WO2020135200A1 - Polyphenylene sulfide resin composition and molded product thereof - Google Patents

Polyphenylene sulfide resin composition and molded product thereof Download PDF

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Publication number
WO2020135200A1
WO2020135200A1 PCT/CN2019/126492 CN2019126492W WO2020135200A1 WO 2020135200 A1 WO2020135200 A1 WO 2020135200A1 CN 2019126492 W CN2019126492 W CN 2019126492W WO 2020135200 A1 WO2020135200 A1 WO 2020135200A1
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Prior art keywords
phenylene sulfide
poly
sulfide
mass
resin composition
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PCT/CN2019/126492
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French (fr)
Chinese (zh)
Inventor
赵宸胄
汤先文
加藤公哉
松田政
胡平
Original Assignee
东丽先端材料研究开发（中国）有限公司
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Priority claimed from CN201811579437.XA external-priority patent/CN111349340A/en
Priority claimed from CN201811578930.XA external-priority patent/CN111349339A/en
Application filed by 东丽先端材料研究开发（中国）有限公司 filed Critical 东丽先端材料研究开发（中国）有限公司
Priority to CN201980075525.2A priority Critical patent/CN113039244B/en
Publication of WO2020135200A1 publication Critical patent/WO2020135200A1/en

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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
    • 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
    • C08K3/04—Carbon
    • 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
    • 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
    • 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
    • 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

Definitions

  • the invention relates to the field of polymer materials, in particular to a polyphenylene sulfide resin composition and its molded product.
  • Polyphenylene sulfide resin has the characteristics of excellent fluidity, high temperature resistance, corrosion resistance, flame retardancy, balanced physical and mechanical properties, excellent dimensional stability, and excellent electrical properties, so it is widely used in electrical , Electronic parts or auto parts.
  • PPS Polyphenylene sulfide resin
  • Patent Document 1 Japanese Laid-Open Patent Publication No. 2018-1411489 discloses a resin composition containing poly-p-phenylene sulfide and an inorganic filler by increasing the content of metal sodium atoms in the polyphenylene sulfide resin To 1000ppm or more, so as to improve the tensile strength retention rate after wet heat treatment to improve its resistance to heat and humidity.
  • an increase in the content of metal atoms leads to a decrease in the tensile strength of the polyphenylene sulfide resin composition when untreated.
  • Patent Document 2 Japanese Laid-Open Patent Publication No. 2018-1233057 discloses a resin composition containing poly-p-phenylene sulfide, inorganic filler and organic nucleating agent, which is improved by adding an appropriate amount of organic nucleating agent
  • the melt temperature of the polyphenylene sulfide resin is lowered to the crystallization temperature (T mc ), and the crystal area of the polyphenylene sulfide resin is reduced and uniformed, thereby improving the water pressure resistance of the molded product.
  • T mc crystallization temperature
  • PEEK resin added as an organic nucleating agent tends to become a foreign substance relative to the main polyphenylene sulfide resin.
  • Patent Document 3 Japanese Laid-Open Patent Publication No. 2016-69650 discloses a poly-p-phenylene sulfide-m-phenylene sulfide copolymer by copolymerizing m-phenylene sulfide units into polyphenylene sulfide molecules A polymer with lower crystallinity is obtained, thereby improving the adhesion between the formed film and the surface of metal and resin.
  • the film-forming stability is not good when it is not mixed with poly-p-phenylene sulfide homopolymer, and at the same time, the strength of the film formed by the poly-p-phenylene sulfide-m-phenylene sulfide copolymer is lower than that of poly-p-phenylene sulfide.
  • Homopolymer is not suitable for injection molding into cooling water of automobiles, antifreeze circulation systems and other molded products with certain strength requirements that have been in contact with water and other liquids for a long time.
  • the present inventors have found that although the poly-p-phenylene sulfide-m-phenylene sulfide copolymer has low strength and poor heat and humidity resistance, when combined with inorganic fillers, it can not only increase the strength, but also be more specific.
  • the polyphenylene sulfide resin composition thus obtained can not only expand the application of the copolymer in plastic molded products, but also further improve the heat and moisture resistance of plastic molded products.
  • the invention also provides a molded product prepared by the above polyphenylene sulfide resin composition. Because of its excellent resistance to heat and humidity, it is suitable for cooling water, antifreeze circulation systems of automobiles and other parts that have been in contact with liquids such as water for a long time.
  • a polyphenylene sulfide resin composition comprising:
  • the mixing amount of the (B) inorganic filler is 5 to 2000 parts by mass relative to 100 parts by mass of the (A) poly-p-phenylene sulfide-m-phenylene sulfide random copolymer.
  • polyphenylene sulfide resin composition according to the above 1, further comprising (C) a poly(p-phenylene sulfide) homopolymer.
  • the mixing amount of the ether homopolymer is 10-2500 parts by mass.
  • the polyphenylene sulfide resin composition according to the above 5, relative to (A) a poly(p-phenylene sulfide)-m-phenylene sulfide random copolymer and (C) a poly(p-phenylene sulfide) homopolymer The total mass of the phenylene sulfide unit, the content of the m-phenylene sulfide unit in the (A) poly-p-phenylene sulfide-m-phenylene sulfide random copolymer is 1-14 wt%.
  • the polyphenylene sulfide resin composition according to the above 5, relative to the (A) poly-p-phenylene sulfide-m-phenylene sulfide random copolymer and the (C) poly-p-phenylene sulfide The total mass of the homopolymer is 100 parts by mass, and the mixing amount of the (B) inorganic filler is 5-150 parts by mass.
  • the polyphenylene sulfide resin composition according to the above 5, relative to the (A) poly-p-phenylene sulfide-m-phenylene sulfide random copolymer and the (C) poly-p-phenylene sulfide The total mass of the homopolymer is 100 parts by mass, and the mixing amount of the (B) inorganic filler is 26-150 parts by mass.
  • the (A) poly(p-phenylene sulfide)-m-phenylene sulfide random copolymer used in the present invention is a random copolymer having a repeating unit represented by the following structural formula (I) and the following structural formula (II),
  • the content of m-phenyl sulfide unit is preferably 2-25 wt% relative to the total mass of the phenyl sulfide unit in the copolymer .
  • the content of m-phenylene sulfide unit is higher than 25wt% relative to the total mass of phenylene sulfide unit in the copolymer, the melting point and crystallinity of poly-p-phenylene sulfide-m-phenylene sulfide random copolymer show a downward trend, which greatly affects the resin
  • the heat resistance and use temperature of the composition is further preferably 20% by weight or less, and more preferably 13% by weight or less.
  • the content of m-phenylene sulfide unit is less than 2% by weight relative to the total mass of the phenylene sulfide unit in the copolymer, the effect of improving the moisture and heat resistance of the composition is limited, and its content is further preferably 3% by weight or more, more preferably 5% by weight the above.
  • the (A) poly(p-phenylene sulfide)-m-phenylene sulfide random copolymer used in the present invention preferably has a melting point of 210-280°C.
  • the melting point of the poly(p-phenylene sulfide)-m-phenylene sulfide random copolymer is higher than 280°C, the content of m-phenylene sulfide unit is too small, and the effect of improving the composition's resistance to moisture and heat is limited.
  • the melting point is more preferably 270 Below °C.
  • the melting point of the poly(p-phenylene sulfide)-m-phenylene sulfide random copolymer is lower than 210°C, its heat resistance is greatly reduced, which is not conducive to use in a high-temperature environment.
  • the melting point is further preferably 235°C or higher, more preferably 250°C the above.
  • composition formed by (A) poly-p-phenylene sulfide-m-phenylene sulfide random copolymer and (B) inorganic filler is relative to (C) polyphenylene sulfide homopolymer and (B) inorganic filler
  • the resulting composition has higher resistance to moisture and heat.
  • the inorganic filler in the present invention refers to fillers known to be used in resins.
  • the inorganic filler may be a hollow inorganic filler in structure, and further, two or more kinds of these inorganic fillers may be selected for use in combination.
  • the average diameter of the inorganic filler is not particularly limited, and is preferably 0.001 to 20 ⁇ m. Within this range, better fluidity and better appearance can be obtained.
  • 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 chopped strand cut with a fixed length, coarse sand, or abrasive fiber. Generally, the average diameter of the glass fiber used is preferably 5-15 ⁇ m.
  • the length is not particularly limited, but it is preferable to use standard 3 mm length fibers suitable for extrusion and kneading operations.
  • the cross-sectional shape of the fibrous filler is not particularly limited, and any one or more of round and flat fibers may be used in combination.
  • At least one of glass flakes, glass microbeads, hollow glass microbeads, calcium carbonate, silica, talc, or wollastonite is preferred.
  • the content of the (B) inorganic filler is preferably from 5 to 2000 parts by weight with respect to 100 parts by weight of the component (A) poly(p-phenylene sulfide)-m-phenylene sulfide random copolymer.
  • the polyphenylene sulfide resin composition of the present invention can have good mechanical strength while still maintaining good fluidity, processability, and toughness.
  • the amount of component (B) added is preferably 26 parts by mass or more, and more preferably 40 parts by mass or more with respect to 100 parts by mass of the component (A).
  • the addition amount of (B) inorganic filler is preferably 800 parts by mass or less, and more preferably 300 parts by mass or less.
  • the (A) poly(p-phenylene 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 poly(p-phenylene sulfide) homopolymer is not particularly limited.
  • Straight-chain poly(p-phenylene sulfide), oxidized cross-linked poly(phenylene sulfide), or a branch containing a trihalogen functional group reactant may be used.
  • the addition amount of the trihalogen functional group reactant is preferably less than 1 wt%.
  • the polyphenylene sulfide homopolymer used in the present invention is not limited to the production method.
  • the polyphenylene sulfide homopolymer having the structure of the above formula (I) can be selected from those described in Japanese Patent Publication No. 45-3368 It is prepared by the method for obtaining higher fluidity or the method for obtaining lower fluidity described in Japanese Patent Publication No. 52-12240. The difference between the former and the latter is whether there is a polymerization aid alkali metal carboxylate in the polymerization system.
  • the alkali metal carboxylate is not added to the polymerization system, and the fluidity is high; while in the latter method, the alkali metal carboxylate is added to the polymerization system, the fluidity is low, which is beneficial to the toughness of the resin . Therefore, the polyphenylene sulfide polymer prepared by the two methods can be used in combination, thereby balancing the fluidity and toughness of the polyphenylene sulfide resin.
  • polyphenylene sulfide polymer prepared above can be end-treated to obtain a polyphenylene sulfide polymer with lower chlorine content.
  • end-capping treatment with 2-mercaptobenzimidazole under alkaline conditions can provide end-capped poly(p-phenylene sulfide) homopolymer with lower chlorine content.
  • the component (C) poly(p-phenylene sulfide) homopolymer when added to the component (A) poly(p-phenylene sulfide)-m-phenylene sulfide random copolymer, relative to the component (A) 100 parts by mass of poly-p-phenylene sulfide-m-phenylene sulfide random copolymer, and the mixing amount of the component (C) poly-p-phenylene sulfide homopolymer is preferably 10-2500 parts by mass.
  • the components (A) and (C) may be mixed in a more preferable ratio.
  • the component (C) is preferably 40 parts by mass or more, and more preferably 60 parts by mass or more with respect to 100 parts by mass of the component (A).
  • the amount of component (C) added is preferably 1000 parts by mass or less, and more preferably 900 parts by mass or less.
  • the content of component (C) is less than 10 parts by mass relative to 100 parts by mass of component (A)
  • the mechanical strength of the composition decreases.
  • the content of the component (C) is higher than 2500 parts by mass, the effect of improving the moisture and heat resistance of the composition is limited.
  • the polyphenylene sulfide resin composition of the present invention can have good mechanical strength while still maintaining good fluidity, processability, and toughness.
  • the amount of component (B) added is preferably 26 parts by mass or more, and more preferably 40 parts by mass or more, relative to 100 parts by mass of the total mass of the component (A) and the component (C).
  • the added amount of the component (B) inorganic filler is preferably 110 parts by mass or less, and more preferably 80 parts by mass or less.
  • the (D) silane compound may be further added.
  • the silane compound is preferably an alkoxysilane compound having one or more groups selected from epoxy groups, amino groups, isocyanate groups, hydroxyl groups, mercapto groups, and urea groups.
  • alkoxysilane compound having at least one functional group selected from epoxy groups, amino groups, isocyanate groups, hydroxyl groups, mercapto groups, and ureido groups include ⁇ -glycidoxypropyltrimethoxy Epoxy-containing alkoxysilane compounds such as silane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, ⁇ - Mercaptopropyl trimethoxysilane and ⁇ -mercaptopropyltriethoxysilane containing thiol-containing alkoxysilane compounds, ⁇ -ureidopropyltriethoxysilane, ⁇ -ureidopropyltrimethoxysilane Urea group-containing alkoxysilane compounds such as ⁇ -(2-ureidoethyl)aminopropyltrimethoxysilane, ⁇
  • the poly(p-phenylene sulfide)-m-phenylene sulfide random copolymer and the component (C) poly(p-phenylene sulfide) are homopolymerized relative to the component (A)
  • the total mass of the compound and the substance is 100 parts by mass
  • the (D) silane compound is preferably 0.01 to 3 parts by mass.
