[go: up one dir, main page]
More Web Proxy on the site http://driver.im/

WO2009125556A1 - Composition de résine de sulfure de polyarylène et moulages à base de résine de sulfure de polyarylène destinés à être mis en contact avec un solvant organique - Google Patents

Composition de résine de sulfure de polyarylène et moulages à base de résine de sulfure de polyarylène destinés à être mis en contact avec un solvant organique Download PDF

Info

Publication number
WO2009125556A1
WO2009125556A1 PCT/JP2009/001538 JP2009001538W WO2009125556A1 WO 2009125556 A1 WO2009125556 A1 WO 2009125556A1 JP 2009001538 W JP2009001538 W JP 2009001538W WO 2009125556 A1 WO2009125556 A1 WO 2009125556A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyarylene sulfide
sulfide resin
resin composition
weight
parts
Prior art date
Application number
PCT/JP2009/001538
Other languages
English (en)
Japanese (ja)
Inventor
大西克平
小泉智義
昆野明寛
Original Assignee
ポリプラスチックス株式会社
株式会社クレハ
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ポリプラスチックス株式会社, 株式会社クレハ filed Critical ポリプラスチックス株式会社
Priority to JP2010507139A priority Critical patent/JPWO2009125556A1/ja
Publication of WO2009125556A1 publication Critical patent/WO2009125556A1/fr

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/0204—Polyarylenethioethers
    • C08G75/0209—Polyarylenethioethers derived from monomers containing one aromatic ring
    • C08G75/0213—Polyarylenethioethers derived from monomers containing one aromatic ring containing elements other than carbon, hydrogen or sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/0204—Polyarylenethioethers
    • C08G75/025—Preparatory processes
    • C08G75/0254—Preparatory processes using metal sulfides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/0204—Polyarylenethioethers
    • C08G75/025—Preparatory processes
    • C08G75/0259—Preparatory processes metal hydrogensulfides
    • 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
    • C08K3/041—Carbon nanotubes
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene

