylene sulfide homopolymer used in the present invention is not limited to a production method, and for example, a polyphenylene sulfide homopolymer having the structure of the above-mentioned structural formula (I) can be produced by a method for obtaining a high fluidity described in Japanese patent publication No. 45-3368 or a method for obtaining a low fluidity described in Japanese patent publication No. 52-12240. The former differs from the latter in the presence or absence of the polymerization aid alkali metal carboxylate in the polymerization system. In the former method, alkali metal carboxylate is not added into the polymerization system, so that the fluidity is high; in the latter method, an alkali metal carboxylate is added to the polymerization system, and fluidity is low, thereby contributing to toughness of the resin. The polyphenylene sulfide polymer prepared by the two methods may be used in combination, thereby balancing the fluidity and toughness of the polyphenylene sulfide resin.
In addition, the polyphenylene sulfide polymer prepared by the method can be subjected to end capping treatment to obtain the polyphenylene sulfide polymer with lower chlorine content. For example, capping with 2-mercaptobenzimidazole under basic conditions can result in a capped poly (p-phenylene sulfide) homopolymer having a lower chlorine content.
5. The ratio of the component (A) to the component (C)
In the present invention, when the component (C) is added to the component (a) poly (p-phenylene sulfide) -m-phenylene sulfide random copolymer, the blending amount of the component (C) poly (p-phenylene sulfide) homopolymer is preferably 10 to 2500 parts by mass based on 100 parts by mass of the component (a) poly (p-phenylene sulfide) -m-phenylene sulfide random copolymer. In the present invention, the components (a) and (C) may be mixed in a further preferable ratio in order to achieve an improvement in wet heat resistance while maintaining the mechanical strength and heat resistance of the composition. In the present invention, the component (C) is preferably 40 parts by mass or more, more preferably 60 parts by mass or more, per 100 parts by mass of the component (a). On the other hand, the amount of component (C) added is preferably 1000 parts by mass or less, more preferably 900 parts by mass or less. When the content of the component (C) is less than 10 parts by mass per 100 parts by mass of the component (A), the mechanical strength of the composition is lowered. When the content of the component (C) is more than 2500 parts by mass, the composition has a limited effect of improving the wet heat resistance.
In the present invention, the content of the m-phenylene sulfide unit contained in the (A) poly (p-phenylene sulfide) -m-phenylene sulfide random copolymer is preferably 1 to 14% by weight relative to the total mass of the phenylene sulfide unit in the (A) poly (p-phenylene sulfide) -m-phenylene sulfide random copolymer and the (C) poly (p-phenylene sulfide) homopolymer. When the content of the m-phenylene sulfide unit contained in the (a) poly (p-phenylene sulfide) -m-phenylene sulfide random copolymer is less than 1% by weight, the composition is limited in the effect of improving the wet heat resistance, and the content thereof is more preferably 2.5% by weight or more, relative to the total mass of the phenylene sulfide unit in the (a) poly (p-phenylene sulfide) -m-phenylene sulfide random copolymer and the (C) poly (p-phenylene sulfide) homopolymer. When the content of the m-phenylene sulfide unit contained in the (a) poly (p-phenylene sulfide) -m-phenylene sulfide random copolymer is higher than 14% by weight, the mechanical strength and heat resistance of the composition tend to be lowered, and the content thereof is more preferably 13% by weight or less, and still more preferably 11% by weight or less, relative to the total mass of the phenylene sulfide unit in the (a) poly (p-phenylene sulfide) -m-phenylene sulfide random copolymer and the (C) poly (p-phenylene sulfide) homopolymer.
6. The ratio of component (B) to component (A) and component (C)
In the present invention, when the component (a) and the component (C) are mixed, the content of the inorganic filler in the component (B) is preferably 5 to 150 parts by mass based on 100 parts by mass of the total mass of the component (a) and the component (C). Within this addition range, the polyphenylene sulfide resin composition of the present invention can have good mechanical strength while maintaining good fluidity, processability and toughness. In the present invention, the amount of the component (B) to be added is preferably 26 parts by mass or more, more preferably 40 parts by mass or more, based on 100 parts by mass of the total mass of the component (a) and the component (C). On the other hand, the amount of the inorganic filler to be added is preferably 110 parts by mass or less, more preferably 80 parts by mass or less.
