WO2022019204A1 - ハロゲン化ポリフェニレンスルフィド樹脂、樹脂組成物、成形品、及び樹脂用制振化剤 - Google Patents

ハロゲン化ポリフェニレンスルフィド樹脂、樹脂組成物、成形品、及び樹脂用制振化剤 Download PDF

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WO2022019204A1
WO2022019204A1 PCT/JP2021/026578 JP2021026578W WO2022019204A1 WO 2022019204 A1 WO2022019204 A1 WO 2022019204A1 JP 2021026578 W JP2021026578 W JP 2021026578W WO 2022019204 A1 WO2022019204 A1 WO 2022019204A1
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Prior art keywords
resin
mass
polyphenylene sulfide
halogenated
sulfide resin
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PCT/JP2021/026578
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English (en)
French (fr)
Japanese (ja)
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大輔 村野
晴紀 目代
義紀 鈴木
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Kureha Corp
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Kureha Corp
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Priority to US18/005,773 priority Critical patent/US20230279227A1/en
Priority to KR1020227045316A priority patent/KR102833810B1/ko
Priority to CN202180044259.4A priority patent/CN115996988A/zh
Priority to JP2022537961A priority patent/JP7539473B2/ja
Publication of WO2022019204A1 publication Critical patent/WO2022019204A1/ja
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    • 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
    • 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
    • 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
    • C08G75/0231—Polyarylenethioethers containing chain-terminating or chain-branching agents
    • 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
    • C08G75/0245—Block or graft polymers
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • 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 present invention is for a resin composition containing a halogenated polyphenylene sulfide resin, the halogenated polyphenylene sulfide resin and another resin, a molded product comprising the resin composition, and a resin containing the above-mentioned halogenated polyphenylene sulfide resin.
  • anti-vibration agents With respect to anti-vibration agents.
  • Polyphenylene sulfide resin (PAS) represented by polyphenylene sulfide resin (PPS) is an engineering plastic having excellent heat resistance, chemical resistance, flame retardancy, mechanical strength, electrical characteristics, dimensional stability, and the like. PAS can be molded into various molded products, films, sheets, fibers and the like by general melt processing methods such as extrusion molding, injection molding and compression molding. Therefore, PPS is widely used in a wide range of technical fields such as electrical equipment, electronic equipment, automobile equipment, and packaging materials.
  • Examples of the resin composition having excellent vibration damping properties include a polyamide resin composition containing a plate-shaped filler or a needle-shaped filler (see Patent Document 1) and an emulsion resin composition for a vibration damping material (Patent Document 2). ) Etc. are known.
  • the resin composition described in Patent Document 1 cannot be used for fillerless applications because it contains a filler indispensably.
  • the emulsion resin composition for vibration damping material described in Patent Document 2 is an emulsion resin composition, it is difficult to apply it to general resin molding methods such as press molding, extrusion molding, and injection molding. There is a problem.
  • the present invention has been made in view of the above problems, and is a poly (halophenylene) sulfide resin capable of damping the resin without using a filler when added to the resin, and the poly (halophenylene).
  • the present inventors have described above by using a poly (halophenylene) sulfide resin, which is a polycondensate of trihalobenzene and an alkali metal sulfide, as a component for vibration-damping the resin in the resin composition. We have found that the problem can be solved and have completed the present invention.
  • the halogenated polyphenylene sulfide resin according to the present invention is It is a polycondensate of benzene halide and alkali metal sulfide.
  • the halogenated benzene is dihalobenzene and / or trihalobenzene, The ratio of the mass of trihalobenzene to the mass of halogenated benzene is 50% by mass or more.
  • the halogenated benzene has one to three halogen atoms selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the resin composition according to the present invention contains the above-mentioned halogenated polyphenylene sulfide resin and other resins other than the halogenated polyphenylene sulfide resin.