Definitions

  • the present invention has excellent releasability and good organic solvent resistance under contact with various organic solvents, that is, it is caused by contact or immersion in an organic solvent typified by a fuel such as an automobile.
  • the present invention relates to a polyarylene sulfide resin composition and a molded article having a performance of small dimensional change and weight change.
  • PAS resin Polyarylene sulfide (hereinafter sometimes abbreviated as PAS) resin, represented by polyphenylene sulfide (hereinafter sometimes abbreviated as PPS) resin, has high heat resistance, mechanical properties, chemical resistance, dimensional stability and flame retardancy. Therefore, it is widely used in electrical / electronic equipment part materials, automotive equipment part materials, chemical equipment part materials, and the like.
  • PPS resin polyphenylene sulfide
  • PAS resin has very good chemical resistance, it is increasingly used in parts that come into contact with organic solvents in electrical / electronic equipment or automobile equipment.
  • the demand for organic solvent resistance has increased more than ever due to the higher performance of parts in contact with the environment and the higher use environment temperature, and it is necessary to improve the PAS resin.
  • Japanese Patent Publication No. 6-45693 describes the reduction of burrs
  • Japanese Patent No. 3568049 describes the improvement of mechanical properties.
  • the effect on the organic solvent resistance to be solved by the present invention is not described.
  • the addition amount or melt viscosity of the polyhaloaromatic compound implemented in Japanese Patent Publication No. 6-45693 and Japanese Patent No. 3568049 is insufficient as an effect on the organic solvent resistance aimed at by the present invention. Disclosure of the invention
  • the present invention provides an organic solvent resistance by greatly improving the performance of organic solvent resistance, that is, small change in size and weight caused by contact or immersion in an organic solvent such as automobile fuel.
  • the object is to provide a PAS resin composition and a molded article that are preferably used in contact applications.
  • the present invention (A) In an organic amide solvent, (a) at least one metal sulfide selected from the group consisting of alkali metal sulfides and alkali metal hydrosulfides and (b) a dihaloaromatic compound in (c) molecule A polyarylene sulfide resin obtained by polymerizing in the presence of a polyhaloaromatic compound having 3 or more halogen substituents, [(c) / [(b) + (c)]] (molar ratio), which is the ratio of component (c) to the sum of components (b) and (c), is 0.001 to 0.01,
  • the melt viscosity ⁇ * 1000 is 5 to 60 Pa ⁇ s, [However, melt viscosity ⁇ * 1000 is a melt viscosity measured at 310 ° C.
  • a polyarylene sulfide resin having a branched structure derived from a polyhaloaromatic compound having a repeating unit of-(Ar-S)-(wherein Ar is an arylene group) and having 3 or more halogen substituents (B) A polyarylene sulfide resin composition comprising 150 to 300 parts by weight of an inorganic filler, and a polyarylene sulfide resin molded product in contact with an organic solvent obtained by molding the resin composition.
  • the PAS resin as the component (A) used in the present invention comprises (a) at least one metal sulfide selected from the group consisting of alkali metal sulfides and alkali metal hydrosulfides in an organic amide solvent, and (b) A PAS resin obtained by polymerizing a dihaloaromatic compound in the presence of (c) a polyhaloaromatic compound having three or more halogen substituents in the molecule, [(c) / [(b) + (c)]] (molar ratio), which is the ratio of component (c) to the sum of components (b) and (c), is 0.001 to 0.01,
  • the melt viscosity ⁇ * 1000 is 5 to 60 Pa ⁇ s, [However, melt viscosity ⁇ * 1000 is a melt viscosity measured at 310 ° C.
  • the organic amide solvent used in the present invention includes an aprotic polar organic solvent that is usually used for the production of PAS resin and is stable against alkali at high temperatures.
  • NMP N-methyl-2-pyrrolidone
  • NMP N-methyl- ⁇ -caprolactam
  • 1,3-dialkyl-2-imidazolidinone 1,3-dialkyl-2-imidazolidinone and the like
  • metal sulfide selected from the group consisting of (a) alkali metal sulfides and alkali metal hydrosulfides is used as the sulfur source of the PAS resin.
  • alkali metal sulfide examples include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide, and a mixture of two or more thereof.
  • the alkali metal sulfide any of an anhydride, a hydrate, and an aqueous solution may be used.
  • sodium sulfide is preferable from the viewpoint of being industrially available at a low cost and being easy to handle.
  • these alkali metal sulfides those which are commercially available as hydrates can be used in addition to being contained in alkali metal hydrosulfides as by-products.
  • alkali metal hydrosulfide examples include lithium hydrosulfide, sodium hydrosulfide, potassium hydrosulfide, rubidium hydrosulfide, cesium hydrosulfide, and mixtures of two or more thereof.
  • the alkali metal hydrosulfide any of an anhydride, a hydrate, and an aqueous solution may be used.
  • sodium hydrosulfide and lithium hydrosulfide are preferable because they are industrially available at low cost.
  • These alkali metal hydrosulfides are preferably used as an aqueous mixture such as an aqueous solution (that is, a mixture with fluid water) from the viewpoints of processing operation and measurement.
  • the alkali metal hydrosulfide used in the present invention may contain a small amount of alkali metal sulfide.
  • the dihaloaromatic compound used in the present invention is a dihalogenated aromatic compound having two halogen atoms directly bonded to an aromatic ring.