  • the component (D) in order to improve the reactivity with the polyphenylene sulfide resin, preferably has an alkoxysilane compound containing at least one of an epoxy group, an amino group, or an isocyanate group .
  • the polyphenylene sulfide resin composition of the present invention may further include an elastomer, an antioxidant, and a mold release agent (montanic acid and its metal salts, its esters, and its half esters, and stearyl alcohol , Stearamide, biurea or polyethylene wax, etc., in order to reduce gas generation during molding, stearamide is preferred), pigments (cadmium sulfide, phthalocyanine, or colored carbon black masterbatch, etc.), dyes (Aniline black, etc.), crystallizer (talc, titanium dioxide, kaolin, clay, etc.), plasticizer (octyl-p-hydroxybenzoate, or N-butylbenzenesulfonamide, etc.), antistatic agent ( Alkyl sulfate type anionic antistatic agent, quaternary ammonium type cationic antistatic agent, polyoxyethylene sorbitan monostearate and other nonionic antistatic agents,
  • elastomer examples include one or more of olefin-based elastomers, modified olefin-based elastomers, and styrene-based elastomers.
  • olefin-based elastomers are obtained by polymerizing individual ⁇ -olefins such as ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, or isobutene, or a plurality of them Polymer or copolymer, ⁇ -olefin and acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, or butyl methacrylate ⁇ , ⁇ -Copolymers of unsaturated acids and their alkyl esters.
  • ⁇ -olefins such as ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, or isobutene, or a plurality of them
  • Polymer or copolymer ⁇ -olefin and acrylic acid, methyl acrylate, ethyl acrylate, butyl
  • polyethylene polypropylene, ethylene/propylene copolymer, ethylene/1-butene copolymer, ethylene/methyl acrylate copolymer, ethylene/ethyl acrylate copolymer, ethylene/butyl acrylate Copolymer, ethylene/methyl methacrylate copolymer, ethylene/ethyl methacrylate copolymer, ethylene/butyl methacrylate copolymer, etc.
  • 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 above-mentioned olefin elastomer.
  • Examples of the functional group-containing component include maleic anhydride, itaconic anhydride, citraconic anhydride, internal bicyclic [2,2,1] 5-heptene-2,3-dicarboxylic acid, or internal bicyclic [2,2, 1] monomers containing acid anhydride groups such as 5-heptene-2,3-dicarboxylic anhydride, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconic acid, or lemon Epoxy group-containing monomers such as glycidyl carboxylate or ionomer-containing monomers such as metal carboxylate complexes.
  • acid anhydride groups such as 5-heptene-2,3-dicarboxylic anhydride, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconic acid, or lemon Ep
  • the method of introducing these functional group-containing monomer components is not particularly limited, and the following methods may be used: copolymerization with the components used in the polymerization of the olefin-based elastomer; or grafting of an olefin-based (co)polymer using a radical initiator Import methods.
  • the introduction amount of the functional group-containing component is 0.001 to 40 mol%, preferably 0.01 to 35 mol% with respect to all monomers constituting the modified olefin elastomer.
  • modified olefin elastomers obtained by introducing monomer components having functional groups such as epoxy groups, acid anhydride groups, or ionomers into olefin elastomers include ethylene/propylene-g-methacrylic acid Glycidyl ester copolymer ("g" means graft, the same below), ethylene/1-butene-g-glycidyl methacrylate copolymer, ethylene/glycidyl acrylate copolymer, ethylene/methacrylic acid glycidyl Glyceride 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/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.
  • styrene-based elastomer examples include styrene/butadiene copolymer, styrene/ethylene/butadiene copolymer, styrene/ethylene/propylene copolymer, styrene/isoprene copolymer, and the like.
  • the styrene/butadiene copolymer is preferred from the viewpoint of compatibility.
  • the amount of elastomer added is preferably 0.5-20 parts by mass, more preferably 0.8-10 parts by mass, and more preferably 100 parts by mass of component (A) and component (C). 1-6 parts by mass.
  • the above-mentioned elastomers may be used in combination.
  • the antioxidant is preferably at least one selected from phenolic antioxidants and phosphorus antioxidants.
  • phenolic antioxidants and phosphorus antioxidants are used in combination, heat resistance and thermal stability can be efficiently maintained, and therefore it is preferable to use both.
  • a hindered phenol compound is preferably used as the phenolic antioxidant.
  • Specific examples are: triethylene glycol bis(3-tert-butyl-(5-methyl-4-hydroxybenzyl) propionate), N,N′-hexamethylenebis(3,5-di-tert Butyl-4-hydroxy-hydrocinnamide), tetrakis(methylene-3-(3′,5′-di-tert-butyl-4′-hydroxybenzyl)propionate) methane, pentaerythritol tetra(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, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butan
  • ester type polymer hindered phenols are preferred, and specifically, tetrakis(methylene-3-(3′,5′-di-tert-butyl-4′-hydroxybenzyl)propionate)methane, pentaerythritol tetra( 3-(3′,5′-di-tert-butyl)-4′-hydroxybenzyl)propionate), or 3,9-bis(2-(3-(3-tert-butyl-4-hydroxy- 5-methylphenyl) propionyloxy)-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro(5,5)undecane and the like.
  • phosphorus-based antioxidants include bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol-diphosphite and bis(2,4-di-tert-butylphenyl)pentaerythritol-di Phosphite, bis(2,4-dicumylphenyl) pentaerythritol-diphosphite, tri(2,4-di-tert-butylphenyl) phosphite, tetra(2,4-di-tert-butyl) Phenyl)-4,4′-bisphenylene phosphite, distearoyl pentaerythritol-diphosphite, triphenyl phosphite, or 3,5-dibutyl-4-hydroxybenzyl phosphate Ester diethyl ester and so on.
  • the amount of the antioxidant 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 relative to 100 parts by mass of the components (A) and (C).
  • the polyphenylene sulfide resin composition of the present invention can be molded by a general resin molding method, and the polyphenylene sulfide resin composition of the present invention has excellent mechanical strength and heat and humidity resistance, and is particularly suitable for cooling of injection molding into automobiles and the like Water, antifreeze circulation system and other products that have been in contact with water for a long time.
  • Poly-p-phenylene sulfide-m-phenyl sulfide random copolymer (p-PPS/m-PPS random copolymer)
  • A-1 Straight-chain p-phenyl sulfide-m-phenyl sulfide random copolymer (m-benzene Sulfide unit 1wt%, weight average molecular weight: 50,000)
  • Poly-p-phenylene sulfide-m-phenyl sulfide random copolymer (p-PPS/m-PPS random copolymer)
  • A-2 Straight-chain p-phenyl sulfide-m-phenyl sulfide random copolymer (m-benzene Sulfide unit 2wt%, weight average molecular weight: 49,000)
  • Poly-p-phenylene sulfide-m-phenyl sulfide random copolymer (p-PPS/m-PPS random copolymer)
  • A-3 Straight-chain p-phenyl sulfide-m-phenyl sulfide random copolymer (m-benzene Sulfide unit 5wt%, weight average molecular weight: 54,000)
  • Poly-p-phenylene sulfide-m-phenyl sulfide random copolymer (p-PPS/m-PPS random copolymer)
  • A-4 Straight-chain p-phenyl sulfide-m-phenyl sulfide random copolymer (m-benzene Sulfide unit 8wt%, weight average molecular weight: 51,000)
  • Poly-p-phenylene sulfide-m-phenyl sulfide random copolymer (p-PPS/m-PPS random copolymer) A-5: Straight-chain p-phenyl sulfide-m-phenyl sulfide random copolymer (m-benzene Sulfide unit 10wt%, weight average molecular weight: 52,000)
  • Poly-p-phenylene sulfide-m-phenyl sulfide random copolymer (p-PPS/m-PPS random copolymer)
  • A-6 Straight-chain p-phenyl sulfide-m-phenyl sulfide random copolymer (m-benzene Sulfide unit 20wt%, weight average molecular weight: 58,000)
  • Poly-p-phenylene sulfide-m-phenyl sulfide random copolymer (p-PPS/m-PPS random copolymer)
  • A-7 Straight-chain p-phenyl sulfide-m-phenyl sulfide random copolymer (m-benzene Sulfide unit 25wt%, weight average molecular weight: 53,000)
  • A'-1 Straight-chain p-phenylene sulfide-m-phenylene sulfide block copolymer (between Phenyl 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 Nippon Electric Glass Co., Ltd. T-760H (single fiber diameter 10.5 ⁇ m)
  • Silane compound D-1 Dow Chemical Company, XIAMETER TM OFS-6040
  • Release agent E-1 PRIME POLYMER, PE7000FB
  • Pigment F-1 Carbon black masterbatch, Toray S771B2
  • the polyphenylene sulfide resin composition particles obtained by extrusion granulation and drying obtained in Examples and Comparative Examples were cut with a cutter to obtain a sample of about 5 mg. Subsequently, the cut samples were raised from 0°C to 340°C at a heating rate of 20°C/min under a nitrogen atmosphere with a DSC-discover 250 differential scanning calorimeter (DSC) of a TA company under a nitrogen atmosphere. After a constant temperature of 340°C for 5 minutes, The temperature was reduced from 340°C to 0°C at a rate of 20°C/min, and kept at 0°C for 3 minutes. Subsequently, the temperature is increased from 0°C to 340°C at a heating rate of 20°C/min, and the endothermic peak-to-peak temperature that appears during the heating process is the melting point.
  • DSC differential scanning calorimeter
  • the injection molded standard splines obtained in the examples and comparative examples are measured according to the ISO 527-1,-2 standard, the drawing rate is 5 mm/min, the distance between the marking lines is 50 mm, the distance between the fixtures is 115 mm, and the average of 5 pieces in each group is averaged The value is taken as the tensile strength.
  • the injection-molded standard splines obtained in the examples and comparative examples were placed in a constant temperature and humidity chamber of the EHS-221M model manufactured by espec, and treated at 121°C ⁇ 100% relative humidity for 100 hours.
  • the tensile strength test evaluates the tensile strength after PCT treatment, and the average value of 5 of each group is taken as the tensile strength after PCT treatment.
  • the retention rate of tensile strength after PCT treatment is calculated according to the following formula (1):
  • the central part of the standard spline obtained in the examples and comparative examples was cut into thin slice samples along a plane perpendicular to the longitudinal direction of the spline, and the single glass fibers present in the obtained thin slice sample were passed through Hysitron Corporation
  • the hemispherical indenter of the micro hardness tester Triboindenter TI950 is pushed out of the resin matrix in a direction perpendicular to the cross section of the glass fiber in the sliced sample, thereby measuring the shear strength when the resin and glass fiber are peeled off. The higher the shear strength when the resin matrix and the glass fiber are peeled off, the better the adhesion between the resin and the glass fiber.
  • the extruder has 13 heating zones and two feeding devices with measuring instruments And with vacuum exhaust equipment. Except for the glass fiber, after the other raw materials are mixed, they are added from the main feed port of the extruder, and the glass fibers are added from the feed port on the side of the extruder.
  • the temperature of the extruder is set at 200 °C-330 °C, after melting, extruding , Cooling and pelletizing to obtain a granular polyphenylene sulfide resin composition; after drying the pellets in an oven at 130 °C for 3 hours, using a NEX50 model injection molding machine manufactured by Nissei Resin Co., Ltd. according to a molding temperature of 330 °C and a mold temperature of 130 °C
  • the conditions are injection molded into ISO standard splines (spline mold size is 10mm wide x 4mm thick), and the performance test is performed according to the above test method.
  • the composition melting point, tensile strength, and heat and humidity resistance data (evaluated by the tensile strength after 100 hours of PCT treatment and the tensile strength retention ratio) are shown in Table 1.
  • An NEX50 injection molding machine manufactured by Nissei Resin Co., Ltd. was used to injection mold an ISO standard spline (spline mold size is 10 mm wide ⁇ 4 mm thick) under the conditions of a molding temperature of 330° C. and a mold temperature of 70° C. in an oven at 145° C. After 1 hour heat treatment (when the sample shown in Table 1 is molded under the same conditions, the curing speed is too slow, resulting in deformation of the ISO standard spline during demolding, so heat treatment is performed after low temperature molding), according to the above test method Performance Testing.
  • ISO standard spline spline mold size is 10 mm wide ⁇ 4 mm thick
  • Example 2 the composition melting point, tensile strength, and hygrothermal resistance data (evaluated by the tensile strength after 100 hours of PCT treatment and the tensile strength retention ratio) are shown in Table 2.
  • Table 4 shows the data of the peeling shear strength between the glass fiber and the resin matrix of Example 6 and Comparative Example 4 and the resin adhesion ratio on the glass fiber surface.