  • the ratio of the mass of the halogenated polyphenylene sulfide resin to the total of the mass of the halogenated polyphenylene sulfide resin and the mass of the thermoplastic resin may be 1% by mass or more and 30% by mass or less.
  • the ratio of the mass of the halogenated polyphenylene sulfide resin to the total of the mass of the halogenated polyphenylene sulfide resin and the mass of the other resin may be larger than 30% by mass and 90% by mass or less. ..
  • the other resin may be a thermoplastic resin.
  • thermoplastic resin may be a polyarylene sulfide resin.
  • the molded product according to the present invention comprises the above resin composition.
  • the vibration damping agent for the resin of the present invention contains the above-mentioned halogenated polyphenylene sulfide resin.
  • a resin composition containing a halogenated polyphenylene sulfide resin which can suppress vibration of the resin without using a filler when added to the resin, and the halogenated polyphenylene sulfide resin and another resin. It is possible to provide a molded product made of the above-mentioned resin composition and a vibration-damping agent for a resin containing the above-mentioned halogenated polyphenylene sulfide resin.
  • FIG. 1 It is a figure which shows the FT-IR measurement result of the halogenated polyphenylene sulfide resin obtained in Example 1.
  • FIG. 1 shows the FT-IR measurement result of the halogenated polyphenylene sulfide resin obtained in Example 1.
  • the halogenated polyphenylene sulfide resin is a polycondensate of benzene halide and an alkali metal sulfide.
  • the halogenated benzene is dihalobenzene and / or trihalobenzene.
  • the ratio of the mass of trihalobenzene to the mass of halogenated benzene is 50% by mass or more.
  • the halogenated benzene has 1 to 3 halogen atoms selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • halogen atom in the halogenated benzene a chlorine atom is preferable from the viewpoint of the reactivity of the polycondensation of the halogenated halobenzene and the availability of the halogenated halobenzene. That is, as the halogenated benzene, dichlorobenzene and trichlorobenzene are preferable.
  • the halogenated polyphenylene sulfide resin is not limited to a linear polymer in which a halophenylene group or a phenylene group and a sulfur atom are alternately bonded.
  • the halogenated polyphenylene sulfide resin contains a branched structure in the molecular chain in which all three halogen atoms of trihalobenzene have reacted with the alkali metal sulfide.
  • trihalobenzene examples include 1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene, and 1,3,5-trichlorobenzene.
  • 1,2,4-trichlorobenzene is preferable in terms of polycondensation reactivity. Therefore, it is preferable that the trihalobenzene contains 1,2,4-trichlorobenzene, and it is more preferable that the total amount of trihalobenzene is 1,2,4-trichlorobenzene.
  • the ratio of the mass of 1,2,4-trichlorobenzene to the mass of trihalobenzene is preferably 70% by mass or more, more preferably 80% by mass or more, and 90% by mass. By mass or more is even more preferable, 95% by mass or more is even more preferable, and 100% by mass is most preferable.
  • dichlorobenzene examples include p-dichlorobenzene, m-dichlorobenzene, and o-dichlorobenzene.
  • p-dichlorobenzene is preferable because it is easily available and inexpensive, and the obtained halogenated polyphenylene sulfide resin has good molding processability and mechanical identification.
  • trihalobenzene may contain dihalobenzene as an impurity. Such trihalobenzene containing dihalobenzene as an impurity can be preferably used as a raw material for halogenated polyphenylene sulfide.
  • the purity of trihalobenzene in trihalobenzene containing dihalobenzene as an impurity is preferably 90% by mass or more and 99.9% by mass or less, and the content of dihalobenzene is preferably 0.1% by mass or more and 10% or less. It is more preferable that the purity of trihalobenzene is 95% by mass or more and 99.9% by mass or less, and the content of dihalobenzene is 0.1% by mass or more and 5% by mass or less.
  • the ratio of the mass of trichlorobenzene to the total mass of trichlorobenzene and dichlorobenzene used in the production of the halogenated polyphenylene sulfide resin is that the vibration damping performance of the halogenated polyphenylene sulfide resin is good. 70% by mass or more is preferable, 90% by mass or more is more preferable, and 100% by mass is further preferable.