7. (D) Silane compound
In the present invention, (D) a silane compound may be further added from the viewpoint of enhancing the adhesion between the resin and the inorganic filler. The silane compound is preferably an alkoxysilane compound having one or more groups selected from epoxy group, amino group, isocyanate group, hydroxyl group, mercapto group, and urea group.
Specific examples of the alkoxysilane compound having at least 1 functional group selected from the group consisting of epoxy group, amino group, isocyanate group, hydroxyl group, mercapto group and ureido group include epoxy group-containing alkoxysilane compounds such as gamma-glycidoxypropyl trimethoxysilane, gamma-glycidoxypropyl triethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, etc., mercapto group-containing alkoxysilane compounds such as gamma-mercaptopropyl trimethoxysilane and gamma-mercaptopropyl triethoxysilane, ureido group-containing alkoxysilane compounds such as gamma-ureidopropyl triethoxysilane, gamma-ureidopropyl trimethoxysilane and gamma- (2-ureidoethyl) aminopropyl trimethoxysilane, etc., isocyanate group-containing alkoxysilane compounds such as gamma-isocyanatopropyl triethoxysilane, gamma-isocyanatopropyl trimethoxysilane, gamma-isocyanatopropyl methyldimethoxy silane, gamma-isocyanatopropyl methyldiethoxysilane, gamma-isocyanatopropyl diethoxysilane, gamma-isocyanatopropyl trichlorosilane, etc., gamma-amino ethyl-amino propyl trimethoxysilane, gamma-amino propyl silane, gamma- (2-ureido) amino propyl silane, gamma-amino propyl trimethoxysilane, etc., and hydroxy-containing alkoxysilane compounds such as gamma-hydroxypropyl trimethoxysilane and gamma-hydroxypropyl triethoxysilane.
In the present invention, the silane compound (D) is preferably 0.01 to 3 parts by mass relative to 100 parts by mass of the total mass of the component (a) poly (p-phenylene sulfide) -m-phenylene sulfide random copolymer and the component (C) poly (p-phenylene sulfide) homopolymer, in view of adhesion and flowability. By adding the silane compound in the above-described range, the adhesion between the polyphenylene sulfide resin and the inorganic filler can be enhanced while maintaining the fluidity of the polyphenylene sulfide resin composition in the present invention. The content of the silane compound is more preferably 0.05 parts by mass or more, and still more preferably 0.1 parts by mass or more. Meanwhile, the content thereof is more preferably 2 parts by mass or less, and still more preferably 1 part by mass or less.
In the present invention, the component (D) preferably has an alkoxysilane compound containing at least one of an epoxy group, an amino group, or an isocyanate group, in order to improve the reactivity with the polyphenylene sulfide resin.
8. Other additives
The polyphenylene sulfide resin composition of the present invention may further include, in addition to the components (a) to (D), an elastomer, an antioxidant, a mold release agent (montanic acid and its metal salts, esters thereof, half esters thereof, stearyl alcohol, stearamide, biurea or polyethylene wax, etc., wherein, in order to reduce gas generation during molding, stearamide is preferable), a pigment (cadmium sulfide, phthalocyanine, or colored carbon black master batch, etc.), a dye (nigrosine, etc.), a crystallization agent (talc, titanium dioxide, kaolin, clay, etc.), a plasticizer (octyl-p-hydroxybenzoate, N-butylbenzenesulfonamide, etc.), an antistatic agent (alkyl sulfate type anionic antistatic agent, quaternary ammonium type cationic antistatic agent, polyoxyethylene sorbitan monostearate, or betaine amphoteric antistatic agent), a flame retardant (e.g., red phosphorus, phosphate, melamine cyanurate, magnesium hydroxide, aluminum hydroxide, ammonium polyphosphate, brominated polystyrene, brominated polyphenylene oxide, polycarbonate bromide, brominated epoxy resin, or a combination of these bromine-containing flame retardants and antimony trioxide), etc., and may be selected from one or more of them to be used in combination.