  • dihaloaromatic compound examples include o-dihalobenzene, m-dihalobenzene, p-dihalobenzene, dihalotoluene, dihalonaphthalene, methoxy-dihalobenzene, dihalobiphenyl, dihalobenzoic acid, dihalodiphenyl ether, dihalodiphenylsulfone, dihalo Examples thereof include diphenyl sulfoxide and dihalodiphenyl ketone, and these dihaloaromatic compounds can be used alone or in combination of two or more.
  • the halogen atom refers to each atom of fluorine, chlorine, bromine and iodine, and in the same dihaloaromatic compound, the two halogen atoms may be the same or different.
  • the dihaloaromatic compound o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, or a mixture of two or more of these is often used. 4).
  • a polyhaloaromatic compound having 3 or more halogen substituents in the molecule is used as the component (c).
  • the halogen substituent is usually a group in which a halogen atom is directly bonded to an aromatic ring.
  • a halogen atom refers to each atom of fluorine, chlorine, bromine and iodine.
  • a plurality of halogen atoms may be the same or different.
  • Polyhaloaromatic compounds include 1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene, 1,3,5-trichlorobenzene, hexachlorobenzene, 1,2,3,4-tetrachlorobenzene, 1, 2,4,5-tetrachlorobenzene, 1,3,5-trichloro-2,4,6-trimethylbenzene, 2,4,6-trichlorotoluene, 1,2,3-trichloronaphthalene, 1,2,4- Examples include trichloronaphthalene, 1,2,3,4-tetrachloronaphthalene, 2,4,2′-trichlorobenzophenone and the like.
  • polyhaloaromatic compounds can be used alone or in combination of two or more.
  • trihalobenzenes such as 1,2,4-trichlorobenzene and 1,3,5-trichlorobenzene are preferable, and trichlorobenzene is more preferable.
  • component (A) (a) a metal sulfide and (b) a dihaloaromatic compound in (c) a molecule having three or more halogen substituents in an organic amide solvent.
  • a PAS resin polymerized in the presence of a compound is used.
  • the ratio of the component (c) to the total of the components (b) and (c) [(c) / [(b) + (c)]] (molar ratio) is required to be 0.001 to 0.01. If this molar ratio is too small, the organic solvent resistance that is the object of the present invention cannot be sufficiently obtained, and if it is too large, the mechanical properties deteriorate, which is not preferable.
  • the PAS resin used in the present invention is manufactured by a method usually performed as a PAS resin.
  • a ratio (b) / (a) (molar ratio) of 1.0 to 1.2 which is the ratio of the component (b) to the component (a). . If this molar ratio is too small, the inside of the polymerization system becomes unstable, resulting in a decrease in yield. If it is too large, it becomes difficult to obtain the desired melt viscosity, or the polymerization time is very long. Therefore, it is not industrially preferable.
  • a catalyst or a polymerization aid in the polymerization reaction, a molecular weight adjusting agent such as a monohalogen aromatic compound or an active hydrogen-containing compound, a liquid property adjusting agent such as an alkali metal hydroxide, a reducing agent, etc. are appropriately used as desired. And can be added to the polymerization reaction system.
  • a molecular weight adjusting agent such as a monohalogen aromatic compound or an active hydrogen-containing compound
  • a liquid property adjusting agent such as an alkali metal hydroxide, a reducing agent, etc.
  • the organic amide solvent various components such as the component (a), the component (b), the component (c), the catalyst used as desired are charged at a predetermined ratio, and the moisture ratio is adjusted as necessary.
  • the obtained reaction solution is usually heated to a temperature in the range of 180 to 330 ° C., preferably 220 to 300 ° C., to carry out the polymerization reaction.
  • the reaction time varies depending on the type and ratio of each component used, the type of catalyst, and the like, and thus cannot be determined unconditionally, but is usually within 20 hours, preferably about 0.1 to 8 hours.
  • the mixture is usually at a temperature of 300 ° C. or less, preferably 100 to 250 ° C., usually 15 minutes to 24 hours, preferably The heating is performed for 30 minutes to 10 hours.
  • a heating method there are a method of maintaining a constant temperature, a method of raising the temperature stepwise or continuously, or a method of combining both.
  • the dehydration step is performed by a batch method, a continuous method, or a combination method of both methods.
  • the apparatus for performing the dehydration process may be the same as or different from the polymerization tank (reaction can) used in the polymerization process.
  • this polycondensation reaction can be carried out in an inert gas atmosphere such as nitrogen, argon, and carbon dioxide.
  • the reaction pressure is not particularly limited, but is usually from the self-pressure to 50 kg / cm 2 (absolute pressure) of a polycondensation reaction system such as a solvent.
  • the polycondensation reaction may be a one-stage reaction performed at a steady temperature, a multi-stage reaction in which the temperature is raised stepwise, or a reaction mode in which the temperature is gradually raised continuously.
  • the synthesized PAS resin is separated from the reaction vessel directly by a standard method such as filtration or centrifugation, or a condensed liquid such as water and / or diluted acid, for example. Can be isolated from the reaction solution after addition.
  • the isolated polymer is usually washed with water, methanol, acetone or the like, so that the alkali metal halide, alkali metal sulfide, polymerization auxiliary agent and side reaction product adhering to the polymer are obtained. Etc. are removed. Further, without isolating the polymer produced from the reaction-terminated liquid, the solvent can be removed by distillation, and the polymer can be obtained by washing the residue as described above. The recovered solvent can be reused.
