CN105593302B - Polyarylene sulfide resin composition and its formed products and electric-vehicle part - Google Patents

Polyarylene sulfide resin composition and its formed products and electric-vehicle part Download PDF

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CN105593302B
CN105593302B CN201480054696.4A CN201480054696A CN105593302B CN 105593302 B CN105593302 B CN 105593302B CN 201480054696 A CN201480054696 A CN 201480054696A CN 105593302 B CN105593302 B CN 105593302B
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polyarylene sulfide
sulfide resin
electric
vehicle part
resin composition
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CN105593302A (en
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山田启介
渡边创
桧森俊男
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DIC Corp
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Dainippon Ink and Chemicals Co Ltd
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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
    • 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
    • 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
    • C08G75/0263—Preparatory processes using elemental sulfur
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets

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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)

Abstract

The present invention provide can inhibit gas generated and resin combination or its formed products caused by heating have excellent resistance to electric trace, mechanical strength, metal adaptation, die cavity equilibrium response polyarylene sulfide resin composition, using the resin combination electric-vehicle part formed products and have the electric-vehicle parts of the formed products.Specifically, provide electric-vehicle part polyarylene sulfide resin composition, using the resin combination electric-vehicle part formed products and have the electric-vehicle parts of the formed products, the electric-vehicle part polyarylene sulfide resin composition contains：Polyarylene sulfide resin；With at least one kind of other ingredients in the group being made of inorganic filler, the thermoplastic resin in addition to polyarylene sulfide resin, elastomer and crosslinkable resin with 2 or more cross-linking functional groups, polyarylene sulfide resin can be obtained using including making the method that diiodo- aromatic compound, elemental sulfur and polymerization inhibitor react in the molten mixture containing diiodo- aromatic compound, elemental sulfur and polymerization inhibitor.

Description

Polyarylene sulfide resin composition and its formed products and electric-vehicle part
Technical field
The present invention relates to polyarylene sulfide resin composition and its formed products and electric-vehicle part.
Background technology
The electric vehicle to attract attention in recent years has many components to work under high voltages, this electric-vehicle part Use resin forming product.As the purposes of resin forming product, for example, can enumerate：Coil box is made in resin forming product, at this Interior composition epoxy resin of coil box etc. seals automobile ignition coil cassette obtained from ignition coil；Alternatively, spark plug with Distributorless ignition system made of ignition coil integration is (hereinafter sometimes referred to simply as " DLI systems ".) in coil box.
For this electric-vehicle part, it is desirable that even if being not easy to such resistance to electric trace on fire under high voltages.In addition, Such as about coil box as described above, it is expected that its with epoxy resin or metal it is excellent in adhesion.
On the other hand, such as, it is proposed that will include with polyphenylene sulfide resin (hereinafter sometimes referred to simply as " PPS trees Fat ".) (be hereinafter sometimes referred to simply as " pas resin " for the polyarylene sulfide resin of representative.) resin combination processing is formed, For automobile component as described above (referring for example to patent document 1).
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2000-103964 bulletins
Invention content
Problems to be solved by the invention
But in the existing composition comprising polyarylene sulfide resin, the gas that generates due to heating when forming etc. The amount of body is relatively more.Therefore, become what the metal materials such as the gas componant i.e. low molecular weight compound of sulfur atom-containing and copper contacted When state, the two is made to react by applying high voltage repeatedly, generates the possibility of trees (depredation of resin-like) Also high, thus worry causes resistance to electric trace to reduce.Especially driving force in the electric vehicle of engine, when starting using needing The driving energy of petrol engine is opposed, therefore has lithium rechargeable battery, is driven under with 100~400V of battery voltage gauge, When further equipped with booster circuit, driven under the high voltage of 650V.For requiring the automotive field component, outstanding of high security It is component for electric vehicle, since the component to work under high voltage, high current is more, and uses the existing of lead accumulator Type automobile is compared, and prevents on fire, anti-burning extension energy when requiring abnormal with higher level, it is desirable that not only excellent in flame retardance, Er Qiejin One step inhibits the creepage trace phenomenon as reason of fire.In addition, in resin combination or its formed products, mechanical strength, epoxy Also there is still room for improvement for the characteristics such as resin closed, metal adaptation, die cavity balance.
Therefore, the problem to be solved in the present invention is, the gas generated and resin caused by heating can be inhibited by providing The poly arylidene thio-ester of composition or its formed products with excellent resistance to electric trace, mechanical strength, metal adaptation, die cavity equilibrium response Resin combination, using the resin combination formed products for electric vehicle and have the electric-vehicle parts of the formed products.
The solution to the problem
The inventors of the present invention have carried out various researchs, as a result, it has been found that, by using by diiodo- aromatic compound and elemental sulfur With polyarylene sulfide resin obtained from polymerization inhibitor melt polymerization, can solve the above problems, so as to complete the present invention.
That is, the present invention relates to a kind of electric-vehicle part polyarylene sulfide resin composition, contain：Poly arylidene thio-ester tree Fat；With selected from being crosslinked by inorganic filler, the thermoplastic resin in addition to polyarylene sulfide resin, elastomer and with 2 or more Property functional group crosslinkable resin composition group at least one kind of other ingredients (hereinafter sometimes referred to simply as " and it is aforementioned it is other at Point "), polyarylene sulfide resin can be by including making diiodo- aromatic compound, elemental sulfur and polymerization inhibitor comprising diiodo- fragrance The method reacted in the molten mixture of compounds of group, elemental sulfur and polymerization inhibitor and obtain.
The effect of invention
In accordance with the invention it is possible to inhibit gas generated caused by heating.In addition, in accordance with the invention it is possible to obtaining resistance to The polyarylphosphorus of the excellents such as electric trace, mechanical strength, epoxy resin adaptation, metal adaptation, die cavity balance, hot water resistance The formed products of ether resin composition.