The elastomer may be exemplified by: one or more of an olefin elastomer, a modified olefin elastomer, a styrene elastomer, and the like.
Examples of the olefin-based elastomer include: and a copolymer of an alpha-olefin such as ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, or isobutylene, or a copolymer of an alpha-olefin and an alpha, beta-unsaturated acid such as acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, or butyl methacrylate, or an alkyl ester thereof. From the viewpoint of excellent toughness, preferable are: polyethylene, polypropylene, ethylene/propylene copolymers, ethylene/1-butene copolymers, ethylene/methyl acrylate copolymers, ethylene/ethyl acrylate copolymers, ethylene/butyl acrylate copolymers, ethylene/methyl methacrylate copolymers, ethylene/ethyl methacrylate copolymers, ethylene/butyl methacrylate copolymers, and the like.
The modified olefin elastomer can be obtained by introducing a monomer component (functional group-containing component) having a functional group such as an epoxy group, an acid anhydride group, or an ionomer into the olefin elastomer. The functional group-containing component may be exemplified by: monomers containing an acid anhydride group such as maleic anhydride, itaconic anhydride, citraconic anhydride, endobicyclo [ 2,1 ] 5-heptene-2, 3-dicarboxylic acid, or endobicyclo [ 2,1 ] 5-heptene-2, 3-dicarboxylic anhydride, monomers containing an epoxy group such as glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, or glycidyl citraconate, or monomers containing an ionomer such as a carboxylic acid metal complex.
The method of introducing these functional group-containing monomer components is not particularly limited, and the following methods may be employed: copolymerization with a component used in polymerization of the olefin elastomer; or a method of grafting an olefin-based (co) polymer with a radical initiator. The amount of the functional group-containing component to be introduced is 0.001 to 40mol%, preferably 0.01 to 35mol%, based on the total monomers constituting the modified olefin elastomer.
Particularly useful modified olefin elastomers obtained by introducing a monomer component having a functional group such as an epoxy group, an acid anhydride group, or an ionomer into an olefin elastomer include: ethylene/propylene-g-glycidyl methacrylate copolymer ("g" means grafting, the same applies hereinafter), ethylene/1-butene-g-glycidyl methacrylate copolymer, ethylene/glycidyl acrylate copolymer, ethylene/glycidyl methacrylate copolymer, ethylene/methyl acrylate/glycidyl methacrylate copolymer, ethylene/methyl methacrylate/glycidyl methacrylate copolymer, ethylene/propylene-g-maleic anhydride copolymer, ethylene/1-butene-g-maleic anhydride copolymer, ethylene/methyl acrylate-g-maleic anhydride copolymer, ethylene/ethyl acrylate-g-maleic anhydride copolymer, ethylene/methyl methacrylate-g-maleic anhydride copolymer, ethylene/ethyl methacrylate-g-maleic anhydride copolymer, zinc complex of ethylene/methacrylic acid copolymer, magnesium complex of ethylene/methacrylic acid copolymer, or sodium complex of ethylene/methacrylic acid copolymer, and the like.
From the standpoint of compatibility, preferable are: ethylene/glycidyl methacrylate copolymer, ethylene/methyl acrylate/glycidyl methacrylate copolymer, ethylene/methyl methacrylate/glycidyl methacrylate copolymer, ethylene/1-butene-g-maleic anhydride copolymer, or ethylene/ethyl acrylate-g-maleic anhydride copolymer. Further preferred are: ethylene/glycidyl methacrylate copolymer, ethylene/methyl acrylate/glycidyl methacrylate copolymer, or ethylene/methyl methacrylate/glycidyl methacrylate copolymer.
The styrene-based elastomer may be exemplified by: styrene/butadiene copolymers, styrene/ethylene/propylene copolymers, styrene/isoprene copolymers, etc., are preferable from the standpoint of compatibility.
The addition amount of the elastomer is as follows from the aspects of fluidity and toughness: the amount of the above-mentioned elastomer is preferably 0.5 to 20 parts by mass, more preferably 0.8 to 10 parts by mass, still more preferably 1 to 6 parts by mass, relative to 100 parts by mass of the component (A) and the component (C), and the above-mentioned elastomer may be used in combination in such a range that the effect of the present invention is not impaired.