  • the PAS resin thus obtained can be subjected to various desalting treatments as necessary to further reduce the salt content such as sodium chloride in the polymer.
  • the PAS resin as the base resin used in the present invention needs to have a melt viscosity ⁇ * 1000 as defined above of 5 to 60 Pa ⁇ s, preferably 10 to 60 Pa ⁇ s, particularly preferably 10 to 40 Pa ⁇ s. s. If the melt viscosity is too low, it is not preferable because the mechanical strength is not sufficient, and if the melt viscosity is too high, not only the fluidity during injection molding becomes poor and the molding operation becomes difficult, but also the resistance to organic solvents decreases. It is not preferable.
  • the (A) PAS resin used in the present invention may be used in combination with a linear PAS having no branched structure or a crosslinked PAS obtained by heat treatment within a range not impairing the organic solvent resistance effect. it can.
  • the melt viscosity is preferably 5 to 60 Pa ⁇ s, but is not limited as long as desired properties such as organic solvent resistance, mechanical properties and moldability are not impaired.
  • the (B) inorganic filler used in the present invention is not particularly limited, but is important for obtaining sufficient mechanical strength.
  • inorganic fillers include, for example, calcium carbonate such as light calcium carbonate, heavy or finely powdered calcium carbonate, special calcium-based fillers; calcined clay such as nepheline, feldspar fine powder, montmorillonite, bentonite, silane modified clay, etc.
  • Clay aluminum silicate powder
  • talc silica (silicon dioxide) powder such as fused silica and crystalline silica
  • silicic acid-containing compounds such as diatomaceous earth and silica sand
  • pulverization of natural minerals such as pumice powder, pumice balloon, slate powder and mica powder Products: Alumina, alumina colloids (alumina sol), alumina-containing compounds such as alumina white, aluminum sulfate, etc .; minerals such as barium sulfate, lithopone, calcium sulfate, molybdenum disulfide, graphite (graphite); glass fibers, glass beads, glass flakes Glass-based fillers such as foam glass beads; Yash sphere, volcanic glass hollow body, synthetic inorganic hollow body, single crystal potassium titanate, carbon nanotube, carbon hollow sphere, carbon 64 fullerene, anthracite powder, artificial cryolite, titanium oxide, magnesium oxide, basic Examples include magnesium, dolomite, potassium
  • the blending amount of the component (B) is 150 to 300 parts by weight, preferably 170 to 250 parts by weight with respect to 100 parts by weight of the PAS resin of the component (A). If the blending amount of component (B) is too small, sufficient mechanical strength and organic solvent resistance may not be obtained, and if it is too large, problems such as decreased toughness or deteriorated workability due to decreased fluidity A point is generated.
  • n is a straight chain having 15 or more Or it is preferable to mix
  • the olefin compound is not particularly limited as long as it has a linear or branched structure in which — (CH 2 ) n — is a basic structural unit and n is 15 or more. If n is less than 15 in the above formula, problems such as increased gas generated during molding due to low thermal stability.
  • the (C) olefin compound include high-density polyethylene, low-density polyethylene, and paraffin, and preferably low-density polyethylene (density 0.90 to 0.93 g / cm 3 ).
  • the blending amount of the (C) olefin compound is 0.01 to 1.0 part by weight, preferably 0.1 to 0.6 part by weight, particularly preferably 0.1 to 0.4 part by weight based on 100 parts by weight of the PAS resin as the component (A). .
  • the blending amount of the olefin compound is too small, it is difficult to release from the mold during molding. On the other hand, if it is too large, the organic solvent resistance is lowered, which is not preferable.
  • the effect of the present invention is further increased by further using (D) a crystal nucleating agent in combination.
  • a crystal nucleating agent used for this purpose, any of known organic nucleating agents and inorganic nucleating agents can be used.
  • inorganic materials include metal oxides such as ZnO, MgO, Al 2 O 3 , TiO 2 , MnO 2 , SiO 2 , and Fe 3 O 4 , nitrides such as boron nitride, Na 2 CO 3 , CaCO 3 , and MgCO 3.
  • organic salts such as calcium oxalate, sodium oxalate, calcium benzoate, calcium phthalate, calcium tartrate, magnesium stearate, heat-resistant polymers, cross-linked products of heat-resistant polymers, etc. be able to.
  • organic salts such as calcium oxalate, sodium oxalate, calcium benzoate, calcium phthalate, calcium tartrate, magnesium stearate, heat-resistant polymers, cross-linked products of heat-resistant polymers, etc. be able to.
  • Particularly preferred are boron nitride and carbon nanotubes.
  • the polymer compound having a crosslinked or branched structure is, for example, a polymer compound having a branched or crosslinked structure produced by polycondensation of a monomer having 3 or more functional groups, or an existing polymer. It may be any of those obtained by later giving a crosslinked or branched structure to the substance, and may be a crosslinked PAS.
  • the carbon nanotube used as the crystal nucleating agent is not particularly limited by the production method or structure, but is preferably a carbon nanotube having an average diameter of 5 to 100 nm and an average aspect ratio of 20 to 2500. If the average diameter is too small, it may be difficult to produce carbon nanotubes. On the other hand, if the average diameter is excessive, a sufficient effect as a crystal nucleating agent cannot be exhibited, and at the same time sufficient organic solvent resistance cannot be obtained, which is not preferable.