It should be noted that die cavity equilibrium relation to the injection moulding by using the mold with multiple die cavitys simultaneously at The uniformity of the compactedness of each die cavity when the multiple formed products of shape.If the die cavity balance of moulding material is insufficient, exists and be easy Generate the tendency that a part of die cavity is not fully filled such cob webbing.
Specific implementation mode
Hereinafter, being described in detail for the preferred embodiment of the present invention.But the present invention is not limited to below Embodiment.
The polyarylene sulfide resin used in present embodiment can utilize include make diiodo- aromatic compound, elemental sulfur and Method that polymerization inhibitor reacts in the molten mixture containing diiodo- aromatic compound, elemental sulfur and polymerization inhibitor obtains.Root It, can be with the shape of the higher polymer of molecular weight compared with using Phillips methods as the existing method of representative according to such method Formula obtains polyarylene sulfide resin.
Diiodo- aromatic compound has aromatic ring and 2 iodine atoms with aromatic ring Direct Bonding.As diiodo- Aromatic compound, can enumerate diiodo-benzene, two iodotoluenes, diiodo- dimethylbenzene, diiodonaphthalene, diiodide, diiodobenzophenone, Diiodo- diphenyl ether and diiodo- diphenyl sulphone (DPS) etc., but it is not limited to these.The position of substitution of 2 iodine atoms is not particularly limited, excellent It is ideal to select the position that 2 the position of substitution are located in the molecule as far as possible.Preferred the position of substitution is contraposition and 4,4 '- Position.
The aromatic ring of diiodo- aromatic compound can by selected from phenyl, in addition to iodine atom halogen atom, hydroxyl, At least one kind of substituent group in nitro, amino, the alkoxy of carbon atom number 1~6, carboxyl, carboxylate, aryl sulfone and aryl ketones takes Generation.But from the viewpoints such as the crystallinity of polyarylene sulfide resin and heat resistance, the diiodo- aromatic compound being substituted is opposite In the ratio of unsubstituted diiodo- aromatic compound be preferably the range of 0.0001~5 mass %, more preferably 0.001~1 The range of quality %.
Elemental sulfur refers to the substance (S being only made of sulphur atom8、S6、S4、S2Deng), form is not particularly limited.Specifically For, can used as Pharmacopeia of Japan drug commercially available elemental sulfur, or can generally obtain include S8And S6Deng Mixture.The purity of elemental sulfur is also not particularly limited.Then can be grain as long as elemental sulfur is solid under room temperature (23 DEG C) Shape is powdered.The grain size of elemental sulfur is not particularly limited, preferably the range of 0.001~10mm, more preferably 0.01~5mm Range, the further preferably range of 0.01~3mm.
As long as polymerization inhibitor prevents or terminates the compound of the polymerisation in the polymerisation of polyarylene sulfide resin, then It can use without particular limitation.Polymerization inhibitor preferably comprise can the end of the main chain of polyarylene sulfide resin import selected from by The compound of at least one of the group of salt composition of hydroxyl, amino, carboxyl and carboxyl group.That is, as polymerization inhibitor, preferably have By the chemical combination of at least one of 1 or 2 or more the group for selecting the salt of free hydroxyl, amino, carboxyl and carboxyl to form group Object.In addition, polymerization inhibitor there can be above-mentioned functional group, above-mentioned functional group can also be generated by the termination of polymerization reaction etc..
As the polymerization inhibitor with hydroxyl or amino, following formula (1) or (2) compound represented conduct can be used for example Polymerization inhibitor.
According to general formula (1) compound represented, terminal groups of the univalent perssad as main chain shown in following formula (1-1) are imported Group.Y in formula (1-1) is hydroxyl, amino etc. from polymerization inhibitor.
According to general formula (2) compound represented, terminal groups of the univalent perssad as main chain shown in following formula (2-1) are imported Group.Hydroxyl from general formula (1) compound represented can for example pass through the carbon atom and Thiyl Radical key of the carbonyl in formula (2) It closes and is directed in polyarylene sulfide resin.
Think：Be originated from the main chain of polyarylene sulfide resin raw material (elemental sulfur) and existing disulfide bond under melting temperature from The Thiyl Radical that is generated by basic capsule solution is bonded with general formula (1) compound represented or general formula (2) compound represented, to Group is directed in polyarylene sulfide resin shown in formula (1-1) or (2-1).The presence of the structural unit of these specific structures It is the feature by using polyarylene sulfide resin obtained from general formula (1) or the melt polymerization of (2) compound represented.
As general formula (1) compound represented, for example, 2- iodophenols, 2- amino anilines etc..As general formula (2) Compound represented can enumerate 2- iodine benzophenone.
As the polymerization inhibitor with carboxyl, can be used for example selected from the following general formula (3), (4) or (5) compound represented One or more of compound.
In general formula (3), R1And R2Each independently represent hydrogen atom or the following general formula (a), (b) or (c) shown in monovalence Group, R1Or R2At least either be general formula (a), (b) or (c) shown in univalent perssad.In general formula (4), Z indicates iodine atom Or sulfydryl, R3Indicate the following general formula (a), (b) or (c) shown in univalent perssad.In general formula (5), R4Indicate general formula (a), (b) or (c) univalent perssad shown in.
X in general formula (a)~(c) is hydrogen atom or alkali metal atom, becomes good aspect from reactivity, preferably Hydrogen atom.As alkali metal atom, sodium, lithium, potassium, rubidium and caesium etc., preferably sodium can be enumerated.In general formula (b), R10Indicate carbon atom The alkyl of number 1~6.In general formula (c), R11Indicate hydrogen atom or the alkyl of carbon atom number 1~3, R12Indicate carbon atom number 1~5 Alkyl.