The antioxidant is preferably at least one selected from a phenolic antioxidant and a phosphorus antioxidant. When the phenolic antioxidant and the phosphorus antioxidant are used in combination, heat resistance and thermal stability can be maintained efficiently, and therefore, the combination of both is preferable.
As the phenolic antioxidant, a hindered phenol compound is preferably used. Specific examples are: triethylene glycol bis (3-tert-butyl- (5-methyl-4-hydroxybenzyl) propionate), N '-hexamethylenebis (3, 5-di-tert-butyl-4-hydroxy-hydrocinnamamide), tetrakis (methylene-3- (3', 5 '-di-tert-butyl-4' -hydroxybenzyl) propionate) methane, pentaerythritol tetrakis (3- (3 ',5' -di-tert-butyl) -4 '-hydroxybenzyl) propionate), 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -s-triazine-2, 4,6- (1H, 3H, 5H) -trione, 1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 4' -butylidenebis (3-methyl-6-tert-butylphenyl), N-octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 3, 9-bis (2- (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1, 1-dimethylethyl) -2,4,8, 10-tetraoxaspiro (5, 5) undecane, or 1,3, 5-trimethyl-2, 4, 6-tris- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, and the like. Among them, preferred are ester type high molecular hindered phenols, and specifically preferred are tetrakis (methylene-3- (3 ',5' -di-t-butyl-4 '-hydroxybenzyl) propionate) methane, pentaerythritol tetrakis (3- (3', 5 '-di-t-butyl) -4' -hydroxybenzyl) propionate), 3, 9-bis (2- (3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1, 1-dimethylethyl) -2,4,8, 10-tetraoxaspiro (5, 5) undecane and the like.
Examples of the phosphorus antioxidant include bis (2, 6-di-t-butyl-4-methylphenyl) pentaerythritol-bisphosphite, bis (2, 4-di-t-butylphenyl) pentaerythritol-bisphosphite, bis (2, 4-dicumylphenyl) pentaerythritol-bisphosphite, tris (2, 4-di-t-butylphenyl) phosphite, tetrakis (2, 4-di-t-butylphenyl) -4,4' -bisphenylphosphite, distearyl pentaerythritol-bisphosphite, triphenyl phosphite, and diethyl 3, 5-dibutyl-4-hydroxybenzyl phosphate.
The amount of the antioxidant to be added is preferably 0.01 to 3 parts by mass, more preferably 0.05 to 2 parts by mass, and most preferably 0.1 to 1 part by mass based on 100 parts by mass of the relative components (A) and (C).
The polyphenylene sulfide resin composition of the present invention can be molded by a general resin molding method, and has excellent mechanical strength and wet heat resistance, and is particularly suitable for injection molding into cooling water for automobiles and the like, antifreeze circulation systems, and other products which are in long-term contact with liquids such as water.
The present invention is further illustrated by the following examples, which are given by way of illustration of detailed embodiments and specific procedures, but the scope of the present invention is not limited to the following examples.