  • alkali metal sulfide examples include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, and cesium sulfide. Of these, sodium sulfide and potassium sulfide are preferable, and sodium sulfide is more preferable.
  • Alkali metal sulfides as sulfur sources can also be treated, for example, in the form of either an aqueous slurry or an aqueous solution.
  • the method of the polycondensation reaction between benzene halide and the alkali metal sulfide is not particularly limited, and the same method as the conventionally known method for producing polyarylene sulfide can be appropriately adopted.
  • Preferred methods include a method of heating and polymerizing benzene halide and alkali metal sulfide in the presence of a solvent.
  • the amount of the halogenated benzene used when reacting the halogenated benzene with the alkali metal sulfide is not particularly limited as long as the halogenated polyphenylene sulfide resin having desired properties can be obtained.
  • the amount of benzene halide used is preferably 1.30 mol or more and 1.90 mol or less, and more preferably 1.40 mol or more and 1.80 mol, with respect to 1 mol of the alkali metal sulfide charged as a sulfur source. It is not more than a molar amount, and more preferably 1.50 mol or more and 1.70 mol or less. By using the above amount of trihalobenzene, it is easy to obtain a halogenated polyphenylene sulfide resin having a desired high molecular weight.
  • the solvent is not particularly limited as long as the polycondensation reaction proceeds well.
  • an organic polar solvent is preferable because the raw material compound, the oligomer, and the produced polymer have good solubility and dispersibility.
  • Examples of the organic polar solvent include an organic amide solvent; an aprotic organic polar solvent composed of an organic sulfur compound; and an aprotic organic polar solvent composed of a cyclic organic phosphorus compound.
  • Examples of the organic amide solvent include amide compounds such as N, N-dimethylformamide and N, N-dimethylacetamide; N-alkylcaprolactam compounds such as N-methyl- ⁇ -caprolactam; and N-methyl-2-pyrrolidone (hereinafter, "" NMP ”), N-alkylpyrrolidone compounds such as N-cyclohexyl-2-pyrrolidone or N-cycloalkylpyrrolidone compounds; N, N-dialkylimidazolidinones such as 1,3-dialkyl-2-imidazolidinone.
  • Tetraalkylurea compounds such as tetramethylurea
  • Hexaalkylphosphoric acid triamide compounds such as hexamethylphosphoric acid triamide
  • the aprotic organic polar solvent composed of an organic sulfur compound include dimethyl sulfoxide and diphenyl sulfone.
  • the aprotic organic polar solvent composed of a cyclic organic phosphorus compound include 1-methyl-1-oxophosphoran.
  • an organic amide solvent is preferable in terms of availability, handleability, etc.
  • N-alkylpyrrolidone compound, N-cycloalkylpyrrolidone compound, N-alkylcaprolactum compound, and N, N-dialkylimidazolidinone compound are more preferable.
  • NMP, N-methyl- ⁇ -caprolactum, and 1,3-dialkyl-2-imidazolidinone are even more preferred, with NMP being particularly preferred.
  • the amount of the solvent used is preferably 1 or more and 30 mol or less, and more preferably 3 mol or more and 15 mol or less, with respect to 1 mol of the alkali metal sulfide as a sulfur source from the viewpoint of the efficiency of the polymerization reaction.
  • the reaction solution to be subjected to the polycondensation reaction may be charged with an alkali metal hydroxide together with a halogenated benzene and an alkali metal sulfide.
  • alkali metal hydroxide examples include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide. It has been found that a method of reacting a sulfur source with trihalobenzene in the presence of an alkali metal hydroxide is suitable for obtaining a halogenated polyphenylene sulfide resin having a good balance of various properties.
  • the amount of the alkali metal hydroxide used is not particularly limited as long as it does not impair the object of the present invention.