  • Example 5 As can be seen from the comparison between Example 5 and Comparative Example 3, and between Example 6 and Comparative Example 5, when no inorganic filler is added, the tensile strength and strength retention rate of the polyphenylene sulfide resin composition after 100 hours of PCT treatment are low .
  • Example 6 As can be seen from the comparison between Example 6 and Comparative Examples 6-8, when the amount of the inorganic filler added is too small, the tensile strength and strength retention rate of the polyphenylene sulfide resin composition after 100 hours of PCT treatment are low. Conversely, when the amount of the inorganic filler added is too large, the composition cannot be kneaded by the extruder.
  • the present invention is a resin composition formed by mixing (A) a poly(p-phenylene sulfide)-m-phenylene sulfide random copolymer and (B) an inorganic filler, compared to A resin composition formed of a poly(p-phenylene sulfide) homopolymer and an inorganic filler has a higher shear strength for peeling between the glass fiber and the resin matrix after 100 hours of PCT treatment, and the resin adhered to the surface of the glass fiber The proportion is greater.

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Abstract

The present invention relates to a polyphenylene sulfide resin composition, comprising 5-2000 parts by mass of an inorganic filler relative to 100 parts by mass of a poly(p-phenylene sulfide)-m-phenylene sulfide random copolymer. The composition of the present invention has excellent heat and humidity resistance, can maintain a high mechanical strength when in contact with water for a long time, and is therefore particularly suitable as a water coolant for injection molding and in antifreeze circulation systems of an automobile, etc., and in other articles which are in contact with liquids, such as water, for a long time.

Description

聚苯硫醚树脂组合物及其成型品Polyphenylene sulfide resin composition and its molded product 技术领域Technical field
本发明涉及聚合物材料领域，具体涉及一种聚苯硫醚树脂组合物及其成型品。The invention relates to the field of polymer materials, in particular to a polyphenylene sulfide resin composition and its molded product.
背景技术Background technique
聚苯硫醚树脂(PPS)具有优良的流动性、耐高温、耐腐蚀、阻燃性、均衡的物理机械性能和极好的尺寸稳定性以及优良的电性能等特点，因此被广泛用于电气、电子零部件或汽车零部件等领域。而近年来，随着聚苯硫醚树脂材料在汽车等的冷却水、防冻液循环***中的广泛运用，进一步要求其还具有优异的耐水性与耐湿热性。Polyphenylene sulfide resin (PPS) has the characteristics of excellent fluidity, high temperature resistance, corrosion resistance, flame retardancy, balanced physical and mechanical properties, excellent dimensional stability, and excellent electrical properties, so it is widely used in electrical , Electronic parts or auto parts. In recent years, with the widespread use of polyphenylene sulfide resin materials in the cooling water and antifreeze circulation systems of automobiles and the like, it is further required to have excellent water resistance and humidity resistance.
对此，专利文献1(日本公开号特开2018-141149号公报)公开了一种含有聚对苯硫醚和无机填料的树脂组合物，其通过提高聚苯硫醚树脂中的金属钠原子含量到1000ppm以上，从而提高湿热处理后的拉伸强度保持率以改善其耐湿热性。但是，金属原子含量的增加导致未处理时聚苯硫醚树脂组合物的拉伸强度下降。In this regard, Patent Document 1 (Japanese Laid-Open Patent Publication No. 2018-141149) discloses a resin composition containing poly-p-phenylene sulfide and an inorganic filler by increasing the content of metal sodium atoms in the polyphenylene sulfide resin To 1000ppm or more, so as to improve the tensile strength retention rate after wet heat treatment to improve its resistance to heat and humidity. However, an increase in the content of metal atoms leads to a decrease in the tensile strength of the polyphenylene sulfide resin composition when untreated.
专利文献2(日本公开号特开2018-123307号公报)公开了一种含有聚对苯硫醚、无机填料和有机成核剂的树脂组合物，通过添加范围适量的有机成核剂，以提高聚苯硫醚树脂的熔体降温结晶温度(T mc)，并使聚苯硫醚树脂晶区尺寸减小并且均一化，从而改善成型品的耐水压性。但是，作为有机成核剂添加的PEEK树脂相对于主体聚苯硫醚树脂，容易成为异物。 Patent Document 2 (Japanese Laid-Open Patent Publication No. 2018-123307) discloses a resin composition containing poly-p-phenylene sulfide, inorganic filler and organic nucleating agent, which is improved by adding an appropriate amount of organic nucleating agent The melt temperature of the polyphenylene sulfide resin is lowered to the crystallization temperature (T mc ), and the crystal area of the polyphenylene sulfide resin is reduced and uniformed, thereby improving the water pressure resistance of the molded product. However, PEEK resin added as an organic nucleating agent tends to become a foreign substance relative to the main polyphenylene sulfide resin.
另一方面，专利文献3(日本公开号特开2016-69650号公报)公开了一种聚对苯硫醚-间苯硫醚共聚物，通过将间苯硫醚单元共聚到聚苯硫醚分子内得到了结晶性更低的聚合物，从而改善了所形成的薄膜与金属、树脂表面之间的 结合性。但是，未与聚对苯硫醚均聚物混合时制膜稳定性不佳，同时，由该聚对苯硫醚-间苯硫醚共聚物所形成的薄膜的强度低于聚对苯硫醚均聚物，并不适用于注塑成汽车等的冷却水、防冻液循环***及其他长期与水等液体接触的具有一定强度要求的成型品。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 by copolymerizing m-phenylene sulfide units into polyphenylene sulfide molecules A polymer with lower crystallinity is obtained, thereby improving the adhesion between the formed film and the surface of metal and resin. However, the film-forming stability is not good when it is not mixed with poly-p-phenylene sulfide homopolymer, and at the same time, the strength of the film formed by the poly-p-phenylene sulfide-m-phenylene sulfide copolymer is lower than that of poly-p-phenylene sulfide. Homopolymer is not suitable for injection molding into cooling water of automobiles, antifreeze circulation systems and other molded products with certain strength requirements that have been in contact with water and other liquids for a long time.
发明内容Summary of the invention
本发明人为了解决上述问题，经过深入研究后，发现虽然聚对苯硫醚-间苯硫醚共聚物强度低、耐湿热性差，但与无机填料组合时，不仅能够提高强度，更能特异性地提高耐湿热性，由此得到的聚苯硫醚树脂组合物，不仅能够拓展共聚物在塑料成型品中的应用，并且进一步改善了塑料成型品的耐湿热性。In order to solve the above problems, the present inventors have found that although the poly-p-phenylene sulfide-m-phenylene sulfide copolymer has low strength and poor heat and humidity resistance, when combined with inorganic fillers, it can not only increase the strength, but also be more specific. The polyphenylene sulfide resin composition thus obtained can not only expand the application of the copolymer in plastic molded products, but also further improve the heat and moisture resistance of plastic molded products.
本发明还提供了一种上述的聚苯硫醚树脂组合物所制得的成型品。由于其拥有优异的耐湿热性，适用于汽车等的冷却水、防冻液循环***及其他长期与水等液体接触的部品。The invention also provides a molded product prepared by the above polyphenylene sulfide resin composition. Because of its excellent resistance to heat and humidity, it is suitable for cooling water, antifreeze circulation systems of automobiles and other parts that have been in contact with liquids such as water for a long time.
即本发明的技术方案为：That is, the technical solution of the present invention is:
1.一种聚苯硫醚树脂组合物，其包含：1. A polyphenylene sulfide resin composition comprising:
(A)聚对苯硫醚-间苯硫醚无规共聚物，和(A) Poly-p-phenylene sulfide-m-phenylene sulfide random copolymer, and
(B)无机填料，(B) inorganic filler,
相对于所述(A)聚对苯硫醚-间苯硫醚无规共聚物100质量份，所述(B)无机填料的混合量为5-2000质量份。The mixing amount of the (B) inorganic filler is 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.根据上述1所述的聚苯硫醚树脂组合物，其中，所述(A)聚对苯硫醚-间苯硫醚无规共聚物中，相对于无规共聚物中苯硫醚单元总质量，间苯硫醚单元的含量为2-25wt％。2. The polyphenylene sulfide resin composition according to the above 1, wherein in the (A) poly(p-phenylene sulfide)-m-phenylene sulfide random copolymer, relative to the phenylene sulfide unit in the random copolymer The total mass, the content of m-phenylene sulfide unit is 2-25wt%.
3.根据上述1所述的聚苯硫醚树脂组合物，其中，所述(A)聚对苯硫醚-间苯硫醚无规共聚物的熔点为210-280℃。3. The polyphenylene sulfide resin composition according to the above 1, wherein the (A) poly-p-phenylene sulfide-m-phenylene sulfide random copolymer has a melting point of 210-280°C.
4.根据上述1所述的聚苯硫醚树脂组合物，其中，相对于所述(A)聚对苯 硫醚-间苯硫醚无规共聚物100质量份，所述(B)无机填料的混合量为26-2000质量份。4. The polyphenylene sulfide resin composition according to 1 above, wherein the (B) inorganic filler is based on 100 parts by mass of the (A) poly-p-phenylene sulfide-m-phenylene sulfide random copolymer The mixing amount is 26-2000 parts by mass.
5.根据上述1所述的聚苯硫醚树脂组合物，其还包含(C)聚对苯硫醚均聚物。5. The polyphenylene sulfide resin composition according to the above 1, further comprising (C) a poly(p-phenylene sulfide) homopolymer.
6.根据上述5所述的聚苯硫醚树脂组合物，其中，相对于所述(A)聚对苯硫醚-间苯硫醚共聚物100质量份，所述(C)聚对苯硫醚均聚物的混合量为10-2500质量份。6. The polyphenylene sulfide resin composition according to the above 5, wherein the (C) poly-p-phenylene sulfide is (C) poly-p-phenylene sulfide with respect to 100 parts by mass of the (A) poly-p-phenylene sulfide-m-phenylene sulfide copolymer The mixing amount of the ether homopolymer is 10-2500 parts by mass.
7.根据上述5所述的聚苯硫醚树脂组合物，其中，相对于(A)聚对苯硫醚-间苯硫醚无规共聚物以及(C)聚对苯硫醚均聚物中苯硫醚单元的总质量，所述(A)聚对苯硫醚-间苯硫醚无规共聚物中的间苯硫醚单元的含量为1-14wt％。7. The polyphenylene sulfide resin composition according to the above 5, relative to (A) a poly(p-phenylene sulfide)-m-phenylene sulfide random copolymer and (C) a poly(p-phenylene sulfide) homopolymer The total mass of the phenylene sulfide unit, the content of the m-phenylene sulfide unit in the (A) poly-p-phenylene sulfide-m-phenylene sulfide random copolymer is 1-14 wt%.
8.根据上述5所述的聚苯硫醚树脂组合物，其中，相对于所述(A)聚对苯硫醚-间苯硫醚无规共聚物及所述(C)聚对苯硫醚均聚物的总质量100质量份，所述(B)无机填料的混合量为5-150质量份。8. The polyphenylene sulfide resin composition according to the above 5, relative to the (A) poly-p-phenylene sulfide-m-phenylene sulfide random copolymer and the (C) poly-p-phenylene sulfide The total mass of the homopolymer is 100 parts by mass, and the mixing amount of the (B) inorganic filler is 5-150 parts by mass.
9.根据上述5所述的聚苯硫醚树脂组合物，其中，相对于所述(A)聚对苯硫醚-间苯硫醚无规共聚物及所述(C)聚对苯硫醚均聚物的总质量100质量份，所述(B)无机填料的混合量为26-150质量份。9. The polyphenylene sulfide resin composition according to the above 5, relative to the (A) poly-p-phenylene sulfide-m-phenylene sulfide random copolymer and the (C) poly-p-phenylene sulfide The total mass of the homopolymer is 100 parts by mass, and the mixing amount of the (B) inorganic filler is 26-150 parts by mass.
10.根据上述1所述的聚苯硫醚树脂组合物，其中，所述(B)无机填料为选自玻璃纤维、玻璃薄片、玻璃微珠、碳纤维、碳酸钙、二氧化硅、滑石粉或硅灰石中的至少一种。10. The polyphenylene sulfide resin composition according to the above 1, wherein the (B) inorganic filler is selected from glass fibers, glass flakes, glass beads, carbon fibers, calcium carbonate, silica, talc or At least one of wollastonite.
11.根据上述1所述的聚苯硫醚树脂组合物，其还包含(D)硅烷化合物。11. The polyphenylene sulfide resin composition according to the above 1, further comprising (D) a silane compound.
12.根据上述11所述的聚苯硫醚树脂组合物，其中，所述(D)硅烷化合物为含有环氧基、氨基或异氰酸酯基中的至少一种的烷氧基硅烷化合物。12. The polyphenylene sulfide resin composition according to 11 above, wherein the (D) silane compound is an alkoxysilane compound containing at least one of an epoxy group, an amino group, or an isocyanate group.