Examples
1. Raw material of polyphenylene sulfide resin composition
Poly (p-phenylene sulfide) -m-phenylene sulfide random copolymer (p-PPS/m-PPS random copolymer) A-1: linear type p-phenylene sulfide-m-phenylene sulfide random copolymer (m-phenylene sulfide unit 1wt%, weight average molecular weight: 50,000)
Poly (p-phenylene sulfide) -m-phenylene sulfide random copolymer (p-PPS/m-PPS random copolymer) A-2: linear type p-phenylene sulfide-m-phenylene sulfide random copolymer (m-phenylene sulfide unit 2wt%, weight average molecular weight: 49,000)
Poly (p-phenylene sulfide) -m-phenylene sulfide random copolymer (p-PPS/m-PPS random copolymer) A-3: linear type p-phenylene sulfide-m-phenylene sulfide random copolymer (m-phenylene sulfide unit 5wt%, weight average molecular weight: 54,000)
Poly (p-phenylene sulfide) -m-phenylene sulfide random copolymer (p-PPS/m-PPS random copolymer) A-4: linear type p-phenylene sulfide-m-phenylene sulfide random copolymer (m-phenylene sulfide unit 8wt%, weight average molecular weight: 51,000)
Poly (p-phenylene sulfide) -m-phenylene sulfide random copolymer (p-PPS/m-PPS random copolymer) A-5: linear type p-phenylene sulfide-m-phenylene sulfide random copolymer (m-phenylene sulfide unit 10wt%, weight average molecular weight: 52,000)
Poly (p-phenylene sulfide) -m-phenylene sulfide random copolymer (p-PPS/m-PPS random copolymer) A-6: linear type p-phenylene sulfide-m-phenylene sulfide random copolymer (m-phenylene sulfide unit 20wt%, weight average molecular weight: 58,000)
Poly (p-phenylene sulfide) -m-phenylene sulfide random copolymer (p-PPS/m-PPS random copolymer) A-7: linear type p-phenylene sulfide-m-phenylene sulfide random copolymer (m-phenylene sulfide unit 25wt%, weight average molecular weight: 53,000)
Poly (p-phenylene sulfide) -m-phenylene sulfide block copolymer (p-PPS/m-PPS block copolymer) a' -1: linear para-phenylene sulfide-m-phenylene sulfide block copolymer (m-phenylene sulfide unit 10wt%, weight average molecular weight: 54,000)
Poly (p-phenylene sulfide) homopolymer (p-PPS) C-1: linear p-PPS resin (weight average molecular weight: 49,000)
Glass fiber B-1: japanese electric Nitro Co Ltd.T-760H (Single fiber diameter 10.5 μm)
Calcium carbonate B-2: calfine KSS-1000 from Kagaku Co., ltd
Silane compound D-1: dow Chemical Company, XIAMETER TM OFS-6040
Mold release agent E-1: PRIME POLYMER, PE7000FB
Pigment F-1: carbon black masterbatch, toli Co., ltd.S 771B2
2. The tests involved in the examples and comparative examples are illustrated below:
1) Melting point determination
About 5mg of the polyphenylene sulfide resin composition particles obtained in the examples and comparative examples after extrusion granulation and drying were cut out with a cutter. The cut sample was then raised from 0℃to 340℃at a temperature-raising rate of 20℃per minute under a nitrogen atmosphere by a DSC-discover model 250 Differential Scanning Calorimeter (DSC), kept at 340℃for 5 minutes, and then lowered from 340℃to 0℃at a temperature-lowering rate of 20℃per minute, and kept at 0℃for 3 minutes. Then the temperature is increased from 0 ℃ to 340 ℃ at the heating rate of 20 ℃/min, and the peak-to-peak temperature of the endothermic peak appearing in the heating process is the melting point.
2) Tensile strength test:
the injection molded standard bars obtained in examples and comparative examples were measured according to ISO 527-1, -2 standard, the stretching rate was 5mm/min, the distance between the bars was 50mm, the distance between the jigs was 115mm, and the average value of 5 bars per group was taken as the tensile strength.
3) Tensile strength test after PCT treatment:
the injection molded standard bars obtained in examples and comparative examples were placed in a constant temperature and humidity cabinet of EHS-221M type manufactured by espec Co., ltd. And treated at 121 ℃ X100% relative humidity for 100 hours, and then taken out to evaluate the tensile strength after PCT treatment by the tensile strength test described above, and 5 pieces each were averaged to obtain the tensile strength after PCT treatment.
4) Tensile strength retention calculation after PCT treatment:
assuming that the tensile strength evaluated in the above test method is S1 and the tensile strength after PCT treatment is S2, the tensile strength retention after PCT treatment is calculated according to the following formula (1):
5) Shear strength test at resin matrix and glass fiber peel:
the center portions of the standard bars obtained in examples and comparative examples were cut into sheet samples along a plane perpendicular to the long side direction of the bars, and individual glass fibers present in the obtained sheet cut samples were pushed out from the resin matrix by a hemispherical indenter of a high-resolution ultra-fine durometer Triboindinder TI950 of Hysicron Co., ltd.) along a direction perpendicular to the cross-section of the glass fibers in the cut samples, whereby the shear strength at which peeling of the resin and glass fibers occurred was measured. The higher the shear strength at which the resin matrix and glass fibers are peeled off, the better the adhesion of the resin to the glass fibers.