  • the average aspect ratio is preferably 50 or more for the purpose of obtaining sufficient nucleating agent performance and organic solvent resistance, but an excessive aspect ratio is not preferable because it is difficult to produce.
  • crystal nucleating agents overlap with inorganic fillers, and these substances can fulfill both functions, but the amount used as (C) crystal nucleating agent is (A) component 100 weight 0.01 to 3 parts by weight per part is sufficient, preferably 0.1 to 2 parts by weight. If it is less than 0.01 parts by weight, the organic solvent resistance is not sufficient.
  • thermoplastic elastomer can be used in combination as appropriate in order to improve the high and low temperature impact characteristics of the molded product.
  • thermoplastic elastomers include polyolefin elastomers, polyester elastomers, fluorine elastomers, silicone elastomers, butadiene elastomers, polyamide elastomers, polystyrene elastomers, urethane elastomers, and various particle elastomers with a cross-linked structure at the center. 1 type or 2 types or more can be used.
  • thermoplastic elastomer an olefin-based elastomer is preferable, and an olefin-based copolymer mainly containing an ⁇ -olefin and a glycidyl ester of ⁇ , ⁇ -unsaturated acid is used. Further, an olefin-based elastomer obtained by copolymerizing various graft copolymers with main components of ⁇ -olefin and glycidyl ester of ⁇ , ⁇ -unsaturated acid can also be preferably used.
  • the blending amount of the thermoplastic elastomer is 1 to 25 parts by weight, preferably 1 to 15 parts by weight, and more preferably 1 to 8 parts by weight with respect to 100 parts by weight of the PAS resin as the component (A). If the blending amount of the thermoplastic elastomer is too small, the effect of improving the high and low temperature impact characteristics is not sufficient, and if it is too large, there arises a problem that the mold deposit attached to the mold during molding is increased.
  • a silane compound can be blended in the resin composition of the PAS molded product of the present invention for the purpose of improving burrs and the like within a range not impairing the effects of the present invention.
  • the silane compound include various types such as vinyl silane, methacryloxy silane, epoxy silane, amino silane, mercapto silane, etc., for example, vinyl trichlorosilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysila. Examples include, but are not limited to, silane, ⁇ -aminopropyltriethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, and the like.
  • thermoplastic resins can be used in combination with a small amount in addition to the above components depending on the purpose.
  • the other thermoplastic resin used here may be any thermoplastic resin that is stable at high temperatures.
  • a known substance added to a general thermoplastic resin that is, a stabilizer such as an antioxidant, a flame retardant, and the like, within a range not impairing the effects of the present invention.
  • Colorants such as dyes and pigments, lubricants, crystallization accelerators, and the like can be appropriately added according to the required performance.
  • the resin composition of the molded product used in the present invention can be prepared by equipment and methods generally used for preparing a synthetic resin composition. Generally, necessary components are mixed, melt-kneaded using a single-screw or twin-screw extruder, and extruded to form pellets for molding. Also, it is one of preferred methods to melt-extrude the resin component and add and blend the fibrous filler in the middle.
  • the resin molding method used in the present invention is not particularly limited, and can be molded using generally known thermoplastic resin molding methods such as injection molding, extrusion molding, vacuum molding, compression molding, etc., but is most preferable. Is injection molding.
  • the mold temperature at the time of molding is preferably 120 to 180 ° C., particularly preferably 130 to 180 ° C., in order to sufficiently crystallize the PAS resin. If the mold temperature is too low, crystallization on the molding surface of the PAS resin becomes insufficient, resulting in a decrease in organic solvent resistance. If the mold temperature is too high, the molding cycle time becomes long. Produce.
  • the molded product used in the present invention is preferably subjected to heat treatment after molding.
  • the heat treatment conditions vary depending on the size, shape, and application of the molded product, but are generally performed at 120 to 240 ° C. If the heat treatment temperature is too low, the heat treatment takes a long time, which is not preferable in terms of production cost. If the heat treatment temperature is too high, the PAS resin deteriorates, which causes a decrease in mechanical strength.
  • the organic solvent with which the molded product used in the present invention is in contact is, for example, as shown below.
  • Alcohol solvents such as methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, phenol, acetone, methyl ethyl ketone, diethyl ketone solvent, dimethyl ether, dipropyl ether, tetrahydrofuran, 1,3-dioxolane, 1,4 -Ether solvents such as dioxane, nitrogen-containing solvents such as N-methylpyrrolidone, dimethylformamide, dimethylacetamide, n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, n-octane, isooctane, n -Aliphatic hydrocarbon solvents such as nonane and n-dode
  • p-DCB p-dichlorobenzene
  • TBC 1,2,4-trichlorobenzene