13.一种成型品，其特征在于：使用上述1-12中任一项所述的聚苯硫醚树脂组合物得到。13. A molded article obtained by using the polyphenylene sulfide resin composition according to any one of 1-12 above.
14.根据上述13所述的成型品，其用于冷却水、防冻液循环***。14. The molded product according to 13 above, which is used in a cooling water and antifreeze circulation system.
具体实施方式detailed description
以下对本发明的具体实施方式进行说明：The specific embodiments of the present invention are described below:
1.(A)聚对苯硫醚-间苯硫醚无规共聚物：1. (A) Poly-p-phenylene sulfide-m-phenylene sulfide random copolymer:
本发明中使用的(A)聚对苯硫醚-间苯硫醚无规共聚物是具有下述结构式(I)和下述结构式(Ⅱ)所示的重复单元的无规共聚物，The (A) poly(p-phenylene sulfide)-m-phenylene sulfide random copolymer used in the present invention is a random copolymer having a repeating unit represented by the following structural formula (I) and the following structural formula (II),
Figure PCTCN2019126492-appb-000001
Figure PCTCN2019126492-appb-000001
Figure PCTCN2019126492-appb-000002
Figure PCTCN2019126492-appb-000002
本发明中所使用的(A)聚对苯硫醚-间苯硫醚无规共聚物中，间苯硫醚单元相对于共聚物中苯硫醚单元总质量，其含量优选为2-25wt％。间苯硫醚单元相对共聚物中苯硫醚单元总质量，其含量高于25wt％时，聚对苯硫醚-间苯硫醚无规共聚物的熔点与结晶度呈下降趋势，大幅影响树脂组合物的耐热性和使用温度。其含量进一步优选为20wt％以下，更优选为13wt％以下。间苯硫醚单元相对于共聚物中苯硫醚单元总质量，其含量低于2wt％时，对组合物耐湿热性能的提高效果有限，其含量进一步优选为3wt％以上，更优选为5wt％以上。In the (A) poly(p-phenylene sulfide)-m-phenylene sulfide random copolymer used in the present invention, the content of m-phenyl sulfide unit is preferably 2-25 wt% relative to the total mass of the phenyl sulfide unit in the copolymer . When the content of m-phenylene sulfide unit is higher than 25wt% relative to the total mass of phenylene sulfide unit in the copolymer, the melting point and crystallinity of poly-p-phenylene sulfide-m-phenylene sulfide random copolymer show a downward trend, which greatly affects the resin The heat resistance and use temperature of the composition. The content is further preferably 20% by weight or less, and more preferably 13% by weight or less. When the content of m-phenylene sulfide unit is less than 2% by weight relative to the total mass of the phenylene sulfide unit in the copolymer, the effect of improving the moisture and heat resistance of the composition is limited, and its content is further preferably 3% by weight or more, more preferably 5% by weight the above.
本发明中所使用的(A)聚对苯硫醚-间苯硫醚无规共聚物，其熔点优选为210-280℃。聚对苯硫醚-间苯硫醚无规共聚物的熔点高于280℃时，其中间苯硫醚单元的含量太少，对组合物耐湿热性能的提高效果有限，其熔点进一步优选为270℃以下。聚对苯硫醚-间苯硫醚无规共聚物的熔点低于210℃时，其耐热性大幅下降，不利于高温环境下使用，其熔点进一步优选为235℃以上，更优选为250℃以上。The (A) poly(p-phenylene sulfide)-m-phenylene sulfide random copolymer used in the present invention preferably has a melting point of 210-280°C. When the melting point of the poly(p-phenylene sulfide)-m-phenylene sulfide random copolymer is higher than 280°C, the content of m-phenylene sulfide unit is too small, and the effect of improving the composition's resistance to moisture and heat is limited. The melting point is more preferably 270 Below ℃. When the melting point of the poly(p-phenylene sulfide)-m-phenylene sulfide random copolymer is lower than 210°C, its heat resistance is greatly reduced, which is not conducive to use in a high-temperature environment. The melting point is further preferably 235°C or higher, more preferably 250°C the above.
2.(B)无机填料：2. (B) Inorganic filler:
由(A)聚对苯硫醚-间苯硫醚无规共聚物与(B)无机填料所形成的组合物相 对于后述由(C)聚苯硫醚均聚物和(B)无机填料所形成的组合物，其具有更高的耐湿热性。The composition formed by (A) poly-p-phenylene sulfide-m-phenylene sulfide random copolymer and (B) inorganic filler is relative to (C) polyphenylene sulfide homopolymer and (B) inorganic filler The resulting composition has higher resistance to moisture and heat.
本发明所述的无机填料是指已知可用于树脂中的填料。例如玻璃纤维、碳纤维、钛酸钾晶须、锌晶须氧化物、硼酸铝晶须、芳族聚酰胺纤维、氧化铝纤维、碳化硅纤维、陶瓷纤维、石棉纤维、石膏纤维、金属纤维、玻璃薄片、硅灰石、沸石、绢云母、高岭土、云母、滑石、粘土、叶蜡石、膨润土、蒙脱石、锂蒙脱石、合成云母、石棉、石墨、硅铝酸盐、氧化铝、二氧化硅、氧化镁、氧化锆、氧化钛、氧化铁、碳酸钙、碳酸镁、白云石、硫酸钙、硫酸钡、氢氧化镁、氢氧化钙、氢氧化铝、玻璃微珠、空心玻璃微珠、陶瓷珠、氮化硼、碳化硅或硅灰石等。所述无机填料也可以是结构上是中空的无机填料，更进一步，也可以从这些无机填料中选择2种或更多种配合使用。无机填料的平均直径不做特别限制，优选0.001-20μm，在此范围内，可以获得较好的流动性和更好的外观。The inorganic filler in the present invention refers to fillers known to be used in resins. For example, glass fiber, carbon fiber, potassium titanate whisker, zinc whisker oxide, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, gypsum fiber, metal fiber, glass Flakes, wollastonite, zeolite, sericite, kaolin, mica, talc, clay, pyrophyllite, bentonite, montmorillonite, hectorite, synthetic mica, asbestos, graphite, aluminosilicate, alumina, di Silicon oxide, magnesium oxide, zirconium oxide, titanium oxide, iron oxide, calcium carbonate, magnesium carbonate, dolomite, calcium sulfate, barium sulfate, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, glass beads, hollow glass beads , Ceramic beads, boron nitride, silicon carbide or wollastonite, etc. The inorganic filler may be a hollow inorganic filler in structure, and further, two or more kinds of these inorganic fillers may be selected for use in combination. The average diameter of the inorganic filler is not particularly limited, and is preferably 0.001 to 20 μm. Within this range, better fluidity and better appearance can be obtained.
特别地，出于对低成型收缩率和流动性的综合考虑，为了获得性能优异的聚苯硫醚树脂组合物，无机填料优选玻璃纤维或碳纤维中的至少一种。所述玻璃纤维没有特定的限制，可以是现有技术中采用的玻璃纤维。玻璃纤维可以是定长切断的短切原丝、粗砂、研磨纤维等形状的纤维。一般情况下优选使用的玻纤平均直径为5-15μm。使用短切原丝的情况下，长度没有特别限制，优选使用适合挤出混炼作业的标准3mm长度的纤维。此外，本发明对上述纤维状填充材料地断面型形状没有特别的限定，可以从圆形、扁平状纤维中选择任意一种或多种配合使用。In particular, for comprehensive consideration of low molding shrinkage and fluidity, in order to obtain a polyphenylene sulfide resin composition excellent in performance, 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 chopped strand cut with a fixed length, coarse sand, or abrasive fiber. Generally, the average diameter of the glass fiber used is preferably 5-15 μm. When using chopped strands, the length is not particularly limited, but it is preferable to use standard 3 mm length fibers suitable for extrusion and kneading operations. In addition, in the present invention, the cross-sectional shape of the fibrous filler is not particularly limited, and any one or more of round and flat fibers may be used in combination.
另一方面，为了获得更好的产品外观，优选玻璃薄片、玻璃微珠、空心玻璃微珠、碳酸钙、二氧化硅、滑石粉或硅灰石中的至少一种。On the other hand, in order to obtain a better product appearance, at least one of glass flakes, glass microbeads, hollow glass microbeads, calcium carbonate, silica, talc, or wollastonite is preferred.
3.成分(B)的配比3. The ratio of component (B)
本发明中，相对于所述成分(A)聚对苯硫醚-间苯硫醚无规共聚物100质量份，所述的(B)无机填料的含量优选为5-2000量份。在此添加范围内，本发明 的聚苯硫醚树脂组合物能够在拥有较好的机械强度的同时仍保持着较好的流动性、加工性及韧性。在本发明中，相对于所述的成分(A)100质量份，成分(B)的添加量，优选为26质量份以上，进一步优选为40质量份以上。另一方面(B)无机填料的添加量优选为800质量份以下，进一步优选为300质量份以下。In the present invention, the content of the (B) inorganic filler is preferably from 5 to 2000 parts by weight with respect to 100 parts by weight of the component (A) poly(p-phenylene sulfide)-m-phenylene sulfide random copolymer. Within this range of addition, the polyphenylene sulfide resin composition of the present invention can have good mechanical strength while still maintaining good fluidity, processability, and toughness. In the present invention, the amount of component (B) added is preferably 26 parts by mass or more, and more preferably 40 parts by mass or more with respect to 100 parts by mass of the component (A). On the other hand, the addition amount of (B) inorganic filler is preferably 800 parts by mass or less, and more preferably 300 parts by mass or less.
4.(C)聚对苯硫醚均聚物4. (C) Poly (p-phenylene sulfide) homopolymer
本发明中使用的(A)聚对苯硫醚均聚物是具有下述结构式(I)所示的重复单元的聚合物。The (A) poly(p-phenylene sulfide) homopolymer used in the present invention is a polymer having a repeating unit represented by the following structural formula (I).
Figure PCTCN2019126492-appb-000003
Figure PCTCN2019126492-appb-000003
本发明对于聚对苯硫醚均聚物的结构没有特别的限定，可以选用直链型聚对苯硫醚，也可使用氧化交联型聚苯硫醚或是加入三卤素官能团反应物的支链型聚苯硫醚，所述三卤素官能团反应物的添加量优选为少于1wt％。In the present invention, the structure of the poly(p-phenylene sulfide) homopolymer is not particularly limited. Straight-chain poly(p-phenylene sulfide), oxidized cross-linked poly(phenylene sulfide), or a branch containing a trihalogen functional group reactant may be used. For the chain-type polyphenylene sulfide, the addition amount of the trihalogen functional group reactant is preferably less than 1 wt%.
本发明中所使用的聚对苯硫醚均聚物并不限定制造方法，例如，具有上述结构式(I)结构的聚苯硫醚均聚物可以选用日本特公昭45-3368号公报记载的用于获得较高流动性的方法或日本特公昭52-12240号公报等记载的用于获得较低流动性的方法来制备。前者与后者的区别在于聚合体系内是否有聚合助剂碱金属羧酸盐。前者的方法中，不向聚合体系内添加碱金属羧酸盐，流动性较高；而后者的方法中，向聚合体系内添加碱金属羧酸盐，流动性较低，从而对树脂的韧性有利。所以可以将通过两种方法制备的聚苯硫醚聚合物组合使用，由此得以平衡聚苯硫醚树脂的流动性和韧性。The polyphenylene sulfide homopolymer used in the present invention is not limited to the production method. For example, the polyphenylene sulfide homopolymer having the structure of the above formula (I) can be selected from those described in Japanese Patent Publication No. 45-3368 It is prepared by the method for obtaining higher fluidity or the method for obtaining lower fluidity described in Japanese Patent Publication No. 52-12240. The difference between the former and the latter is whether there is a polymerization aid alkali metal carboxylate in the polymerization system. In the former method, the alkali metal carboxylate is not added to the polymerization system, and the fluidity is high; while in the latter method, the alkali metal carboxylate is added to the polymerization system, the fluidity is low, which is beneficial to the toughness of the resin . Therefore, the polyphenylene sulfide polymer prepared by the two methods can be used in combination, thereby balancing the fluidity and toughness of the polyphenylene sulfide resin.
此外，将上述制备的聚苯硫醚聚合物作封端处理可以得到氯含量更低的聚苯硫醚聚合物。例如在碱性条件下用2-巯基苯并咪唑封端处理，可以得到氯含量更低的封端的聚对苯硫醚均聚物。In addition, the polyphenylene sulfide polymer prepared above can be end-treated to obtain a polyphenylene sulfide polymer with lower chlorine content. For example, end-capping treatment with 2-mercaptobenzimidazole under alkaline conditions can provide end-capped poly(p-phenylene sulfide) homopolymer with lower chlorine content.