According to general formula (3), (4) or (5) compound represented, univalent perssad conduct shown in following formula (6) or (7) is imported The end group of main chain.The presence of the structural unit of the end of these specific structures is by using general formula (3), (4) or (5) The feature of polyarylene sulfide resin obtained from the melt polymerization of compound represented.
(in formula, R5Indicate general formula (a), (b) or (c) shown in univalent perssad.)
(in formula, R6Indicate general formula (a), (b) or (c) shown in univalent perssad.)
As polymerization inhibitor, the compound etc. for not having the functional groups such as carboxyl can be used.As such compound, such as It can use selected from diphenyl disulfide, single iodobenzene, benzenethiol, 2,2 '-dibenzothiazyl disulfides, 2-mercaptobenzothiazole, N- Cyclohexyl -2-[4-morpholinodithio sulfenamide, 2- (morpholinothio) benzothiazoles and N, N '-dicyclohexyl -1,3- benzothiazoles - At least one kind of compound in 2- sulfenamides.
The polyarylene sulfide resin of present embodiment generates as follows：To include diiodo- aromatic compound, elemental sulfur, inhibition Melt polymerization is carried out in molten mixture obtained from the heating of the mixture of agent and the catalyst being added as needed on, to raw At.For the ratio of the diiodo- aromatic compound in molten mixture, relative to 1 mole of elemental sulfur, preferably 0.5~2 rubs Your range, more preferably 0.8~1.2 mole of range.In addition, for the ratio of the polymerization inhibitor in mixture, relative to solid 1 mole of body sulphur, preferably 0.0001~0.1 mole of range, more preferably 0.0005~0.05 mole of range.
The period of addition polymerization inhibitor is not particularly limited, and can will include diiodo- aromatic compound, elemental sulfur and root According to the range, more excellent for needing the mixture of catalyst to be added to heat and the temperature of mixture being made to reach preferably 200 DEG C~320 DEG C Polymerization inhibitor is added at the time of the range for selecting 250~320 DEG C.
Nitro compound can be added in molten mixture as the catalyst to adjusting polymerization speed.As the nitration Object is closed, various nitrobenzene derivatives can be usually used.As nitrobenzene derivative, for example, 1,3- bis- iodo- 4- nitre Bis- iodo- 4- nitra-amines of the iodo- 4- nitrobenzenes of base benzene, 1-, bis- iodo- 4- nitrophenols of 2,6- and 2,6-.The amount of catalyst is usually to make For the amount of catalyst addition, such as relative to 100 mass parts of elemental sulfur, the preferably range of 0.01~20 mass parts.
The condition of melt polymerization is carried out suitable for adjusting so that polymerisation suitably carries out.The temperature of melt polymerization is preferred For 175 DEG C or more and generate polyarylene sulfide resin+100 DEG C of fusing point range below, more preferably 180~350 DEG C of model It encloses.Melt polymerization is in the range that absolute pressure is preferably 1 [cPa]~100 [kPa], more preferably 13 [cPa]~60 [kPa] It is carried out in range.The condition of melt polymerization does not need constant.For example, polymerization initial stage can make temperature be preferably 175~270 DEG C Range, more preferable 180~250 DEG C of range, and absolute pressure is made to be the range of 6.7~100 [kPa], then, side is continuously Or periodically heat up and depressurize side and polymerize, the polymerization later stage makes temperature be the poly arylidene thio-ester of preferably 270 DEG C or more and generation + 100 DEG C of fusing point range below, more preferable 300~350 DEG C of the range of resin, also, absolute pressure is made to be 1 [cPa]~6 The range of [kPa] and polymerize.In this specification, the fusing point of resin refers to using differential scanning calorimetry (DSC) (PerkinElmer Co., the DSC device Pyris Diamond of Ltd. manufactures), the value that is measured according to JIS K7121.
For melt polymerization, from the viewpoint of preventing oxidation cross-linked reaction and obtaining high polymerization degree, preferably non-oxygen It is carried out under the property changed atmosphere.In non-oxidizing atmosphere, the oxygen concentration of gas phase is preferably less than the range of 5 volume %, is more preferably Range, further preferred gas phase less than 2 volume % are substantially free of oxygen.Non-oxidizing atmosphere be preferably nitrogen, helium and The non-active gas atmospheres such as argon gas.
Melt polymerization can be used for example have heating device, decompressor and agitating device melting mixing machine come into Row.As melting mixing machine, for example, Banbury mixer, kneader, continuous mixer, single screw extrusion machine and double Screw extruder.
Molten mixture for melt polymerization is preferably substantially free of solvent.More specifically, contain in molten mixture Total of the amount of some solvents relative to diiodo- aromatic compound, elemental sulfur, polymerization inhibitor and the catalyst being added as needed on 100 mass parts, preferably 10 ranges below mass part, more preferably 5 ranges below mass part, further preferably 1 matter Measure part range below.The amount of solvent can be 0 mass parts or more, more than more than 0.01 mass parts range or 0.1 mass parts Range.
Molten mixture (reaction product) cooling after melt polymerization can also obtained the mixture of solid state Afterwards, mixture is heated under reduced pressure or under the atmospheric pressure of non-oxidizing atmosphere, to make polymerisation further carry out.As a result, Molecular weight can not only be further increased, and the iodine molecule of generation is made to distil and be removed, therefore, it is possible to by poly arylidene thio-ester tree Iodine atom concentration in fat inhibits in reduced levels.By be cooled to preferably 100~260 DEG C range, more preferable 130~250 DEG C range, the temperature of further preferred 150~230 DEG C of range, the mixture of solid state can be obtained.It is cooled to solid Heating after state can carry out at temperature same as melt polymerization and pressure condition.