  • the amount of the alkali metal hydroxide used is typically 0.01 mol or more and 0.1 mol or less, preferably 0.03 mol or more and 0.08 mol, relative to 1 mol of the alkali metal sulfide as a sulfur source. The following are more preferable.
  • Water may be charged into the reaction solution to be subjected to the polycondensation reaction together with benzene halide and alkali metal sulfide.
  • alkali metal sulfides and alkali metal hydroxides can be made into a solution in the reaction system.
  • the amount of water used is not particularly limited as long as it does not impair the object of the present invention.
  • the amount of water used is typically 1.0 mol or more and 2.5 mol or less, more preferably 1.2 mol or more and 2.3 mol or less, with respect to 1 mol of the alkali metal sulfide as a sulfur source.
  • the polycondensation reaction may be carried out in air, but is preferably carried out in an inert gas atmosphere from the viewpoints of suppressing decomposition and coloring of the product and suppressing deterioration of the solvent.
  • the inert gas is not particularly limited, and nitrogen gas, helium gas and the like are preferable, and nitrogen gas is more preferable.
  • the polycondensation reaction may be carried out in a batch manner or in a continuous manner.
  • the temperature at which the polycondensation reaction is carried out is preferably 140 ° C. or higher and 300 ° C. or lower, more preferably 150 ° C. or higher and 280 ° C. or lower, and further preferably 160 ° C. or higher and 265 ° C. or lower.
  • the reaction time is not particularly limited, and the time for the polycondensation reaction to proceed to a desired degree is appropriately selected. Typically, the reaction time is preferably 0.5 hours or more and 12 hours or less, and more preferably 1 hour or more and 6 hours or less.
  • the halogenated polyphenylene sulfide resin is recovered from the reaction solution.
  • the reaction solution is cooled to a temperature near room temperature of, for example, 0 ° C. or higher and 50 ° C. or lower, preferably 10 ° C. or higher and 40 ° C. or lower, and then the halogenated polyphenylene sulfide resin contained in the cooled reaction solution is crude. Clean and collect the product.
  • the crude product of the halogenated polyphenylene sulfide resin is washed by a known method. Examples of the cleaning method include a method in which acetone cleaning and water cleaning are performed in this order.
  • the acetone used for washing may contain, for example, 10% by mass or less, preferably 5% by mass or less of water.
  • the halogenated polyphenylene sulfide resin For washing with acetone and water, it is preferable to wash the halogenated polyphenylene sulfide resin with an aqueous acetic acid solution.
  • concentration of the acetic acid aqueous solution is not particularly limited, but may be, for example, 0.05% by mass or more and 5% by mass or less, and 0.1% by mass or more and 2% by mass or less.
  • the temperature conditions for performing the above cleaning are not particularly limited as long as the desired cleaning effect can be obtained.
  • the temperature at which each of the above cleaning operations is carried out may be, for example, 0 ° C. or higher and 80 ° C. or lower, 10 ° C. or higher and 60 or lower, and 20 ° C. or higher and 50 ° C. or lower.
  • the halogenated polyphenylene sulfide resin washed as described above is dried as necessary to obtain a halogenated polyphenylene sulfide resin.
  • the halogenated polyphenylene sulfide resin obtained by the above method preferably has a glass transition temperature (Tg) in the range of 80 ° C. or higher and 130 or lower. Further, the weight average molecular weight (Mw) is preferably 1000 or more and 5000 or less.
  • the halogenated polyphenylene sulfide resin described above is preferably used by being mixed with a resin other than the halogenated polyphenylene sulfide resin.
  • a resin other than the halogenated polyphenylene sulfide resin By using the halogenated polyphenylene sulfide resin in combination with another resin, the vibration damping property of the other resin can be improved.
  • thermoplastic resin As the other resin, either a curable resin or a thermoplastic resin may be used.
  • a thermoplastic resin is preferable as the other resin because it is easy to uniformly mix the halogenated polyphenylene sulfide resin with the other resin.