5.成分(A)与成分(C)的配比5. The ratio of component (A) and component (C)
本发明中，相对于所述成分(A)聚对苯硫醚-间苯硫醚无规共聚物添加所述 成分(C)聚对苯硫醚均聚物的情况下，相对于所述成分(A)聚对苯硫醚-间苯硫醚无规共聚物100质量份，所述成分(C)聚对苯硫醚均聚物的混合量优选为10-2500质量份。本发明中，为了达到在保持组合物机械强度及耐热性的同时实现耐湿热性的提高，可以将成分(A)、(C)以进一步优选的比例进行混合。本发明中，优选地，相对于成分(A)100质量份，成分(C)为40质量份以上，更优选为60质量份以上。另一方面，优选地，成分(C)的添加量为1000质量份以下，更优选为900质量份以下。相对于成分(A)100质量份，成分(C)含量低于10质量份时，组合物的机械强度有所降低。成分(C)的含量高于2500质量份时，组合物耐湿热性的改善效果有限。In the present invention, when the component (C) poly(p-phenylene sulfide) homopolymer is added to the component (A) poly(p-phenylene sulfide)-m-phenylene sulfide random copolymer, relative to the component (A) 100 parts by mass of poly-p-phenylene sulfide-m-phenylene sulfide random copolymer, and the mixing amount of the component (C) poly-p-phenylene sulfide homopolymer is preferably 10-2500 parts by mass. In the present invention, in order to achieve the improvement of moisture and heat resistance while maintaining the mechanical strength and heat resistance of the composition, the components (A) and (C) may be mixed in a more preferable ratio. In the present invention, the component (C) is preferably 40 parts by mass or more, and more preferably 60 parts by mass or more with respect to 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, and more preferably 900 parts by mass or less. When the content of component (C) is less than 10 parts by mass relative to 100 parts by mass of component (A), the mechanical strength of the composition decreases. When the content of the component (C) is higher than 2500 parts by mass, the effect of improving the moisture and heat resistance of the composition is limited.
本发明中，相对于(A)聚对苯硫醚-间苯硫醚无规共聚物及(C)聚对苯硫醚均聚物中苯硫醚单元总质量，(A)聚对苯硫醚-间苯硫醚无规共聚物中所含有的间苯硫醚单元的含量优选为1-14wt％。相对于(A)聚对苯硫醚-间苯硫醚无规共聚物及(C)聚对苯硫醚均聚物中苯硫醚单元总质量，(A)聚对苯硫醚-间苯硫醚无规共聚物中所含有的间苯硫醚单元的含量低于1wt％时，组合物耐湿热性的改善效果有限，其含量进一步优选为2.5wt％以上。相对于(A)聚对苯硫醚-间苯硫醚无规共聚物及(C)聚对苯硫醚均聚物中苯硫醚单元总质量，(A)聚对苯硫醚-间苯硫醚无规共聚物中所含有的间苯硫醚单元的含量高于14wt％时，组合物的机械强度和耐热性有降低的趋势，其含量进一步优选为13wt％以下，更优选为11wt％以下。In the present invention, relative to the total mass of phenylene sulfide units in (A) poly-p-phenylene sulfide-m-phenylene sulfide random copolymer and (C) poly-p-phenylene sulfide homopolymer, (A) poly-p-phenylene sulfide The content of the m-phenylene sulfide unit contained in the ether-m-phenylene sulfide random copolymer is preferably 1 to 14% by weight. Relative to the total mass of phenylene sulfide units in (A) poly(p-phenylene sulfide)-m-phenylene sulfide random copolymer and (C) poly(p-phenylene sulfide) homopolymer, (A) poly(p-phenylene sulfide)-m-phenylene When the content of the m-phenylene sulfide unit contained in the sulfide random copolymer is less than 1% by weight, the effect of improving the moisture and heat resistance of the composition is limited, and the content is more preferably 2.5% by weight or more. Relative to the total mass of phenylene sulfide units in (A) poly(p-phenylene sulfide)-m-phenylene sulfide random copolymer and (C) poly(p-phenylene sulfide) homopolymer, (A) poly(p-phenylene sulfide)-m-phenylene When the content of the m-phenylene sulfide unit contained in the sulfide random copolymer is higher than 14 wt%, the mechanical strength and heat resistance of the composition tend to decrease, and its content is further preferably 13 wt% or less, and more preferably 11 wt% %the following.
6.成分(B)相对于成分(A)与成分(C)的配比6. The ratio of component (B) to component (A) and component (C)
本发明中，将所述成分(A)聚对苯硫醚-间苯硫醚无规共聚物及所述成分(C)聚对苯硫醚均聚物混合的情况下，相对于成分(A)和成分(C)的总质量100质量份，所述的成分(B)无机填料的含量优选为5-150质量份。在此添加范围内，本发明的聚苯硫醚树脂组合物能够在拥有较好的机械强度的同时仍保持着较好的流动性、加工性及韧性。在本发明中，相对于所述的成分(A)及成分(C)的总质量100质量份，成分(B)的添加量，优选为26质量份以上，进一步优选 为40质量份以上。另一方面成分(B)无机填料的添加量优选为110质量份以下，进一步优选为80质量份以下。In the present invention, when the component (A) poly-p-phenylene sulfide-m-phenylene sulfide random copolymer and the component (C) poly-p-phenylene sulfide homopolymer are mixed, relative to the component (A ) And the total mass of component (C) is 100 parts by mass, and the content of the inorganic filler of component (B) is preferably 5-150 parts by mass. Within this addition range, the polyphenylene sulfide resin composition of the present invention can have good mechanical strength while still maintaining good fluidity, processability, and toughness. In the present invention, the amount of component (B) added is preferably 26 parts by mass or more, and more preferably 40 parts by mass or more, relative to 100 parts by mass of the total mass of the component (A) and the component (C). On the other hand, the added amount of the component (B) inorganic filler is preferably 110 parts by mass or less, and more preferably 80 parts by mass or less.
7.(D)硅烷化合物7. (D) Silane compound
本发明中，出于增强树脂与无机填料之间的粘结性的角度考虑，可以进一步添加(D)硅烷化合物。所述硅烷化合物优选是具有选自环氧基、氨基、异氰酸酯基、羟基、巯基、脲基中的一种以上基团的烷氧基硅烷化合物。In the present invention, from the viewpoint of enhancing the adhesion between the resin and the inorganic filler, the (D) silane compound may be further added. The silane compound is preferably an alkoxysilane compound having one or more groups selected from epoxy groups, amino groups, isocyanate groups, hydroxyl groups, mercapto groups, and urea groups.
作为上述具有选自环氧基、氨基、异氰酸酯基、羟基、巯基和脲基中的至少1种官能团的烷氧基硅烷化合物的具体例，可举出γ-环氧丙氧基丙基三甲氧基硅烷、γ-环氧丙氧基丙基三乙氧基硅烷、β-(3,4-环氧环己基)乙基三甲氧基硅烷等含有环氧基的烷氧基硅烷化合物，γ-巯基丙基三甲氧基硅烷和γ-巯基丙基三乙氧基硅烷等含有巯基的烷氧基硅烷化合物，γ-脲基丙基三乙氧基硅烷、γ-脲基丙基三甲氧基硅烷和γ-(2-脲基乙基)氨基丙基三甲氧基硅烷等含有脲基的烷氧基硅烷化合物，γ-异氰酸酯基丙基三乙氧基硅烷、γ-异氰酸酯基丙基三甲氧基硅烷、γ-异氰酸酯基丙基甲基二甲氧基硅烷、γ-异氰酸酯基丙基甲基二乙氧基硅烷、γ-异氰酸酯基丙基乙基二甲氧基硅烷、γ-异氰酸酯基丙基乙基二乙氧基硅烷和γ-异氰酸酯基丙基三氯硅烷等含有异氰酸酯基的烷氧基硅烷化合物，γ-(2-氨基乙基)氨基丙基甲基二甲氧基硅烷、γ-(2-氨基乙基)氨基丙基三甲氧基硅烷和γ-氨基丙基三甲氧基硅烷等含有氨基的烷氧基硅烷化合物，以及γ-羟基丙基三甲氧基硅烷和γ-羟基丙基三乙氧基硅烷等含有羟基的烷氧基硅烷化合物等。Specific examples of the alkoxysilane compound having at least one functional group selected from epoxy groups, amino groups, isocyanate groups, hydroxyl groups, mercapto groups, and ureido groups include γ-glycidoxypropyltrimethoxy Epoxy-containing alkoxysilane compounds such as silane, γ-glycidoxypropyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ- Mercaptopropyl trimethoxysilane and γ-mercaptopropyltriethoxysilane containing thiol-containing alkoxysilane compounds, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane Urea group-containing alkoxysilane compounds such as γ-(2-ureidoethyl)aminopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane Silane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyl diethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropyl Isocyanate group-containing alkoxysilane compounds such as ethyl diethoxysilane and γ-isocyanatopropyltrichlorosilane, γ-(2-aminoethyl)aminopropylmethyldimethoxysilane, γ- (2-Aminoethyl)aminopropyl trimethoxysilane and γ-aminopropyl trimethoxysilane and other amino group-containing alkoxysilane compounds, as well as γ-hydroxypropyltrimethoxysilane and γ-hydroxypropyl Hydroxy-containing alkoxysilane compounds such as triethoxysilane.
在本发明中，出于粘结性及流动性的考虑，相对于成分(A)聚对苯硫醚-间苯硫醚无规共聚物及所述成分(C)聚对苯硫醚均聚物及的总质量100质量份，所述(D)硅烷化合物优选为0.01-3质量份。通过添加上述范围的硅烷化合物，可以在保证本发明中的聚苯硫醚树脂组合物维持其流动性的同时增强聚苯硫醚树脂与无机填料之间的粘结性。上述硅烷化合物的含量进一步优选为0.05质量份以上，更优选为0.1质量份以上。与此同时，其含量进一步优选为2质 量份以下，更优选为1质量份以下。In the present invention, for the consideration of adhesion and fluidity, the poly(p-phenylene sulfide)-m-phenylene sulfide random copolymer and the component (C) poly(p-phenylene sulfide) are homopolymerized relative to the component (A) The total mass of the compound and the substance is 100 parts by mass, and the (D) silane compound is preferably 0.01 to 3 parts by mass. By adding the silane compound in the above range, the adhesion between the polyphenylene sulfide resin and the inorganic filler can be enhanced while ensuring 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 more preferably 0.1 parts by mass or more. At the same time, the content is more preferably 2 parts by mass or less, and more preferably 1 part by mass or less.
本发明中，出于为了提高与聚苯硫醚树脂之间的反应性的考虑，所述成分(D)优选具有含有环氧基、氨基或异氰酸酯基中的至少一种的烷氧基硅烷化合物。In the present invention, in order to improve the reactivity with the polyphenylene sulfide resin, the component (D) preferably has an alkoxysilane compound containing at least one of an epoxy group, an amino group, or an isocyanate group .
8.其他添加剂8. Other additives
本发明的聚苯硫醚树脂组合物除了成分(A)～(D)以外可以进一步包括弹性体、抗氧化剂、脱模剂(褐煤酸及其金属盐、其酯、其半酯，硬脂醇，硬脂酰胺，联二脲或聚乙烯蜡等，其中，为了在成型过程中减少气体产生，优选硬脂酰胺)，颜料(硫化镉、酞菁、或着色的炭黑母料等)，染料(苯胺黑等)、结晶剂(滑石粉、二氧化钛、高岭土、粘土等)、增塑剂(辛基-对-羟基苯甲酸酯、或N-丁基苯磺酰胺等)、抗静电剂(烷基硫酸盐型阴离子抗静电剂、季铵型阳离子抗静电剂、聚氧乙烯脱水山梨醇单硬脂酸酯等非离子型抗静电剂、或者三甲铵乙内酯两性抗静电剂)、阻燃剂(例如，红磷、磷酸酯、氰尿酸三聚氰胺、氢氧化镁、氢氧化铝、多磷酸铵、溴化聚苯乙烯、溴化聚苯醚、聚碳酸酯溴化物、溴化环氧树脂或这些含溴阻燃剂和三氧化锑的组合)等，可以从中选择一种或多种配合使用。In addition to the components (A) to (D), the polyphenylene sulfide resin composition of the present invention may further include an elastomer, an antioxidant, and a mold release agent (montanic acid and its metal salts, its esters, and its half esters, and stearyl alcohol , Stearamide, biurea or polyethylene wax, etc., in order to reduce gas generation during molding, stearamide is preferred), pigments (cadmium sulfide, phthalocyanine, or colored carbon black masterbatch, etc.), dyes (Aniline black, etc.), crystallizer (talc, titanium dioxide, kaolin, clay, etc.), plasticizer (octyl-p-hydroxybenzoate, or N-butylbenzenesulfonamide, etc.), antistatic agent ( Alkyl sulfate type anionic antistatic agent, quaternary ammonium type cationic antistatic agent, polyoxyethylene sorbitan monostearate and other nonionic antistatic agents, or trimethylammonium lactone amphoteric antistatic agent), resistance Combustion agent (for example, red phosphorus, phosphate ester, 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., one or more of them can be selected and used in combination.