Including the reaction product of the polyarylene sulfide resin obtained by melt polymerization process can be used for by keeping former Sample direct plunges into the methods of melting mixing machine to manufacture resin combination, but addition can dissolve reaction production in the reaction product The solvent of object prepares dissolved matter, and when taking out from reaction unit reaction product with the state of the dissolved matter, not only productivity is excellent It is different, and then reactivity is also good, therefore preferably.The addition that the solvent of the reaction product can be dissolved is preferably laggard in melt polymerization Row, but can also be carried out in the reaction later stage of melt polymerization, alternatively, it is also possible to as described above by molten mixture (reaction production Object) it is cooling obtain the mixture of solid state after, under elevated pressure, under decompression or under the atmospheric pressure of non-oxidizing atmosphere, heating Mixture adds after so that polymerisation is further carried out.The process for preparing the dissolved matter can carry out under non-oxidizing atmosphere. In addition, the temperature as heating for dissolving, as long as the range more than the fusing point of solvent that can dissolve previous reaction product, excellent It is selected as 200~350 DEG C of range, more preferably 210~250 DEG C of range, is preferably carried out under elevated pressure.
Compounding ratio for the solvent that previous reaction product is used, can dissolved to prepare aforementioned dissolved matter, phase For 100 mass parts of reaction product comprising polyarylene sulfide resin, the preferably range of 90~1000 mass parts, more preferably The range of 200~400 mass parts.
As the solvent that can dissolve reaction product, can be used for example in the polymerisation in solutions such as Phillips methods as polymerization The solvent that reaction dissolvent uses.As the example of preferred solvent, can enumerate：N-methyl-2-pyrrolidone is (hereinafter abbreviated as NMP), n-cyclohexyl-2-pyrrolidone, 2-Pyrrolidone, 1,3- dimethyl -2- imidazolidinones, epsilon-caprolactams, N- methyl - The aliphatic cyclics such as epsilon-caprolactams amide compound, hexamethylphosphoric triamide (HMPA), tetramethylurea (TMU), dimethyl The amide compounds such as formamide (DMF) and dimethylacetylamide (DMA), dialkylethers (degree of polymerization be 2000 with Under, the alkyl with carbon atom number 1~20) etc. etherificate polyethylene glycol compound and tetramethylene sulfoxide and dimethyl sulfoxide (DMSO) (DMSO) sulfoxide compounds such as.As the example of other workable solvents, can enumerate selected from the group by following material composition One or more of solvent：Benzophenone, diphenyl ether, diphenyl sulfide, 4,4 '-'-dibromobiphenyls, 1- phenylnaphthalenes, diphenyl -1 2,5-, 3,4- oxadiazoles, 2,5- diphenyl-oxazoles, triphenylcarbinol, N, N- diphenylformamides, benzil, anthracene, 4- benzoyls biphenyl, Dibenzoyl methane, 2- biphenyl carboxylic acids, dibenzothiophenes, pentachlorophenol, 1- benzyls -2-Pyrrolidone, 9-Fluorenone, 2- benzoyls Naphthalene, 1- bromonaphthalenes, bis- phenoxy group benzene of 1,3-, fluorenes, 1- phenyl -2-Pyrrolidone, 1- methoxynaphthalenes, 1- ethyoxyls naphthalene, 1,3- hexichol Benzylacetone, 1,4- dibenzoyls butane, phenanthrene, 4- benzoyls biphenyl, 1,1- diphenyl acetones, neighbour, neighbour '-xenol, 2,6- hexichol Base phenol, benzophenanthrene, 2- phenylphenols, thianthrene, 3- phenoxy benzenemethanols, 4- phenylphenols, bis- chrloroanthracenes of 9,10-, triphenyl first Alkane, 4,4 '-dimethoxy-benzophenones, 9,10- diphenylanthrancenes, fluoranthene, diphenyl phthalate, diphenyl carbonate, 2,6- Dimethoxy-naphthalene, endipalene, 4- dibromodiphenyl ethers, pyrene, 9,9 '-two fluorenes, 4,4 '-isopropylidenes-xenol, ε-are in oneself Amide, n-cyclohexyl-2-pyrrolidone, diphenyl iso-phthalate, diphenyl phthalate and 1- chloronaphthalenes.
The dissolved matter taken out from reaction unit is kneaded after being post-processed, with aforementioned other components fuses and preparation tree When oil/fat composition, reactivity becomes more preferable, therefore preferably.The method of post-processing as dissolved matter, is not particularly limited, such as Following methods can be enumerated.
(1) after keeping intact or being added acid or alkali by the dissolved matter, removal solvent is distilled under reduced pressure or under atmospheric pressure, is connect It, distillation is removed to the solid matter after solvent with the solvent used in water, the dissolved matter (or for low polymer Organic solvent with same solubility), acetone, the solvent in methyl ethyl ketone and alcohols etc. clean 1 time or 2 times or more, Jin Erjin Row is neutralized, washed, filtering and dry method.
(2) it is molten that water, acetone, methyl ethyl ketone, alcohol, ether, halogenated hydrocarbons, aromatic hydrocarbon and aliphatic hydrocarbon etc. are added in the dissolved matter Agent (dissolving in the solvent of the dissolved matter and the solvent at least for polyarylene sulfide resin for poor solvent) is used as sedimentation agent, makes The solid product sedimentation for including polyarylene sulfide resin and inorganic salts etc., is filtered solid product, cleans and dries Method.
(3) solvent used in the dissolved matter is added in the dissolved matter (or to be had low polymer same molten The organic solvent of Xie Du) be stirred after, filter and remove low-molecular weight polymer, then with selected from water, acetone, methyl ethyl ketone and Solvent in alcohol etc. cleans 1 time or 2 times or more, the method for then being neutralized, washed, filtering and being dried.