  • the curable resin a precursor of a curable resin in an uncured state can also be used.
  • the curable resin may be a thermosetting resin or a photocurable resin, and a thermosetting resin is preferable because it is easy to manufacture a molded product having a large size to some extent.
  • a method of mixing the curable resin and the halogenated polyphenylene sulfide resin a powdered or particulate halogenated polyphenylene sulfide resin is mixed with a liquid or solution precursor of the curable resin in an uncured state. After mixing, a method of removing the solvent, if necessary, can be mentioned. In this case, a curing agent may be added to the mixture depending on the type of the curable resin.
  • the mixture obtained as described above is cured by heating and / or exposure by a method according to the type of the curable resin to obtain a resin composition.
  • curable resin examples include thermosetting resins such as phenol resin, melamine resin, epoxy resin, and alkyd resin, and photocurable resin such as (meth) acrylic resin.
  • the ratio of the mass of the halogenated polyphenylene sulfide resin to the total of the mass of the halogenated polyphenylene sulfide resin and the mass of the other resin is, for example, 1% by mass or more and 90% by mass or less. Is preferable, and 5% by mass or more and 50% by mass or less is more preferable.
  • the poly (halophenylene) sulfide resin and the other resin are typically mixed using a melt kneading device such as a single-screw extruder or a twin-screw extruder.
  • a melt kneading device such as a single-screw extruder or a twin-screw extruder.
  • the mixing conditions are not particularly limited, and are appropriately determined in consideration of the melting point, melt viscosity, etc. of the poly (halophenylene) sulfide resin and other resins.
  • thermoplastic resin examples include polyacetal resin, polyamide resin, polycarbonate resin, polyester resin (polybutylene terephthalate, polyethylene terephthalate, polyallylate resin, liquid crystal polyester resin, etc.), FR-AS resin.
  • FR-ABS resin AS resin, ABS resin, polyphenylene oxide resin, polyarylene sulfide resin, polysulfone resin, polyethersulfone resin, polyether ether ketone resin, fluororesin, polyimide resin, polyamideimide resin, polyamidebismaleimide resin , Polyetherimide resin, polybenzoxazole resin, polybenzothiazole resin, polybenzoimidazole resin, BT resin, polymethylpentene, ultrahigh molecular weight polyethylene, FR-polypropylene, polystyrene and the like.
  • the polyarylene sulfide resin is preferable, and the polyphenylene sulfide resin is more preferable, because the compatibility with the halogenated polyphenylene sulfide resin is excellent.
  • a polyp-phenylene sulfide resin which is a polycondensate of p-dichlorobenzene and a sulfide agent (for example, alkali metal sulfide or alkali metal hydrosulfide) is preferable.
  • the polyphenylene sulfide resin is preferably a combination of a p-phenylene sulfide resin and a polym-phenylene sulfide resin in that a resin composition having excellent vibration damping properties can be easily obtained.
  • the polym-phenylene sulfide resin is typically a polycondensate of m-dichlorobenzene and a sulfide agent (eg, alkali metal sulfide or alkali metal hydrosulfide).
  • the polyarylene sulfide resin is not particularly limited, and can be appropriately selected from conventionally known polyarylene sulfide resins.
  • the polyarylene sulfide resin blended with the halogenated polyphenylene sulfide resin preferably has a melting point of 270 ° C. or higher and 300 ° C. or lower, a weight average molecular weight (Mw) of 1000 or higher and 100,000 or lower, and a temperature of 310 ° C.
  • the melt viscosity measured at a shear rate of 1200 sec -1 is preferably 100 Pa ⁇ s or more and 250 Pa ⁇ s or less.
  • the ratio of the mass of the poly (halophenylene) sulfide resin to the total mass of the halogenated polyphenylene sulfide resin and the mass of other resins (particularly thermoplastic resins) is 1 from the viewpoint of molding processability of the resin composition. It is preferably 3% by mass or more and 30% by mass or less, more preferably 3% by mass or more and 25% by mass or less, and more preferably 5% by mass or more and 20% by mass or less.