所述弹性体可以列举：烯烃系弹性体、改性烯烃系弹性体、或苯乙烯系弹性体等中的一种或多种。Examples of the elastomer include one or more of olefin-based elastomers, modified olefin-based elastomers, and styrene-based elastomers.
作为烯烃系弹性体例如有：将乙烯、丙烯、1-丁烯、1-戊烯、4-甲基-1-戊烯、或异丁烯等单独的α-烯烃或它们中的多种聚合得到的聚合物或共聚物，α-烯烃与丙烯酸、丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸、甲基丙烯酸甲酯、甲基丙烯酸乙酯、或甲基丙烯酸丁酯等α,β-不饱和酸及其烷基酯的共聚物等。从优异韧性考虑，优选为：聚乙烯、聚丙烯、乙烯/丙烯共聚物、乙烯/1-丁烯共聚物、乙烯/丙烯酸甲酯共聚物、乙烯/丙烯酸乙酯共聚物、乙烯/丙烯酸丁酯共聚物、乙烯/甲基丙烯酸甲酯共聚物、乙烯/甲基丙烯酸乙酯共聚物、乙烯/甲基丙烯酸丁酯共聚物等。Examples of olefin-based elastomers are obtained by polymerizing individual α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, or isobutene, or a plurality of them Polymer or copolymer, α-olefin and acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, or butyl methacrylate α, β -Copolymers of unsaturated acids and their alkyl esters. From the viewpoint of excellent toughness, preferred are: polyethylene, polypropylene, ethylene/propylene copolymer, ethylene/1-butene copolymer, ethylene/methyl acrylate copolymer, ethylene/ethyl acrylate copolymer, ethylene/butyl acrylate Copolymer, ethylene/methyl methacrylate copolymer, ethylene/ethyl methacrylate copolymer, ethylene/butyl methacrylate copolymer, etc.
作为改性烯烃系弹性体可通过向上述的烯烃系弹性体中导入具有环氧基、酸酐基、或离子键聚合物等官能团的单体成分(含官能团的成分)而获得。该含官能团的成分可以列举：马来酸酐、衣康酸酐、柠康酸酐、内双环〔2，2，1〕5-庚烯-2，3-二羧酸、或内双环〔2，2，1〕5-庚烯-2，3-二羧酸酐等含有酸酐基的单体，丙烯酸缩水甘油酯、甲基丙烯酸缩水甘油酯、乙基丙烯酸缩水甘油酯、衣康酸缩水甘油酯、或柠康酸缩水甘油酯等含有环氧基的单体，或羧酸金属络合物等含有离子键聚合物的单体。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 above-mentioned olefin elastomer. Examples of the functional group-containing component include maleic anhydride, itaconic anhydride, citraconic anhydride, internal bicyclic [2,2,1] 5-heptene-2,3-dicarboxylic acid, or internal bicyclic [2,2, 1] monomers containing acid anhydride groups such as 5-heptene-2,3-dicarboxylic anhydride, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconic acid, or lemon Epoxy group-containing monomers such as glycidyl carboxylate or ionomer-containing monomers such as metal carboxylate complexes.
对于导入这些含有官能团的单体成分的方法没有特别限定，可以采用以下方法：与上述烯烃系弹性体聚合时使用的成分共聚合；或者使用自由基引发剂向烯烃系(共)聚合物接枝导入等的方法。相对于构成改性烯烃系弹性体的全部单体，含官能团的成分的导入量在0.001-40mol％、优选为0.01-35mol％。The method of introducing these functional group-containing monomer components is not particularly limited, and the following methods may be used: copolymerization with the components used in the polymerization of the olefin-based elastomer; or grafting of an olefin-based (co)polymer using a radical initiator Import methods. The introduction amount of the functional group-containing component is 0.001 to 40 mol%, preferably 0.01 to 35 mol% with respect to all monomers constituting the modified olefin elastomer.
向烯烃系弹性体中导入具有环氧基、酸酐基、或离子键聚合物等官能团的单体成分而得到的特别有用的改性烯烃系弹性体可以列举：乙烯/丙烯-g-甲基丙烯酸缩水甘油酯共聚物(“g”表示接枝，以下相同)、乙烯/1-丁烯-g-甲基丙烯酸缩水甘油酯共聚物、乙烯/丙烯酸缩水甘油酯共聚物、乙烯/甲基丙烯酸缩水甘油酯共聚物、乙烯/丙烯酸甲酯/甲基丙烯酸缩水甘油酯共聚物、乙烯/甲基丙烯酸甲酯/甲基丙烯酸缩水甘油酯共聚物、乙烯/丙烯-g-马来酸酐共聚物、乙烯/1-丁烯-g-马来酸酐共聚物、乙烯/丙烯酸甲酯-g-马来酸酐共聚物、乙烯/丙烯酸乙酯-g-马来酸酐共聚物、乙烯/甲基丙烯酸甲酯-g-马来酸酐共聚物、乙烯/甲基丙烯酸乙酯-g-马来酸酐共聚物、乙烯/甲基丙烯酸共聚物的锌络合物、乙烯/甲基丙烯酸共聚物的镁络合物、或乙烯/甲基丙烯酸共聚物的钠络合物等。Examples of particularly useful modified olefin elastomers obtained by introducing monomer components having functional groups such as epoxy groups, acid anhydride groups, or ionomers into olefin elastomers include ethylene/propylene-g-methacrylic acid Glycidyl ester copolymer ("g" means graft, the same below), ethylene/1-butene-g-glycidyl methacrylate copolymer, ethylene/glycidyl acrylate copolymer, ethylene/methacrylic acid glycidyl Glyceride 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, etc.
从相容性考虑，优选为：乙烯/甲基丙烯酸缩水甘油酯共聚物、乙烯/丙烯酸甲酯/甲基丙烯酸缩水甘油酯共聚物、乙烯/甲基丙烯酸甲酯/甲基丙烯酸缩水甘油酯共聚物、乙烯/1-丁烯-g-马来酸酐共聚物、或乙烯/丙烯酸乙酯-g-马来酸酐共聚物。进一步优选为：乙烯/甲基丙烯酸缩水甘油酯共聚物、乙烯/丙烯酸甲酯/甲基丙烯酸缩水甘油酯共聚物、或乙烯/甲基丙烯酸甲酯/甲基丙烯酸缩水 甘油酯共聚物。From the viewpoint of compatibility, preferred 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.
作为苯乙烯系弹性体可以列举：苯乙烯/丁二烯共聚物、苯乙烯/乙烯/丁二烯共聚物、苯乙烯/乙烯/丙烯共聚物、或苯乙烯/异戊二烯共聚物等，从相容性考虑优选苯乙烯/丁二烯共聚物。Examples of the styrene-based elastomer include styrene/butadiene copolymer, styrene/ethylene/butadiene copolymer, styrene/ethylene/propylene copolymer, styrene/isoprene copolymer, and the like. The styrene/butadiene copolymer is preferred from the viewpoint of compatibility.
从流动性和韧性两方面考虑，弹性体的添加量为：相对于100质量份成分(A)和成分(C)优选为0.5-20质量份，进一步优选为0.8-10质量份，更优选为1-6质量份，另外，在不影响本发明效果的范围内，上述弹性体可以将多种结合使用。From the aspects of fluidity and toughness, the amount of elastomer added is preferably 0.5-20 parts by mass, more preferably 0.8-10 parts by mass, and more preferably 100 parts by mass of component (A) and component (C). 1-6 parts by mass. In addition, as long as the effect of the present invention is not affected, the above-mentioned elastomers may be used in combination.
所述抗氧化剂优选为从酚类抗氧化剂和磷类抗氧化剂中选择的至少一种。在并用酚类抗氧化剂和磷类抗氧化剂时，可高效地保持耐热性和热稳定性，因此二者并用是优选的。The antioxidant is preferably at least one selected from phenolic antioxidants and phosphorus antioxidants. When phenolic antioxidants and phosphorus antioxidants are used in combination, heat resistance and thermal stability can be efficiently maintained, and therefore it is preferable to use both.
作为酚类抗氧化剂，优选使用受阻酚类化合物。具体的例子有：三甘醇双(3-叔丁基-(5-甲基-4-羟基苄基)丙酸酯)、N,N′-六亚甲基双(3,5-二叔丁基-4-羟基-氢化肉桂酰胺)、四(亚甲基-3-(3′,5′-二叔丁基-4′-羟基苄基)丙酸酯)甲烷、季戊四醇四(3-(3′,5′-二叔丁基)-4′-羟基苄基)丙酸酯)、1,3,5-三(3,5-二叔丁基-4-羟基苄基)-s-三嗪-2，4，6-(1H,3H,5H)-三酮、1，1，3-三(2-甲基-4-羟基-5-叔丁基苯基)丁烷、4，4′-亚丁基双(3-甲基-6-叔丁基苯基)、正十八烷基-3-(3,5-二叔丁基-4-羟基苯基)丙酸酯、3，9-双(2-(3-(3-叔丁基-4-羟基-5-甲基苯基)丙酰氧基)-1,1-二甲基乙基)-2,4,8,10-四氧杂螺(5,5)十一烷、或1,3,5-三甲基-2,4,6-三-(3,5-二叔丁基-4-羟基苄基)苯等。其中优选酯型高分子受阻酚类，具体地优选使用四(亚甲基-3-(3′,5′-二叔丁基-4′-羟基苄基)丙酸酯)甲烷、季戊四醇四(3-(3′,5′-二叔丁基)-4′-羟基苄基)丙酸酯)、或3，9-双(2-(3-(3-叔丁基-4-羟基-5-甲基苯基)丙酰氧基)-1,1-二甲基乙基)-2,4,8,10-四氧杂螺(5,5)十一烷等。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,N′-hexamethylenebis(3,5-di-tert Butyl-4-hydroxy-hydrocinnamide), tetrakis(methylene-3-(3′,5′-di-tert-butyl-4′-hydroxybenzyl)propionate) methane, pentaerythritol tetra(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, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 4 , 4′-butylene bis(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-tri-(3,5-di-tert-butyl-4-hydroxybenzyl Group) benzene and so on. Among them, ester type polymer hindered phenols are preferred, and specifically, tetrakis(methylene-3-(3′,5′-di-tert-butyl-4′-hydroxybenzyl)propionate)methane, pentaerythritol tetra( 3-(3′,5′-di-tert-butyl)-4′-hydroxybenzyl)propionate), or 3,9-bis(2-(3-(3-tert-butyl-4-hydroxy- 5-methylphenyl) propionyloxy)-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro(5,5)undecane and the like.
作为磷类抗氧化剂，可以列举出双(2,6-二叔丁基-4-甲基苯基)季戊四醇-二亚磷酸酯、双(2,4-二叔丁基苯基)季戊四醇-二亚磷酸酯、双(2,4-二枯基苯基)季戊四醇-二亚磷酸酯、三(2,4-二叔丁基苯基)亚磷酸酯、四(2，4-二叔丁基苯 基)-4,4′-双亚苯基亚磷酸酯、二硬脂酰基季戊四醇-二亚磷酸酯、三苯基亚磷酸酯、或3,5-二丁基-4-羟基苄基磷酸酯二乙酯等。Examples of phosphorus-based antioxidants include bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol-diphosphite and bis(2,4-di-tert-butylphenyl)pentaerythritol-di Phosphite, bis(2,4-dicumylphenyl) pentaerythritol-diphosphite, tri(2,4-di-tert-butylphenyl) phosphite, tetra(2,4-di-tert-butyl) Phenyl)-4,4′-bisphenylene phosphite, distearoyl pentaerythritol-diphosphite, triphenyl phosphite, or 3,5-dibutyl-4-hydroxybenzyl phosphate Ester diethyl ester and so on.
抗氧化剂的添加量，相对于相对成分(A)和(C)100质量份而言优选0.01-3质量份，更优选0.05-2质量份，最优选0.1-1质量份。The amount of the antioxidant 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 relative to 100 parts by mass of the components (A) and (C).
本发明的聚苯硫醚树脂组合物可以通过一般的树脂成型方法进行成型，并且本发明的聚苯硫醚树脂组合物具有优异的机械强度和耐湿热性，尤其适用于注塑成汽车等的冷却水、防冻液循环***及其他长期与水等液体接触的制品。The polyphenylene sulfide resin composition of the present invention can be molded by a general resin molding method, and the polyphenylene sulfide resin composition of the present invention has excellent mechanical strength and heat and humidity resistance, and is particularly suitable for cooling of injection molding into automobiles and the like Water, antifreeze circulation system and other products that have been in contact with water for a long time.
下面通过具体的实施例来进一步说明本发明，以下实施例在本发明技术方案为前提下进行实施，给出了详细的实施方式和具体的操作过程，但本发明的保护范围不限于下述的实施例。The following further describes the present invention through specific examples. The following examples are implemented on the premise of the technical solution of the present invention, and provide detailed embodiments and specific operation procedures, but the scope of protection of the present invention is not limited to the following Examples.