It should be noted that in such post-processing approach illustrated in above-mentioned (1)~(3), polyarylene sulfide resin is done It is dry to carry out in a vacuum, it can also be carried out in air or in the non-active gas atmosphere of nitrogen etc.It can also be in oxygen Gas concentration makes polyarylene sulfide resin to be heat-treated in the oxidizing atmosphere of the range of 5~30 volume % or under reduced pressure It carries out oxidation cross-linked.
It is illustrated below to go out to generate the reaction of polyarylene sulfide resin by melt polymerization.
Reaction equation (1)
Reaction equation (2)
Reaction equation (3)
Reaction equation (4)
Reaction equation (5)
Reaction equation (1)~(5) be using for example with comprising general formula (a), (b) or (c) shown in group substituent R The example of reaction when diphenyl disulfide is as polymerization inhibitor, generating polyphenylene sulfide.Reaction equation (1) is-S-S- in polymerization inhibitor Key is issued in melting temperature is born from by the reaction of basic capsule solution.Reaction equation (2) is the Thiyl Radical attack life generated in reaction equation (1) The adjacent carbon atom of the end iodine atom of main chain in length and so that iodine atom is detached from, to make polymerization and at the same time in main chain End import substituent R reaction.Reaction equation (3) be polyarylene sulfide resin main chain in be originated from raw material (elemental sulfur) and exist Disulfide bond issue and be born from by the reaction of basic capsule solution in melting temperature.Reaction equation (4) be sulphur by generating in reaction equation (3) from Polymerization is made and at the same time substituent R is imported into master by being bonded again for Thiyl Radical generated in base and reaction equation (1) The reaction of the end of chain.The iodine atom of disengaging is in free state (iodine free radical) or the iodine free radical as reaction equation (5) It is bonded again each other and generates iodine molecule.
Including the reaction product of the polyarylene sulfide resin as obtained from melt polymerization contains the iodine atom from raw material.Cause This, polyarylene sulfide resin is usually used for the preparation etc. of spinning resin combination with the state of the mixture containing iodine atom. The concentration of iodine atom in the mixture is for example relative to the range that polyarylene sulfide resin is 0.01~10000ppm, preferably 10 The range of~5000ppm.Using the sublimability of iodine molecule, iodine atom concentration can also be inhibited in reduced levels, such case Under, 900ppm ranges below, preferably 100ppm ranges below, further preferred 10ppm ranges below can also be set as. In turn, although can also remove iodine atom to detection limit hereinafter, it is contemplated that when productivity it is impracticable.Detection limits 0.01ppm or so.For the polyarylene sulfide resin of present embodiment that is obtained by melt polymerization or comprising its reaction product, Comprising iodine atom on this point can with for example using the dichloros such as Phillips methods aromatic compound it is molten in polar organic Poly arylidene thio-ester clearly distinguishes obtained from solution polymerization process in agent.
By above-mentioned reaction equation it is also to be understood that including by the polyarylene sulfide resin that melt polymerization obtains：Mainly by fragrant sulphur The main chain and the defined substituent R being bonded with the end of the main chain that ether unit is constituted, the aromatic sulfide unit include to be originated from two The aromatic ring of iodine aromatic compound and the sulphur atom being directly bonded.Defined substituent R is bonded directly to main chain end The aromatic ring at end is bonded to via the part-structure from polymerization inhibitor on the aromatic ring of the end of main chain.
The polyphenylene sulfide of polyarylene sulfide resin as an embodiment, such as with including the following general formula (10) Shown in repetitive unit (aromatic sulfide unit) main chain.
Repetitive unit shown in formula (10) be more preferably repetitive unit shown in following formula (10a) with para-linkage and With repetitive unit shown in the following formula (10b) of ortho position bonding.
Wherein, excellent in the heat resistance of resin and crystalline aspect with the repetitive unit of para-linkage shown in formula (10a) Choosing.
The polyphenylene sulfide of one embodiment can include the following general formula (11) shown in, have as with aromatic series The repetitive unit of the substituent group of the side chain of ring bonding：
(in formula, R20And R21Each independently represent hydrogen atom, the alkyl of carbon atom number 1~4, nitro, amino, phenyl, Methoxy or ethoxy.).But from the viewpoint of reducing crystallinity and heat resistance, polyphenylene sulfide is preferably substantially not Repetitive unit containing general formula (11).More specifically, the ratio about repetitive unit shown in formula (11), relative to formula (10) institute The summation of repetitive unit shown in the repetitive unit and formula (11) shown, preferably 2 mass % or less, more preferably 0.2 mass % Below.
The polyarylene sulfide resin of present embodiment is mainly made of above-mentioned aromatic sulfide unit, also includes source usually in main chain The structural unit of the disulfide bond shown in the elemental sulfur of raw material, following formula (20).
From heat resistance, mechanical strength aspect, for the ratio of structural unit shown in formula (20), relative to fragrant sulphur The summation of structure position shown in ether unit and formula (20), preferably 2.9 mass % ranges below, more preferably 1.2 matter Measure % ranges below.By making polyarylene sulfide resin include structural unit shown in formula (20), polyarylene sulfide resin is being improved The aspect of the adaptation of composition and metal is preferred.
The Mw/Mtop of the polyarylene sulfide resin of present embodiment be preferably 0.80~1.70 range, more preferably 0.90 ~1.30 range.By making Mw/Mtop be such range, the processability of polyarylene sulfide resin can be improved, can be assigned Good die cavity balance.In this specification, Mw indicates that the weight average molecular weight measured by gel permeation chromatography, Mtop indicate logical The detection intensity for crossing the chromatogram that the measurement obtains reaches the average molecular weight (peak molecular weight) of maximum point.Mw/Mtop tables Show the distribution of the molecular weight of measure object, in general, the value close to the narrowly distributing for indicating molecular weight when 1, as the value becomes larger, indicates The distribution of molecular weight broadens.It should be noted that the determination condition of gel permeation chromatography is using the embodiment with this specification Identical determination condition.However, it is possible to change determination condition in the range of not influencing the value of Mw, Mw/Mtop substantially.