  • the ratio of the mass of the halogenated polyphenylene sulfide resin to the total of the mass of the halogenated polyphenylene sulfide resin and the total of other resins (particularly the thermoplastic resin) is 30% by mass from the viewpoint of vibration damping of the resin composition. It is preferably 90% by mass or less, more preferably 50% by mass or more and 85% by mass or less, and further preferably 60% by mass or more and 80% by mass or less.
  • the resin compositions described above have been conventionally various resin compositions such as colorants, plasticizers, antioxidants, ultraviolet absorbers, flame retardants, mold release agents, fillers, and reinforcing materials, as required. It may contain an additive or an additive compounded in. These additives or additives are used in an appropriate range of amounts depending on the type of additive or additive.
  • the resin composition described above is suitably used as a vibration damping material.
  • a material showing a value of 0.150 or more as a loss coefficient (tan ⁇ ) measured according to a dynamic viscoelasticity measurement is used as a vibration damping material.
  • the loss coefficient of the damping material is preferably 0.170 or more, more preferably 0.200 or more.
  • the resin composition or vibration damping material described above is suitably used as molded products having various shapes by an appropriate method according to the type of other resin.
  • the other resin is a curable resin
  • the resin composition containing the uncured curable resin is in a liquid state, a molded product having a desired shape can be produced by a 3D printing method.
  • the resin composition may be appropriately cured during molding, or the molded product may be cured after obtaining a molded product having a desired shape.
  • the resin composition is typically molded by a conventional method such as press molding, extrusion molding, or injection molding.
  • the use of the molded product is not particularly limited. Specific examples of the use of the molded product include parts of a device that generates vibration in a vehicle such as an automobile and a two-wheeled vehicle, a ship, a railroad, and an aircraft, or peripheral parts of the device; a seat in the above-mentioned transport machine. Alternatively, peripheral parts of seats, parts of devices such as control devices for which reduction of vibration is desired; various household appliances parts; OA equipment parts; building materials; machine tool parts; industrial machine parts. Among the uses described above, examples of the use of the molded product include parts of a coolant circulation device in a transport aircraft equipped with an internal combustion engine such as an automobile. Examples of the component of the coolant circulation device include a pump housing, a pipe for cooling the coolant, and the like. By using the molded product for the above purposes, it is possible to suppress vibration of various products.
  • the vibration damping agent for the resin contains the above-mentioned halogenated polyphenylene sulfide resin.
  • the vibration damping agent may be composed of only a halogenated polyphenylene sulfide resin, or may be composed of a halogenated polyphenylene sulfide resin and other components.
  • the other components are not particularly limited, and examples thereof include a colorant, the above-mentioned thermoplastic resin, a plasticizer, and a compatibilizer.
  • a masterbatch of the vibration damping agent can be obtained. It is preferable to include a plasticizer and a compatibilizer in the masterbatch, if necessary.
  • Example 1 In a 1 L autoclave with a stirrer, 78.0 g of sodium sulfide, 2.5 g of sodium hydroxide, 374.8 g of N-methyl-2-pyrrolidone (NMP), 27.0 g of ion-exchanged water, and 1,2,4- 195.4 g of trichlorobenzene (purity 99.8% by mass) was charged. Then, after replacing the inside of the autoclave with a nitrogen gas atmosphere, the autoclave was sealed. Then, while stirring the reaction solution in the autoclave, the reaction solution was gradually heated to 240 ° C. over about 30 minutes. After the polycondensation reaction was carried out at 240 ° C.
  • NMP N-methyl-2-pyrrolidone
  • the obtained halogenated polyphenylene sulfide resin was subjected to FT-IR measurement by the KBr tablet method. The measurement results are shown in FIG.
  • the weight average molecular weight (Mw) of the obtained halogenated polyphenylene sulfide resin was 3500, and the glass transition temperature was 90 ° C.