6) Measurement of the resin adhesion ratio on the glass fiber surface after PCT treatment:
the center of the PCT treated standard bars obtained in examples and comparative examples was cut out, dissolved in α -chloronaphthalene, filtered at high temperature, and the glass fibers remaining on the funnel after high temperature filtration were washed, recovered and dried, and then elemental analysis was performed on the glass fiber surfaces using the quantia SXM from PHI corporation. The relative content S (atomic%) of the sulfur element derived from the polyphenylene sulfide resin among the detected elements was obtained. The larger the S value is, the larger the proportion of the polyphenylene sulfide resin contained in the detected element is.
Examples 1 to 5 and comparative examples 1 to 3:
the raw materials were pelletized using a TEX30 α twin screw extruder (L/d=45.5) made by japan steel company, which has 13 heating zones, has two sets of feeding devices with metering equipment, and has a vacuum exhaust apparatus, as shown in table 1. After mixing other raw materials except glass fiber, adding the raw materials from a main feeding port of an extruder, adding the glass fiber from a side feeding port of the extruder, setting the temperature of the extruder to be 200-330 ℃, and obtaining the granular polyphenylene sulfide resin composition through melting, extruding, cooling and granulating; after the pellets were dried in an oven at 130℃for 3 hours, they were injection molded into ISO standard bars (bar mold size 10mm wide by 4mm thick) using an NEX50 model injection molding machine manufactured by Nikkin resin industries Co., ltd.) at a molding temperature of 330℃and a mold temperature of 130℃and tested for performance according to the test method described above. The melting point, tensile strength, and wet heat resistance data (evaluated by tensile strength and tensile strength retention after 100 hours PCT treatment) of the composition are shown in table 1.
Examples 6 to 7 and comparative examples 4 to 8:
the test method was carried out by performing an ISO standard test specimen (specimen mold size: 10mm wide by 4mm thick) by injection molding using an NEX50 model injection molding machine manufactured by Nikkin resin industries, inc. at a molding temperature of 330℃and a mold temperature of 70℃and performing a heat treatment in an oven at 145℃for 1 hour (when the specimens shown in Table 1 were molded under the same conditions, the curing speed was too slow, and the ISO standard specimen was deformed during demolding, so that the heat treatment was performed after the low-temperature molding). Otherwise, the melting point, tensile strength and wet heat resistance data (evaluated by tensile strength and retention of tensile strength after 100 hours PCT treatment) of the composition are shown in table 2, as in the preparation method of example 1. The peel shear strength between the glass fibers and the resin matrix of example 6 and comparative example 4 and the resin adhesion ratio data of the glass fiber surfaces are shown in table 4.
Examples 8 to 15:
the melting point, tensile strength and wet heat resistance data (evaluated by tensile strength and tensile strength retention after 100 hours PCT treatment) of the composition are shown in table 3, as in the preparation method and evaluation method of example 1, except that the polyphenylene sulfide homopolymer was added.
TABLE 1
TABLE 2
TABLE 3 Table 3
TABLE 4 Table 4
1) The shear strength of the glass fiber-resin matrix separation was calculated by taking the strength of the standard bar of comparative example 4 before PCT treatment as 100%
As can be seen from the comparison of examples 1 to 5 with comparative examples 1 to 2 and the comparison of examples 6 to 7 with comparative example 4, the resin composition of the present invention formed by mixing (A) the polyphenylene sulfide-m-phenylene sulfide random copolymer and (B) the inorganic filler has a higher tensile strength and strength retention after 100 hours PCT treatment than the resin composition formed of the polyphenylene sulfide-m-phenylene sulfide block copolymer or the polyphenylene sulfide homopolymer and the inorganic filler, and the resin composition has better wet heat resistance.
As is clear from the comparison of example 5 with comparative example 3 and the comparison of example 6 with comparative example 5, the polyphenylene sulfide resin composition has a low tensile strength and strength retention after 100 hours of PCT treatment without adding an inorganic filler.