For the weight average molecular weight of the polyarylene sulfide resin of present embodiment, as long as not damaging the effect of the present invention, do not have It is particularly limited to, for its lower limit, from mechanical strength aspect, preferably 28000 or more and then more preferably 30000 or more range.On the other hand, for the upper limit, from the aspect that can assign more good die cavity balance, preferably 100000 ranges below, and then more preferably 60000 ranges below, and then most preferably 55000 ranges below.Into And from the viewpoint of mechanical strength and good die cavity balance can be assigned, model that can be with 28000~60000 The polyarylene sulfide resin that encloses, more preferable 30000~55000 the polyarylene sulfide resin of range be used together weight average molecular weight and be in Polyarylene sulfide resin more than 60000 and for 100000 ranges below.
The non-newtonian index of polyarylene sulfide resin is preferably 0.95~1.75 range, more preferably 1.0~1.70 model It encloses.By making non-newtonian index be such range, the processability of polyarylene sulfide resin can be improved, good mould can be assigned Chamber balances.In this specification, non-newtonian index refers under shear velocity and shear stress under conditions of meeting 300 DEG C of temperature State the index of relational expression.Non-newtonian index can become the molecular weight or straight chain, branch, molecule as crosslinking of measure object The relevant index of structure indicates that the molecular structure of resin is straight-chain, as the value becomes larger, indicates in general, when the value is close to 1 Including more branch, cross-linked structure.
D=α × Sn
(in above-mentioned formula, D indicates that shear velocity, S indicate that shear stress, α indicate that constant, n indicate non-newtonian index.)
The polyarylene sulfide resin of Mw/Mtop and non-newtonian index with above-mentioned particular range can for example obtain as follows： Make diiodo- aromatic compound, elemental sulfur and polymerization inhibitor in the melting containing diiodo- aromatic compound, elemental sulfur and polymerization inhibitor In the method for reacting (polymerisation in solution) in mixture, make the polyarylene sulfide resin somewhat molecular weight, to It arrives.
The fusing point of the polyarylene sulfide resin of present embodiment is preferably 250~300 DEG C of range, is more preferably 265~300 DEG C range.Melt viscosity (V6) at 300 DEG C of polyarylene sulfide resin be preferably 1~2000 [Pas] range, more preferably For the range of 5~1700 [Pas].Herein, melt viscosity (V6) refers to using flow tester in 300 DEG C of temperature, load After the aperture for the use of the ratio between orifice length and orifice diameter (orifice length/orifice diameter) being 10/1 under 1.96MPa is kept for 6 minutes Melt viscosity.
The polyarylene sulfide resin composition of present embodiment can contain one kind or two or more inorganic filler.By matching Mixed inorganic filler, can obtain high rigidity, high heat-resistant stability composition.As inorganic filler, for example,：Charcoal The plate-like fillers such as the pulverulent fillers such as black, calcium carbonate, silica and titanium oxide, talcum and mica, glass microballoon, silica Bat wools and the glass squama such as microballon and glass hollow ball equigranular filler, glass fibre, carbon fiber and calcium silica fiber Piece.Polyarylene sulfide resin composition is particularly preferably containing in the group being made of glass fibre, carbon fiber, carbon black and calcium carbonate At least one kind of inorganic filler.
The content of inorganic filler is relative to 100 mass parts of polyarylene sulfide resin, the preferably range of 1~300 mass parts, more The preferably range of 5~200 mass parts, the range of further preferably 15~150 mass parts.By making containing for inorganic filler Amount can obtain superior effect in the range in terms of the mechanical strength holding of formed products.
The polyarylene sulfide resin composition of present embodiment, which can contain, is selected from thermoplastic resin, elastomer and bridging property Resin, resin in addition to polyarylene sulfide resin.These resins can also be compounded in resin combination together with inorganic filler In object.
As the thermoplastic resin being compounded in polyarylene sulfide resin composition, for example, polyester, polyamide, polyamides Imines, makrolon, polyphenylene oxide, polysulfones, polyether sulfone, polyether-ether-ketone, polyether-ketone, polyethylene, polypropylene, gathers at polyetherimide Tetrafluoroethene, poly- difluoroethylene, polystyrene, ABS resin, organic siliconresin and liquid crystal polymer (liquid crystal polyester etc.).
Polyamide is the polymer for having amido bond (- NHCO-).As polyamide, for example,：(i) by The polymer and (iii) that polymer that the polycondensation of diamines and dicarboxylic acids obtains, (ii) are obtained by the polycondensation of amino carboxylic acid are by interior acyl The polymer etc. that the ring-opening polymerisation of amine obtains.Polyamide can be used alone or two or more is applied in combination.
As the example of the diamines for obtaining polyamide, fatty family diamines, aromatic system diamines and fat can be enumerated Ring family Diamines.As fatty family diamines, the preferably diamines of straight-chain or the carbon number 3~18 with side chain.As suitable Fatty family diamines example, 1,3- propane diamine, Putriscine, 1,5- pentanediamines, 1,6- hexamethylene diamines, 1,7- can be enumerated Heptamethylene diamine, 1,8- octamethylenediamines, 2- methyl-1s, 8- octamethylenediamines, 1,9-nonamethylene diamine, 1,10- decamethylene diamines, 1,11- hendecanes diamines, 1, 12- dodecamethylene diamines, 1,13- tridecane diamines, 1,14- tetradecanes diamines, 1,15- pentadecanes diamines, 1,16- hexadecanes two Amine, 1,17- heptadecanes diamines, 1,18- octadecamethylene diamines, 2,2,4- trimethylhexane diamines and 2,4,4- trimethylhexane diamines.It Can be used alone or two or more is applied in combination.