  • 13 g (0.071 mol) and 143 g of water were added, and the mixture was reacted at 220 ° C. for 3 hours while stirring at a rotational speed of 250 rpm of the stirrer to carry out pre-stage polymerization.
  • the mixture is cooled to near room temperature, the contents are passed through a 100 mesh screen, the granular polymer is sieved, washed with acetone three times, washed three times with water, and washed with an acetic acid aqueous solution adjusted to pH 4. And then again with water four times to obtain a washed granular polymer.
  • the granular polymer was dried at 100 ° C. overnight.
  • the granular polymer thus obtained had an average particle diameter of 480 ⁇ m and a melt viscosity of 20 Pa ⁇ s.
  • Branch PPS-2 A 20-liter autoclave was charged with 6006g of NMP, 2001g of sodium hydrosulfide (purity 62%) and 1170g of caustic soda (purity 74%). After replacing with nitrogen gas, the temperature was gradually raised to 200 ° C while stirring over about 4 hours. Then, 995 g of water, 1269 g of NMP, and 12 g of hydrogen sulfide were distilled out.
  • the number of revolutions of the stirrer was increased to 400 rpm, 444 g of water was injected while stirring was continued, the temperature was raised to 255 ° C., and the reaction was allowed to proceed for 5 hours to perform post-stage polymerization.
  • Branch PPS-3 A 20 liter autoclave is charged with 6000 g of NMP, 2001 g of sodium hydrosulfide (purity 62%) and 1170 g of caustic soda (purity 74%). After replacing with nitrogen gas, the temperature is gradually raised to 200 ° C while stirring for about 4 hours. Then, 995 g of water, 1269 g of NMP, and 12 g of hydrogen sulfide were distilled out.
  • Branch PPS-4 A 20-liter autoclave is charged with 6000 g of NMP, 2000 g of sodium hydrosulfide (purity 62%), and 1180 g of caustic soda (purity 74%). After replacing with nitrogen gas, the temperature is gradually raised to 200 ° C. while stirring for about 4 hours. Then, 979 g of water, 1294 g of NMP, and 12 g of hydrogen sulfide were distilled out.
  • the mixture was cooled to 150 ° C., added with 3580 g (24.35 mol) of p-DCB, 3510 g of NMP, 22 g of TCB (0.12 mol), and 131 g of water, and reacted at 220 ° C. for 4 hours while stirring at a rotation speed of 250 rpm. And pre-stage polymerization was performed.
  • Branch PPS-5 A 20 liter autoclave is charged with 6000 g of NMP, 2001 g of sodium hydrosulfide (purity 62%), and 1180 g of caustic soda (purity 74%). After replacing with nitrogen gas, the temperature is gradually raised to 200 ° C. while stirring for about 4 hours. Then, 971 g of water, 1243 g of NMP, and 12 g of hydrogen sulfide were distilled out.
  • the mixture was cooled to 150 ° C., added with p-DCB 3634 g (24.72 mol), NMP 3461 g, TCB 32 g (0.17 mol), and 122 g of water, and reacted at 220 ° C. for 4 hours with stirring at 250 rpm. And pre-stage polymerization was performed.
  • Branch PPS-6 A 20 liter autoclave is charged with 6000 g of NMP, 2001 g of sodium hydrosulfide (purity 62%), and 1180 g of caustic soda (purity 74%). After replacing with nitrogen gas, the temperature is gradually raised to 200 ° C. while stirring for about 4 hours. Then, 978 g of water, 1245 g of NMP, and 12 g of hydrogen sulfide were distilled out.
  • the mixture was cooled to 150 ° C., added with 3964 g (26.97 mol) of p-DCB, 3463 g of NMP, 60 g of TCB (0.33 mol), and 129 g of water, and reacted at 220 ° C. for 4 hours while stirring at a rotation speed of 250 rpm. And pre-stage polymerization was performed.
  • the mixture is cooled to 150 ° C., 3398 g (23.12 mol) of p-DCB, 3456 g of NMP and 147 g of water are added, and the mixture is reacted at 220 ° C. for 4 hours while stirring at 250 rpm of the stirrer to carry out pre-stage polymerization. It was.
  • the number of revolutions of the stirrer was increased to 400 rpm, 444 g of water was injected while stirring was continued, the temperature was raised to 255 ° C., and the reaction was allowed to proceed for 5 hours to perform post-stage polymerization.
  • the obtained resin composition pellets were put into an injection molding machine having a cylinder temperature of 320 ° C. and molded to produce a target molded product (test piece), and the above evaluation was performed. The results are shown in Table 1.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L’invention concerne une composition de résine de sulfure de polyarylène (PAS) qui comprend (A) 100 parties en poids d’une résine PAS et (B) 150 à 300 parties en poids d’une charge inorganique, et des moulages de la composition qui sont destinés à être mis en contact avec un solvant organique. Selon l’invention, la résine PAS est une résine qui est obtenue par polymérisation de (a) au moins un composé choisi parmi les sulfures de métaux alcalins et les hydrogénosulfures de métaux alcalins avec (b) un composé dihalogénoaromatique dans un solvant amide organique en présence de (c) un composé polyhalogénoaromatique contenant trois substituants halogéno ou plus dans la molécule, qui a un rapport molaire [(c)/[(b)+(c)]] de 0,001 à 0,01 et une viscosité à l’état fondu η*1000 de 5 à 60 Pa s [la viscosité à l’état fondu η*1000 étant une viscosité à l’état fondu déterminée à 310 °C et à un taux de cisaillement de 1000 (1/s) en utilisant un dispositif Capirograph équipé d’une buse ayant un diamètre d’orifice de 1,0 mmΦ et une longueur de 20,0 mm], et qui comprend des unités de répétition -(Ar-S)- (dans lesquelles Ar représente arylène) en tant que constituant principal et présente une structure ramifiée résultant du composant (c).
PCT/JP2009/001538 2008-04-09 2009-04-01 Composition de résine de sulfure de polyarylène et moulages à base de résine de sulfure de polyarylène destinés à être mis en contact avec un solvant organique WO2009125556A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2010507139A JPWO2009125556A1 (ja) 2008-04-09 2009-04-01 ポリアリーレンサルファイド樹脂組成物及び有機溶剤に接するポリアリーレンサルファイド樹脂成形品