As is clear from the comparison of example 6 and comparative examples 6 to 8, when the amount of the inorganic filler added is too small, the tensile strength and the strength retention after 100 hours of PCT treatment of the polyphenylene sulfide resin composition are low. On the other hand, when the amount of the inorganic filler is too large, the composition cannot be kneaded by an extruder.
As is clear from the comparison of examples 8 to 15 and comparative example 2, the tensile strength and the strength retention after 100 hours PCT treatment were high by mixing (A) the polyphenylene sulfide-m-phenylene sulfide random copolymer, (B) the resin composition formed of the inorganic filler and (C) the resin composition formed of the polyphenylene sulfide homopolymer.
As can be seen from a comparison of example 6 and comparative example 4, the resin composition of the present invention formed by mixing (a) the polyphenylene sulfide-m-phenylene sulfide random copolymer and (B) the inorganic filler has a higher shear strength at which peeling occurs between the glass fiber and the resin matrix after 100 hours PCT treatment and a larger proportion of the resin attached to the glass fiber surface than the resin composition formed of the polyphenylene sulfide homopolymer and the inorganic filler.
Claims (7)
1. Use of a polyphenylene sulfide resin composition for producing a molded article resistant to moist heat, the polyphenylene sulfide resin composition comprising:
(A) A poly (p-phenylene sulfide) -m-phenylene sulfide random copolymer,
(B) An inorganic filler, and
(C) A poly (p-phenylene sulfide) homopolymer, wherein,
the inorganic filler (B) is mixed in an amount of 5 to 2000 parts by mass relative to 100 parts by mass of the (A) poly (p-phenylene sulfide) -m-phenylene sulfide random copolymer,
the content of the m-phenylene sulfide units in the (A) poly (p-phenylene sulfide) -m-phenylene sulfide random copolymer is 1 to 14 weight percent relative to the total mass of the phenylene sulfide units in the (A) poly (p-phenylene sulfide) -m-phenylene sulfide random copolymer and the (C) poly (p-phenylene sulfide) homopolymer,
in the (A) poly (p-phenylene sulfide) -m-phenylene sulfide random copolymer, the content of m-phenylene sulfide units is 2-25wt% relative to the total mass of phenylene sulfide units in the random copolymer,
the inorganic filler (B) is mixed in an amount of more than 71.6 parts by mass and 80 parts by mass or less relative to 100 parts by mass of the total mass of the (A) poly-p-phenylene sulfide-m-phenylene sulfide random copolymer and the (C) poly-p-phenylene sulfide homopolymer.
2. Use according to claim 1, wherein the (a) poly-p-phenylene sulfide-m-phenylene sulfide random copolymer has a melting point of 210-280 ℃.
3. The use according to claim 1, wherein the inorganic filler (B) is blended in an amount of 26 to 800 parts by mass relative to 100 parts by mass of the (a) poly (p-phenylene sulfide) -m-phenylene sulfide random copolymer.
4. The use according to claim 1, wherein the blending amount of the (C) poly (p-phenylene sulfide) homopolymer is 10 to 2500 parts by mass relative to 100 parts by mass of the (a) poly (p-phenylene sulfide) -m-phenylene sulfide copolymer.
5. The use according to claim 1, wherein the (B) inorganic filler is at least one selected from glass fibers, glass flakes, glass microspheres, carbon fibers, calcium carbonate, silica, talc or wollastonite.
6. The use according to claim 1, wherein the polyphenylene sulfide resin composition further comprises (D) a silane compound.
7. The use according to claim 6, wherein the (D) silane compound is an alkoxysilane compound containing at least one of an epoxy group, an amino group, or an isocyanate group.
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| CN201811578930.XA CN111349339A (en) | 2018-12-24 | 2018-12-24 | Polyphenylene sulfide resin composition and molded article thereof |
| CN201811579437.XA CN111349340A (en) | 2018-12-24 | 2018-12-24 | Polyphenylene sulfide resin composition and molded article thereof |
| PCT/CN2019/126492 WO2020135200A1 (en) | 2018-12-24 | 2019-12-19 | Polyphenylene sulfide resin composition and molded product thereof |
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