  • Examples 2 to 7 and Comparative Example 1 In Examples 2 to 6, the polyp-phenylene sulfide resin (manufactured by Kureha Corporation, W-214A) and the halogenated polyphenylene sulfide resin obtained in Example 1 were mixed at the ratios shown in Table 1. , A resin composition was obtained. In Example 7, a polyp-phenylene sulfide resin (manufactured by Kureha Corporation, W-214A), the polym-phenylene sulfide resin obtained in Preparation Example 1 above, and the halogenated polyphenylene sulfide resin obtained in Example 1 were used. And were mixed at the ratios shown in Table 1 to obtain a resin composition.
  • the mixture is melt-kneaded with a barrel of R60 (capacity 60 mL) and a full-flight screw.
  • a resin composition was obtained by melt-kneading with an apparatus (Laboplast Mill, manufactured by Toyo Seiki Seisakusho) under the conditions of a test temperature of 320 ° C., a test time of 5 minutes, and a rotation speed of 100 rpm.
  • polyphenylene sulfide resin alone was used as a sample.
  • Examples 2 to 7 and Comparative Example 1 a sample of the resin composition or the resin alone was compression-molded at 320 ° C. under the conditions of 5 MPa and 1 minute to prepare a sheet having a size of 55 mm ⁇ 55 mm ⁇ 1 mm.
  • the brittleness of the prepared sheet was confirmed by touch and visual inspection, and the moldability was evaluated.
  • the case where there was no problem with the strength of the sheet was evaluated as ⁇
  • the case where compression molding was possible but some brittleness was felt in the sheet was evaluated as ⁇
  • the case where compression molding was not possible was evaluated as ⁇ . If it is evaluated as ⁇ , specifically, it is a case where the sheet is brittle to the extent that cracks are easily generated by bending.
  • a strip-shaped test piece for DMA measurement was cut out from the obtained sheet with a cutter knife, the dynamic viscoelasticity by DMA was evaluated, and the loss coefficient was measured.
  • the test piece was annealed at 150 ° C. for 1 hour before the DMA measurement.
  • the DMA measurement conditions are as follows.
  • the value of the loss coefficient is the maximum value measured at 20 ° C to 240 ° C.
  • the measurement results of the loss coefficient are shown in Table 1.
  • ⁇ DMA measurement conditions> Sample size: 10 mm x 5 mm x 1 mm
  • Tensile temperature 20 ° C to 240 ° C
  • Temperature rise rate 2 ° C / min Frequency: 10Hz
  • Example 8 To change 1,2,4-trichlorobenzene (purity 99.8%) to 1,2,4-trichlorobenzene (purity 97.5% by mass) containing 2.3% by mass of p-dichlorobenzene as an impurity.
  • a halogenated polyphenylene sulfide resin was obtained in the same manner as in Example 1.
  • the obtained halogenated polyphenylene sulfide resin had a weight average molecular weight (Mw) of 3500 and a glass transition temperature of 90 ° C.
  • the resin composition was prepared and evaluated in the same manner as in Example 3. The evaluation results of the resin composition were the same as in Example 3.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)
PCT/JP2021/026578 2020-07-22 2021-07-15 ハロゲン化ポリフェニレンスルフィド樹脂、樹脂組成物、成形品、及び樹脂用制振化剤 Ceased WO2022019204A1 (ja)

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US18/005,773 US20230279227A1 (en) 2020-07-22 2021-07-15 Halogenated polyphenylene sulfide resin, resin composition, molded article, and vibration-damping agent for resin
KR1020227045316A KR102833810B1 (ko) 2020-07-22 2021-07-15 할로겐화 폴리페닐렌 설파이드 수지, 수지 조성물, 성형품 및 수지용 제진화제
CN202180044259.4A CN115996988A (zh) 2020-07-22 2021-07-15 卤化聚苯硫醚树脂、树脂组合物、成型品以及树脂用减振化剂
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