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2008100977 2008-04-09
JP2008-100977 2008-04-09

Publications (1)

Publication Number Publication Date
WO2009125556A1 true WO2009125556A1 (fr) 2009-10-15

Family

ID=41161693

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2009/001538 WO2009125556A1 (fr) 2008-04-09 2009-04-01 Composition de résine de sulfure de polyarylène et moulages à base de résine de sulfure de polyarylène destinés à être mis en contact avec un solvant organique

Country Status (3)

Country Link
JP (1) JPWO2009125556A1 (fr)
TW (1) TW200951181A (fr)
WO (1) WO2009125556A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102719098A (zh) * 2011-06-03 2012-10-10 湖北孚龙管业科技有限公司 用于给水管件内嵌件的复合改性聚苯硫醚材料及其制备方法
JP2013023608A (ja) * 2011-07-22 2013-02-04 Tosoh Corp ポリアリーレンスルフィド系組成物
WO2013090168A1 (fr) * 2011-12-16 2013-06-20 Ticona Llc Moulage par injection de compositions de polysulfure d'arylène
WO2013090163A1 (fr) * 2011-12-16 2013-06-20 Ticona Llc Agent de nucléation contenant du bore pour polysulfure de phénylène
US10647818B2 (en) 2015-01-09 2020-05-12 Kureha Corporation Polyarylene sulfide production method and polyarylene sulfide
WO2021161864A1 (fr) * 2020-02-14 2021-08-19 ポリプラスチックス株式会社 Composition de résine de poly(sulfure d'arylène)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116057116B (zh) * 2020-09-15 2024-02-20 Dic株式会社 聚芳硫醚树脂组合物、成型品和它们的制造方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005298669A (ja) * 2004-04-12 2005-10-27 Polyplastics Co ポリアリーレンサルファイド樹脂組成物及びその成形品
WO2007046451A1 (fr) * 2005-10-19 2007-04-26 Polyplastics Co., Ltd. Composition de résine de polysulfure d'arylène et article moulé en résine de polysulfure d'arylène pouvant être mis en contact avec un solvant organique