As aromatic system diamines, preferably there is the diamines of the carbon number 6~27 of phenylene.As suitable aromatic system two The example of amine can be enumerated：O-phenylenediamine, m-phenylene diamine (MPD), p-phenylenediamine, m-xylene diamine, p dimethylamine, 3,4- diamino Diphenyl ether, 4,4 '-diaminodiphenyl ethers, 4,4 '-diaminodiphenyl-methanes, 3,3 '-diaminodiphenylsulfones, 4,4 '-diamino Diphenyl sulphone (DPS), 4,4 '-diaminodiphenyl sulfides, 4,4 '-two (m-aminophenyl oxygroup) diphenyl sulphone (DPS)s, 4,4 '-two (p-aminophenyl oxygroups) Bis- (4- aminophenyls) propane of diphenyl sulphone (DPS), benzidine, 3,3 '-diaminobenzophenones, 4,4 '-diaminobenzophenones, 2,2-, 1,5- diaminonaphthalenes, 1,8- diaminonaphthalenes, 4,4 '-bis- (4- amino-benzene oxygens) biphenyl, bis- [4- (4- amino-benzene oxygens) benzene of 2,2- Base] hexafluoropropane, bis- (4- amino-benzene oxygens) benzene of 1,4-, bis- (4- amino-benzene oxygens) benzene of 1,3-, bis- (the 3- aminobenzene oxygen of 1,3- Base) benzene, bis- (3- amino-benzene oxygens) benzene of 1,3-, 4,4 '-diamino -3,3 '-diethyl -5,5 '-dimethyl diphenylmethane, 4, 4 '-diamino -3,3 ', 5,5 '-tetramethyl diphenyl methanes, 2,4 di amino toluene and 2,2 '-dimethylbenzidines.They It can be used alone or two or more is applied in combination.
As alicyclic ring family diamines, preferably there is the diamines of the carbon number 4~15 of cyclohexylidene.As suitable alicyclic ring family The example of diamines can enumerate-two cyclohexylidene methane of 4,4 '-diamino ,-two cyclohexylidene propane of 4,4 '-diamino, 4, - two cyclohexylidene methane of 4 '-diamino -3,3 '-dimethyl, 1,4- diaminocyclohexanes and piperazine.They can be used alone Or two or more is applied in combination.
As the dicarboxylic acids for obtaining polyamide, fatty family dicarboxylic acids, aromatic system dicarboxylic acids and fat can be enumerated Ring family dicarboxylic acids.
As fatty family dicarboxylic acids, the preferably saturated or unsaturated dicarboxylic acids of carbon atom number 2~18.As suitable The example of fatty family dicarboxylic acids can be enumerated：Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, Azelaic acid, decanedioic acid, heneicosanedioic acid, dodecanedioic acid, tridecandioic acid, tetracosandioic acid, pentacosandioic acid, octadecane two Acid, maleic acid and fumaric acid.They can be used alone or two or more is applied in combination.
As aromatic system dicarboxylic acids, preferably there is the dicarboxylic acids of the carbon number 8~15 of phenylene.As suitable aromatic series It is the example of dicarboxylic acids, can enumerates：M-phthalic acid, terephthalic acid (TPA), methylterephthalic acid, biphenyl -2,2 '-diformazan Acid, biphenyl -4,4 '-dioctyl phthalate, diphenyl methane -4,4 '-dioctyl phthalate, diphenyl ether -4,4 '-dioctyl phthalate, diphenyl sulphone (DPS) -4,4 '-two Formic acid, 2,6- naphthalenedicarboxylic acids, 2,7- naphthalenedicarboxylic acids and 1,4- naphthalenedicarboxylic acids.They can be used alone or be applied in combination 2 kinds with On.In turn, can also can melt-shaping in the range of it is more using trimellitic acid, trimesic acid and Pyromellitic Acid etc. First carboxylic acid.
As amino carboxylic acid, the preferably amino carboxylic acid of carbon number 4~18.As the example of suitable amino carboxylic acid, Ke Yiju Go out：4-Aminobutanoicacid, 6-aminocaprolc acid, 7- aminoheptylic acids, 8- aminocaprylic acids, 9 aminononanoic acid, 10- aminocapric acids, 11- amino Hendecanoic acid, 12 amino dodecanoic acid, 14- amino tetradecanoic acid, 16- aminohexadecanoic acids and 18- amino octadecanoid acids.It Can be used alone or two or more is applied in combination.
As the lactams for obtaining polyamide, for example, epsilon-caprolactams, omega-lauric lactam, ζ-heptan Lactams and η-spicy inner formyl amine.They can be used alone or two or more is applied in combination.
The combination of raw material as preferred polyamide can enumerate：Epsilon-caprolactams (nylon 6), 1,6- hexamethylene diamines/oneself Diacid (nylon 6,6), 1,4- butanediamine/adipic acid (nylon 4,6), 1,6- hexamethylene diamines/terephthalic acid (TPA), 1,6- hexamethylene diamines/right Phthalic acid/epsilon-caprolactams, 1,6- hexamethylene diamines/terephthalic acid (TPA)/adipic acid, 1,9-nonamethylene diamine/terephthalic acid (TPA), 1,9- nonyls Diamines/terephthalic acid (TPA)/epsilon-caprolactams, 1,9-nonamethylene diamine/1,6- hexamethylene diamines/terephthalic acid (TPA)/adipic acid and isophthalic diformazan Amine/adipic acid.Wherein, further preferably by Putriscine/adipic acid (nylon 4,6), 1,6- hexamethylene diamines/terephthalic acid (TPA)/ Epsilon-caprolactams, 1,6- hexamethylene diamines/terephthalic acid (TPA)/adipic acid, 1,9-nonamethylene diamine/terephthalic acid (TPA), 1,9-nonamethylene diamine/to benzene The polyamide that dioctyl phthalate/epsilon-caprolactams or 1,9-nonamethylene diamine/1,6- hexamethylene diamines/terephthalic acid (TPA)/adipic acid obtain.