实施例Examples
1.聚苯硫醚树脂组合物的原料1. Raw material of polyphenylene sulfide resin composition
聚对苯硫醚-间苯硫醚无规共聚物(p-PPS/m-PPS无规共聚物)A-1：直链型对苯硫醚-间苯硫醚无规共聚物(间苯硫醚单元1wt％，重均分子量：50,000)Poly-p-phenylene sulfide-m-phenyl sulfide random copolymer (p-PPS/m-PPS random copolymer) A-1: Straight-chain p-phenyl sulfide-m-phenyl sulfide random copolymer (m-benzene Sulfide unit 1wt%, weight average molecular weight: 50,000)
聚对苯硫醚-间苯硫醚无规共聚物(p-PPS/m-PPS无规共聚物)A-2：直链型对苯硫醚-间苯硫醚无规共聚物(间苯硫醚单元2wt％，重均分子量：49,000)Poly-p-phenylene sulfide-m-phenyl sulfide random copolymer (p-PPS/m-PPS random copolymer) A-2: Straight-chain p-phenyl sulfide-m-phenyl sulfide random copolymer (m-benzene Sulfide unit 2wt%, weight average molecular weight: 49,000)
聚对苯硫醚-间苯硫醚无规共聚物(p-PPS/m-PPS无规共聚物)A-3：直链型对苯硫醚-间苯硫醚无规共聚物(间苯硫醚单元5wt％，重均分子量：54,000)Poly-p-phenylene sulfide-m-phenyl sulfide random copolymer (p-PPS/m-PPS random copolymer) A-3: Straight-chain p-phenyl sulfide-m-phenyl sulfide random copolymer (m-benzene Sulfide unit 5wt%, weight average molecular weight: 54,000)
聚对苯硫醚-间苯硫醚无规共聚物(p-PPS/m-PPS无规共聚物)A-4：直链型对苯硫醚-间苯硫醚无规共聚物(间苯硫醚单元8wt％，重均分子量：51,000)Poly-p-phenylene sulfide-m-phenyl sulfide random copolymer (p-PPS/m-PPS random copolymer) A-4: Straight-chain p-phenyl sulfide-m-phenyl sulfide random copolymer (m-benzene Sulfide unit 8wt%, weight average molecular weight: 51,000)
聚对苯硫醚-间苯硫醚无规共聚物(p-PPS/m-PPS无规共聚物)A-5：直链型对苯硫醚-间苯硫醚无规共聚物(间苯硫醚单元10wt％，重均分子量：52,000)Poly-p-phenylene sulfide-m-phenyl sulfide random copolymer (p-PPS/m-PPS random copolymer) A-5: Straight-chain p-phenyl sulfide-m-phenyl sulfide random copolymer (m-benzene Sulfide unit 10wt%, weight average molecular weight: 52,000)
聚对苯硫醚-间苯硫醚无规共聚物(p-PPS/m-PPS无规共聚物)A-6：直链型对苯硫醚-间苯硫醚无规共聚物(间苯硫醚单元20wt％，重均分子量：58,000)Poly-p-phenylene sulfide-m-phenyl sulfide random copolymer (p-PPS/m-PPS random copolymer) A-6: Straight-chain p-phenyl sulfide-m-phenyl sulfide random copolymer (m-benzene Sulfide unit 20wt%, weight average molecular weight: 58,000)
聚对苯硫醚-间苯硫醚无规共聚物(p-PPS/m-PPS无规共聚物)A-7：直链型对苯硫醚-间苯硫醚无规共聚物(间苯硫醚单元25wt％，重均分子量：53,000)Poly-p-phenylene sulfide-m-phenyl sulfide random copolymer (p-PPS/m-PPS random copolymer) A-7: Straight-chain p-phenyl sulfide-m-phenyl sulfide random copolymer (m-benzene Sulfide unit 25wt%, weight average molecular weight: 53,000)
聚对苯硫醚-间苯硫醚嵌段共聚物(p-PPS/m-PPS嵌段共聚物)A’-1：直链型对苯硫醚-间苯硫醚嵌段共聚物(间苯硫醚单元10wt％，重均分子量：54,000)Poly(p-phenylene sulfide)-m-phenylene sulfide block copolymer (p-PPS/m-PPS block copolymer) A'-1: Straight-chain p-phenylene sulfide-m-phenylene sulfide block copolymer (between Phenyl sulfide unit 10wt%, weight average molecular weight: 54,000)
聚对苯硫醚均聚物(p-PPS)C-1：直链型p-PPS树脂(重均分子量：49,000)Poly-p-phenylene sulfide homopolymer (p-PPS) C-1: linear p-PPS resin (weight average molecular weight: 49,000)
玻璃纤维B-1：日本电气硝子株式会社T-760H(单纤直径10.5μm)Glass fiber B-1: Nippon Electric Glass Co., Ltd. T-760H (single fiber diameter 10.5 μm)
碳酸钙B-2：株式会社Calfine KSS-1000Calcium carbonate B-2: Calfine KSS-1000
硅烷化合物D-1：Dow Chemical Company,XIAMETER TM OFS-6040 Silane compound D-1: Dow Chemical Company, XIAMETER TM OFS-6040
脱模剂E-1：PRIME POLYMER,PE7000FBRelease agent E-1: PRIME POLYMER, PE7000FB
颜料F-1：炭黑母料，东丽株式会社S771B2Pigment F-1: Carbon black masterbatch, Toray S771B2
2.实施例和比较例中涉及的测试说明如下：2. The test descriptions involved in the examples and comparative examples are as follows:
1)熔点测定1) Melting point determination
将实施例与比较例所得的经挤出造粒并干燥好的聚苯硫醚树脂组合物粒子用切刀切出约5mg的样品。随后将切出的样品通过TA社DSC-discover 250型号示差扫描量热仪(DSC)在氮气气氛下以20℃/min的升温速率从0℃升至340℃，于340℃恒温5分钟后，再以20℃/min的降温速率从340℃降至0℃，在0℃保持3分钟。随后再以20℃/min的升温速率从0℃升至340℃升温，并对此升温过程中所出现的的吸热峰峰尖温度即为熔点。The polyphenylene sulfide resin composition particles obtained by extrusion granulation and drying obtained in Examples and Comparative Examples were cut with a cutter to obtain a sample of about 5 mg. Subsequently, the cut samples were raised from 0°C to 340°C at a heating rate of 20°C/min under a nitrogen atmosphere with a DSC-discover 250 differential scanning calorimeter (DSC) of a TA company under a nitrogen atmosphere. After a constant temperature of 340°C for 5 minutes, The temperature was reduced from 340°C to 0°C at a rate of 20°C/min, and kept at 0°C for 3 minutes. Subsequently, the temperature is increased from 0°C to 340°C at a heating rate of 20°C/min, and the endothermic peak-to-peak temperature that appears during the heating process is the melting point.
2)拉伸强度测试：2) Tensile strength test:
将实施例和比较例中所得注塑成型好的标准样条按照ISO 527-1,-2标准测定，拉伸速率5mm/min，标线间距离50mm，夹具间距离115mm，每组5根取平均值作为拉伸强度。The injection molded standard splines obtained in the examples and comparative examples are measured according to the ISO 527-1,-2 standard, the drawing rate is 5 mm/min, the distance between the marking lines is 50 mm, the distance between the fixtures is 115 mm, and the average of 5 pieces in each group is averaged The value is taken as the tensile strength.
3)PCT处理后的拉伸强度测试：3) Tensile strength test after PCT treatment:
将实施例和比较例中所得注塑成型好的标准样条放置于espec公司制EHS-221M型号的恒温恒湿箱内，在121℃×100％相对湿度的条件下处理100小时后，取出进行上述的拉伸强度测试评价PCT处理后的拉伸强度，每组5 根取平均值作为PCT处理后的拉伸强度。The injection-molded standard splines obtained in the examples and comparative examples were placed in a constant temperature and humidity chamber of the EHS-221M model manufactured by espec, and treated at 121°C×100% relative humidity for 100 hours. The tensile strength test evaluates the tensile strength after PCT treatment, and the average value of 5 of each group is taken as the tensile strength after PCT treatment.
4)PCT处理后的拉伸强度保持计算：4) Calculation of tensile strength retention after PCT treatment:
假设上述测试方法中评价得出的拉伸强度为S1，PCT处理后的拉伸强度为S2，根据下述公式(1)计算出PCT处理后的拉伸强度保持率：Assuming that the tensile strength evaluated in the above test method is S1 and the tensile strength after PCT treatment is S2, the retention rate of tensile strength after PCT treatment is calculated according to the following formula (1):
Figure PCTCN2019126492-appb-000004
Figure PCTCN2019126492-appb-000004
5)树脂基体与玻璃纤维剥离时的剪切强度测试：5) Shear strength test when the resin matrix and glass fiber are peeled:
将实施例和比较例中所得的标准样条中心部分顺着与样条长边方向垂直的平面切成薄片样品，将所得薄片切片样品中所存在的单根玻璃纤维通过Hysitron社高分辨率超微小硬度计Triboindenter TI950的半球状压头顺着垂直于切片样品中的玻璃纤维断面方向将其从树脂基体中推出，从而测定树脂和玻璃纤维发生剥离时的剪切强度。树脂基体与玻璃纤维发生剥离时的剪切强度越高，表明树脂与玻璃纤维的粘结性越好。The central part of the standard spline obtained in the examples and comparative examples was cut into thin slice samples along a plane perpendicular to the longitudinal direction of the spline, and the single glass fibers present in the obtained thin slice sample were passed through Hysitron Corporation The hemispherical indenter of the micro hardness tester Triboindenter TI950 is pushed out of the resin matrix in a direction perpendicular to the cross section of the glass fiber in the sliced sample, thereby measuring the shear strength when the resin and glass fiber are peeled off. The higher the shear strength when the resin matrix and the glass fiber are peeled off, the better the adhesion between the resin and the glass fiber.
6)PCT处理后玻璃纤维表面树脂附着比例测定：6) Determination of the resin adhesion ratio of the glass fiber surface after PCT treatment:
将实施例和比较例中所得的PCT处理后的标准样条的中心部切出，将其溶解于α-氯萘中，于高温下进行过滤，将高温过滤后残留于漏斗上的玻璃纤维清洗回收干燥后，使用PHI社Quantera SXM对玻璃纤维表面进行元素分析。得到检出元素中来源于聚苯硫醚树脂的硫元素的相对含量S(atomic％)。S数值越大表明检出元素中所含有的聚苯硫醚树脂的比例越多。The central part of the PCT-treated standard spline obtained in Examples and Comparative Examples was cut out, dissolved in α-chloronaphthalene, filtered at high temperature, and the glass fiber remaining on the funnel after high temperature filtration was washed After recycling and drying, PHI Quantera SXM was used to perform elemental analysis on the glass fiber surface. The relative content S (atomic%) of the sulfur element derived from the polyphenylene sulfide resin in the detected elements was obtained. The larger the value of S, the greater the proportion of polyphenylene sulfide resin contained in the detected element.
实施例1-5、比较例1-3：Examples 1-5, Comparative Examples 1-3:
原料如表1中所示，采用日本制钢所社制TEX30α型双轴挤出机(L/D＝45.5)造粒，挤出机有13个加热区，有两套带计量仪器的加料装置并且带有真空排气设备。除玻璃纤维以外，其他原料混合后，从挤出机主喂料口加入，玻璃纤维从挤出机侧喂料口加入，挤出机温度设定为200℃-330℃，经熔融、挤出、冷却、切粒得到粒状聚苯硫醚树脂组合物；将此粒状物在130℃的烘箱中干燥3h后，采用日精树脂工业株式会社制NEX50型号注塑机按照成型温度 330℃、模具温度130℃的条件注塑成型成ISO标准样条(样条模具尺寸为宽10mm×厚4mm)，按上述测试方法进行性能测试。组合物熔点、拉伸强度、耐湿热性数据(以进行100小时PCT处理后的拉伸强度和拉伸强度保持率来评价)如表1所示。The raw materials are as shown in Table 1. Pelletizing is carried out by TEX30α type twin-screw extruder (L/D=45.5) manufactured by Japan Steel Co., Ltd. The extruder has 13 heating zones and two feeding devices with measuring instruments And with vacuum exhaust equipment. Except for the glass fiber, after the other raw materials are mixed, they are added from the main feed port of the extruder, and the glass fibers are added from the feed port on the side of the extruder. The temperature of the extruder is set at 200 ℃-330 ℃, after melting, extruding , Cooling and pelletizing to obtain a granular polyphenylene sulfide resin composition; after drying the pellets in an oven at 130 ℃ for 3 hours, using a NEX50 model injection molding machine manufactured by Nissei Resin Co., Ltd. according to a molding temperature of 330 ℃ and a mold temperature of 130 ℃ The conditions are injection molded into ISO standard splines (spline mold size is 10mm wide x 4mm thick), and the performance test is performed according to the above test method. The composition melting point, tensile strength, and heat and humidity resistance data (evaluated by the tensile strength after 100 hours of PCT treatment and the tensile strength retention ratio) are shown in Table 1.