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005298669A (ja) * 2004-04-12 2005-10-27 Polyplastics Co ポリアリーレンサルファイド樹脂組成物及びその成形品
WO2007046451A1 (fr) * 2005-10-19 2007-04-26 Polyplastics Co., Ltd. Composition de résine de polysulfure d'arylène et article moulé en résine de polysulfure d'arylène pouvant être mis en contact avec un solvant organique

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102719098A (zh) * 2011-06-03 2012-10-10 湖北孚龙管业科技有限公司 用于给水管件内嵌件的复合改性聚苯硫醚材料及其制备方法
JP2013023608A (ja) * 2011-07-22 2013-02-04 Tosoh Corp ポリアリーレンスルフィド系組成物
WO2013090168A1 (fr) * 2011-12-16 2013-06-20 Ticona Llc Moulage par injection de compositions de polysulfure d'arylène
WO2013090163A1 (fr) * 2011-12-16 2013-06-20 Ticona Llc Agent de nucléation contenant du bore pour polysulfure de phénylène
US10647818B2 (en) 2015-01-09 2020-05-12 Kureha Corporation Polyarylene sulfide production method and polyarylene sulfide
WO2021161864A1 (fr) * 2020-02-14 2021-08-19 ポリプラスチックス株式会社 Composition de résine de poly(sulfure d'arylène)
JP2021127403A (ja) * 2020-02-14 2021-09-02 ポリプラスチックス株式会社 ポリアリーレンサルファイド樹脂組成物

Also Published As

Publication number Publication date
TW200951181A (en) 2009-12-16
JPWO2009125556A1 (ja) 2011-07-28

Similar Documents

Publication Publication Date Title
EP2578637B1 (fr) Composition de résine pour article évidé moulé par soufflage et procédé de production de ladite composition de résine, article évidé moulé par soufflage et son procédé de production
TWI542634B (zh) 聚苯硫樹脂組成物之製造方法
WO2009125556A1 (fr) Composition de résine de sulfure de polyarylène et moulages à base de résine de sulfure de polyarylène destinés à être mis en contact avec un solvant organique
JP2008144002A (ja) ポリアリーレンスルフィド組成物
JP5222474B2 (ja) ポリアリーレンスルフィド樹脂組成物及びその製造方法
KR20130138538A (ko) 폴리아릴렌 설파이드 수지 조성물 및 이의 제조 방법
JP4961921B2 (ja) ポリアリーレンスルフィド組成物
EP2787042A1 (fr) Composition de résine de sulfure de polyphénylène, procédé pour la production de ladite composition, et plaque réfléchissante
JP2018009148A (ja) ポリアリーレンスルフィド樹脂組成物の製造方法
JP6194623B2 (ja) ポリアリーレンスルフィド樹脂組成物
JP2005298669A (ja) ポリアリーレンサルファイド樹脂組成物及びその成形品
JP3618018B2 (ja) ポリフェニレンスルフィド樹脂組成物
JP2012131968A (ja) 金属膜を形成した反射板
JP7424181B2 (ja) ポリフェニレンスルフィド樹脂組成物および成形体
KR102502509B1 (ko) 유동성이 우수한 폴리아릴렌 설파이드 수지 조성물
JP2010007014A (ja) ポリフェニレンスルフィド樹脂組成物
JPWO2007046451A1 (ja) ポリアリーレンサルファイド樹脂組成物及び有機溶剤に接するポリアリーレンサルファイド樹脂成形品
JP5601171B2 (ja) ポリアリーレンスルフィド組成物
JP4090880B2 (ja) ポリアリーレンスルフィド樹脂
JP4954516B2 (ja) ポリアリーレンサルファイド樹脂組成物
JP2015101632A (ja) ポリアリーレンスルフィド系組成物
JP3501165B2 (ja) ポリアリーレンスルフィド樹脂組成物
JP6056504B2 (ja) 高強度ポリアリーレンスルフィド系組成物
JP3603431B2 (ja) ポリアリーレンスルフィド樹脂組成物
CN114729189A (zh) 汽车冷却部件用聚苯硫醚树脂组合物及汽车冷却部件

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09729459

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2010507139

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 09729459

Country of ref document: EP

Kind code of ref document: A1