实施例6-7、比较例4-8：Example 6-7, Comparative Example 4-8:
采用日精树脂工业株式会社制NEX50型号注塑机按照成型温度330℃、模具温度70℃的条件注塑成型成ISO标准样条(样条模具尺寸为宽10mm×厚4mm)，在145℃的烘箱中进行1小时热处理后(和表1所示样品在相同条件下进行成型时，固化速度太慢，导致脱模时ISO标准样条会发生变形，所以在低温成型后进行热处理)，按上述测试方法进行性能测试。除此以外与实施例1制备方法相同，组合物熔点、拉伸强度以及耐湿热性数据(以进行100小时PCT处理后的拉伸强度和拉伸强度保持率来评价)如表2所示。实施例6及比较例4的玻璃纤维与树脂基体之间的剥离剪切强度和玻璃纤维表面的树脂附着比例数据如表4所示。An NEX50 injection molding machine manufactured by Nissei Resin Co., Ltd. was used to injection mold an ISO standard spline (spline mold size is 10 mm wide × 4 mm thick) under the conditions of a molding temperature of 330° C. and a mold temperature of 70° C. in an oven at 145° C. After 1 hour heat treatment (when the sample shown in Table 1 is molded under the same conditions, the curing speed is too slow, resulting in deformation of the ISO standard spline during demolding, so heat treatment is performed after low temperature molding), according to the above test method Performance Testing. Except for this, it is the same as the preparation method of Example 1, and the composition melting point, tensile strength, and hygrothermal resistance data (evaluated by the tensile strength after 100 hours of PCT treatment and the tensile strength retention ratio) are shown in Table 2. Table 4 shows the data of the peeling shear strength between the glass fiber and the resin matrix of Example 6 and Comparative Example 4 and the resin adhesion ratio on the glass fiber surface.
实施例8-15：Examples 8-15:
除了添加了聚苯硫醚均聚物以外，与实施例1制备方法和评价方法相同，组合物熔点、拉伸强度以及耐湿热性数据(以进行100小时PCT处理后的拉伸强度和拉伸强度保持率来评价)如表3所示。Except for the addition of polyphenylene sulfide homopolymer, the same as the preparation method and evaluation method of Example 1, the composition melting point, tensile strength, and heat and humidity resistance data (in 100 hours after the PCT treatment of tensile strength and tensile The strength retention rate was evaluated) as shown in Table 3.
表1Table 1
Figure PCTCN2019126492-appb-000005
Figure PCTCN2019126492-appb-000005
Figure PCTCN2019126492-appb-000006
Figure PCTCN2019126492-appb-000006
表2Table 2
Figure PCTCN2019126492-appb-000007
Figure PCTCN2019126492-appb-000007
表3table 3
Figure PCTCN2019126492-appb-000008
Figure PCTCN2019126492-appb-000008
表4Table 4
Figure PCTCN2019126492-appb-000009
Figure PCTCN2019126492-appb-000009
1)玻璃纤维与树脂基体间剥离时的剪切强度以比较例4的标准样条进行PCT处理前的强度作为100％进行计算1) The shear strength at the time of peeling between the glass fiber and the resin matrix was calculated based on the strength of the standard sample of Comparative Example 4 before PCT treatment as 100%
从实施例1-5与比较例1-2的对比、实施例6-7与比较例4的对比可见，本发明通过以混合(A)聚对苯硫醚-间苯硫醚无规共聚物和(B)无机填料所形成的树脂组合物，相比于聚对苯硫醚-间苯硫醚嵌段共聚物或聚对苯硫醚均聚物和无机填料所形成的树脂组合物，其进行100小时PCT处理后的拉伸强度和强度保持率高，树脂组合物拥有更好的耐湿热性。It can be seen from the comparison between Examples 1-5 and Comparative Examples 1-2, and between Examples 6-7 and Comparative Example 4, that the present invention is achieved by mixing (A) a poly(p-phenylene sulfide)-m-phenylene sulfide random copolymer Compared with the resin composition formed by (B) inorganic filler, compared to the resin composition formed by poly-p-phenylene sulfide-m-phenylene sulfide block copolymer or poly-p-phenylene sulfide homopolymer and inorganic filler, After 100 hours of PCT treatment, the tensile strength and strength retention rate are high, and the resin composition has better resistance to moisture and heat.
从实施例5与比较例3的对比、实施例6与比较例5的对比可见，不添加无机填料时，聚苯硫醚树脂组合物进行100小时PCT处理后的拉伸强度和强度保持率低。As can be seen from the comparison between Example 5 and Comparative Example 3, and between Example 6 and Comparative Example 5, when no inorganic filler is added, the tensile strength and strength retention rate of the polyphenylene sulfide resin composition after 100 hours of PCT treatment are low .
从实施例6与比较例6-8的对比可见，添加无机填料量过少时，聚苯硫醚树脂组合物进行100小时PCT处理后的拉伸强度和强度保持率低。反之，当添加无机填料量过多时，组合物无法通过挤出机进行混炼加工。As can be seen from the comparison between Example 6 and Comparative Examples 6-8, when the amount of the inorganic filler added is too small, the tensile strength and strength retention rate of the polyphenylene sulfide resin composition after 100 hours of PCT treatment are low. Conversely, when the amount of the inorganic filler added is too large, the composition cannot be kneaded by the extruder.
从实施例8-15和比较例2的对比可见，通过混合(A)聚对苯硫醚-间苯硫醚无规共聚物、(B)无机填料所形成的树脂组合物和(C)聚对苯硫醚均聚物所形成的树脂组合物，进行100小时PCT处理后的拉伸强度和强度保持率高。From the comparison between Examples 8-15 and Comparative Example 2, it can be seen that the resin composition and (C) polymer formed by mixing (A) a poly(p-phenylene sulfide)-m-phenylene sulfide random copolymer, (B) an inorganic filler The resin composition formed of the phenylene sulfide homopolymer has a high tensile strength and strength retention rate after 100 hours of PCT treatment.
从实施例6与比较例4的对比可见，本发明通过以混合(A)聚对苯硫醚- 间苯硫醚无规共聚物和(B)无机填料所形成的树脂组合物，相比于聚对苯硫醚均聚物和无机填料所形成的树脂组合物，其在进行100小时PCT处理后玻璃纤维与树脂基体之间发生剥离的剪切强度更高，并且玻璃纤维表面附着的树脂的比例更大。It can be seen from the comparison between Example 6 and Comparative Example 4 that the present invention is a resin composition formed by mixing (A) a poly(p-phenylene sulfide)-m-phenylene sulfide random copolymer and (B) an inorganic filler, compared to A resin composition formed of a poly(p-phenylene sulfide) homopolymer and an inorganic filler has a higher shear strength for peeling between the glass fiber and the resin matrix after 100 hours of PCT treatment, and the resin adhered to the surface of the glass fiber The proportion is greater.

Claims (14)

  1. 一种聚苯硫醚树脂组合物，其包含：A polyphenylene sulfide resin composition, comprising:
    (A)聚对苯硫醚-间苯硫醚无规共聚物，和(A) Poly-p-phenylene sulfide-m-phenylene sulfide random copolymer, and
    (B)无机填料，(B) inorganic filler,
    相对于所述(A)聚对苯硫醚-间苯硫醚无规共聚物100质量份，所述(B)无机填料的混合量为5-2000质量份。The mixing amount of the (B) inorganic filler is 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. 根据权利要求1所述的聚苯硫醚树脂组合物，其中，所述(A)聚对苯硫醚-间苯硫醚无规共聚物中，相对于无规共聚物中苯硫醚单元总质量，间苯硫醚单元的含量为2-25wt％。The polyphenylene sulfide resin composition according to claim 1, wherein in the (A) poly(p-phenylene sulfide)-m-phenylene sulfide random copolymer, relative to the total phenyl sulfide unit in the random copolymer Mass, the content of m-phenylene sulfide unit is 2-25wt%.
  3. 根据权利要求1所述的聚苯硫醚树脂组合物，其中，所述(A)聚对苯硫醚-间苯硫醚无规共聚物的熔点为210-280℃。The polyphenylene sulfide resin composition according to claim 1, wherein the (A) poly-p-phenylene sulfide-m-phenylene sulfide random copolymer has a melting point of 210-280°C.
  4. 根据权利要求1所述的聚苯硫醚树脂组合物，其中，相对于所述(A)聚对苯硫醚-间苯硫醚无规共聚物100质量份，所述(B)无机填料的混合量为26-2000质量份。The polyphenylene sulfide resin composition according to claim 1, wherein the (B) inorganic filler is relative to 100 parts by mass of the (A) poly(p-phenylene sulfide)-m-phenylene sulfide random copolymer. The mixing amount is 26-2000 parts by mass.
  5. 根据权利要求1所述的聚苯硫醚树脂组合物，其还包含(C)聚对苯硫醚均聚物。The polyphenylene sulfide resin composition according to claim 1, further comprising (C) a poly(phenylene sulfide) homopolymer.
  6. 根据权利要求5所述的聚苯硫醚树脂组合物，其中，相对于所述(A)聚对苯硫醚-间苯硫醚共聚物100质量份，所述(C)聚对苯硫醚均聚物的混合量为10-2500质量份。The polyphenylene sulfide resin composition according to claim 5, wherein the (C) poly p-phenylene sulfide is (C) poly p-phenylene sulfide with respect to 100 parts by mass of the (A) poly p-phenylene sulfide-m-phenylene sulfide copolymer The mixing amount of the homopolymer is 10-2500 parts by mass.
  7. 根据权利要求5所述的聚苯硫醚树脂组合物，其中，相对于(A)聚对苯硫醚-间苯硫醚无规共聚物以及(C)聚对苯硫醚均聚物中苯硫醚单元的总质量，所述(A)聚对苯硫醚-间苯硫醚无规共聚物中的间苯硫醚单元的含量为1-14wt％。The polyphenylene sulfide resin composition according to claim 5, wherein the poly(phenylene sulfide)-m-phenylene sulfide random copolymer and (C) poly(phenylene sulfide) homopolymer in benzene The total mass of the sulfide unit, the content of the m-phenylene sulfide unit in the (A) poly-p-phenylene sulfide-m-phenylene sulfide random copolymer is 1-14 wt%.
  8. 根据权利要求5所述的聚苯硫醚树脂组合物，其中，相对于所述(A)聚对苯硫醚-间苯硫醚无规共聚物及所述(C)聚对苯硫醚均聚物的总质量100 质量份，所述(B)无机填料的混合量为5-150质量份。The polyphenylene sulfide resin composition according to claim 5, wherein the poly(phenylene sulfide)-m-phenylene sulfide random copolymer (A) and the (C) poly(phenylene sulfide) are both The total mass of the polymer is 100 parts by mass, and the mixing amount of the (B) inorganic filler is 5-150 parts by mass.
  9. 根据权利要求5所述的聚苯硫醚树脂组合物，其中，相对于所述(A)聚对苯硫醚-间苯硫醚无规共聚物及所述(C)聚对苯硫醚均聚物的总质量100质量份，所述(B)无机填料的混合量为26-150质量份。The polyphenylene sulfide resin composition according to claim 5, wherein the poly(phenylene sulfide)-m-phenylene sulfide random copolymer (A) and the (C) poly(phenylene sulfide) are both The total mass of the polymer is 100 parts by mass, and the mixing amount of the (B) inorganic filler is 26-150 parts by mass.
  10. 根据权利要求1所述的聚苯硫醚树脂组合物，其中，所述(B)无机填料为选自玻璃纤维、玻璃薄片、玻璃微珠、碳纤维、碳酸钙、二氧化硅、滑石粉或硅灰石中的至少一种。The polyphenylene sulfide resin composition according to claim 1, wherein the (B) inorganic filler is selected from glass fibers, glass flakes, glass beads, carbon fibers, calcium carbonate, silica, talc or silicon At least one of limestone.
  11. 根据权利要求1所述的聚苯硫醚树脂组合物，其还包含(D)硅烷化合物。The polyphenylene sulfide resin composition according to claim 1, further comprising (D) a silane compound.
  12. 根据权利要求11所述的聚苯硫醚树脂组合物，其中，所述(D)硅烷化合物为含有环氧基、氨基或异氰酸酯基中的至少一种的烷氧基硅烷化合物。The polyphenylene sulfide resin composition according to claim 11, wherein the (D) silane compound is an alkoxysilane compound containing at least one of an epoxy group, an amino group, or an isocyanate group.
  13. 一种成型品，其特征在于：使用权利要求1-12中任一项所述的聚苯硫醚树脂组合物得到。A molded article obtained by using the polyphenylene sulfide resin composition according to any one of claims 1-12.
  14. 根据权利要求13所述的成型品，其用于冷却水、防冻液循环***。The molded article according to claim 13, which is used in a cooling water and antifreeze circulation system.
PCT/CN2019/126492 2018-12-24 2019-12-19 Polyphenylene sulfide resin composition and molded product thereof WO2020135200A1 (en)

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