The content of thermoplastic resin relative to the range that 100 mass parts of polyarylene sulfide resin are preferably 1~300 mass parts, The more preferably range of 3~100 mass parts, the range of further preferably 5~45 mass parts.By making to remove polyarylene sulfide resin The content of thermoplastic resin in addition within the above range, can obtain heat resistance, chemical resistance and mechanical properties into one Step improves such effect.
As the elastomer being compounded in polyarylene sulfide resin composition, thermoplastic elastomer (TPE) is usually used.As thermoplasticity Elastomer, for example, polyolefin elastomer, Fuoroelastomer and silicon-type elastomer.It should be noted that this In specification, thermoplastic elastomer (TPE) is classified as elastomer, without being classified as aforementioned thermoplastic resin.
Elastomer (especially thermoplastic elastomer (TPE)) preferably have can with select free hydroxyl, amino, carboxyl and carboxyl The functional group of at least one of group of salt composition group reaction.Thus, it is possible to obtain in cementability and impact resistance etc. It is especially excellent and the gas generated resin combination caused by heating can be inhibited.It, can be with as the functional group It enumerates：Epoxy group, amino, hydroxyl, carboxyl, sulfydryl, isocyanate group, oxazolinyls and formula：R (CO) O (CO)-or R (CO) O- Group shown in (in formula, R indicates the alkyl of carbon atom number 1~8).Thermoplastic elastomer with the functional group such as can be with It is obtained by alpha-olefin and the copolymerization of the vinyl polymerized compound with aforementioned functional groups.Alpha-olefin for example, The alpha-olefines of the carbon numbers 2~8 such as ethylene, propylene and 1- butylene.As the vinyl polymerized compound with aforementioned functional groups, For example,：The alpha, beta-unsaturated carboxylic acids such as (methyl) acrylic acid and (methyl) acrylate and its Arrcostab, maleic acid, richness The α of horse acid, itaconic acid and other carbon numbers 4~10, β-unsaturated dicarboxylic and its derivative (monoesters or diester and its acid anhydrides Deng) and (methyl) glycidyl acrylate etc..Wherein, from toughness and the raising aspect of impact resistance, preferably have Have selected from by epoxy group, carboxyl and formula：R (CO) O (CO)-or R (CO) O- (in formula, R indicates the alkyl of carbon atom number 1~8) institute The ethylene-propylene copolymer and ethylene-butene copolymer of at least one kind of functional group in the group of the group composition shown.
The content of elastomer is different according to its type, purposes, therefore cannot entirely provide, for example, relative to polyarylphosphorus 100 mass parts of ether resin, the preferably range of 1~300 mass parts, more preferably 3~100 mass parts range, further it is excellent It is selected as the range of 5~45 mass parts.Content by making elastomer within the above range, can obtain ensuring the resistance to of formed products Hot, toughness the superior effect of aspect.
The crosslinkable resin being compounded in polyarylene sulfide resin composition has 2 or more cross-linking functional groups.As crosslinking Property functional group, can enumerate epoxy group, phenolic hydroxyl group, amino, amide groups, carboxyl, anhydride group and isocyanate group etc..As friendship Connection property resin, for example, epoxy resin, phenolic resin and polyurethane resin.
As epoxy resin, preferred fragrance family epoxy resin.Aromatic system epoxy resin can have halogen group or Hydroxyl etc..As the example of suitable aromatic system epoxy resin, can enumerate：Bisphenol A type epoxy resin, bisphenol F type epoxy Resin, bisphenol-s epoxy resin, biphenyl type epoxy resin, tetramethyl biphenyl type epoxy resin, phenol novolak-type epoxy tree Fat, cresol novolak type epoxy resin, phenol novolak type epoxy resin, bisphenol A novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenyl Ethane type epoxy resin, Dicyclopentadiene-phenol addition reaction-type epoxy resin, phenol aralkyl type epoxy resin, naphthols phenol Novolac type epoxy resin, naphthols aralkyl-type epoxy resin, naphthols-phenol cocondensation phenolic resin varnish type epoxy resin, naphthols-first Phenol cocondensation phenolic resin varnish type epoxy resin, aromatic hydrocarbon formaldehyde resin phenol-formaldehyde resin modified type epoxy resin and biphenyl phenolic aldehyde are clear Paint shaped epoxy resin.These aromatic system epoxy resin can be used alone or two or more is applied in combination.These aromatic system rings In oxygen resin, from the aspect excellent in compatibility with other resin components, particularly preferred phenolic resin varnish type epoxy resin, more It is preferred that cresol novolak type epoxy resin.
The content of crosslinkable resin relative to 100 mass parts of polyarylene sulfide resin, the preferably range of 1~300 mass parts, The more preferably range of 3~100 mass parts, the further preferably range of 5~30 mass parts.By making containing for crosslinkable resin Amount within the above range, can particularly marked degree obtain the rigidity of formed products and heat resistance improves such effect.
Polyarylene sulfide resin composition can contain silane compound, the silane compound have can with selected from by hydroxyl The functional group of at least one of the group of salt composition of base, amino, carboxyl and carboxyl group reaction.Polyarylene sulfide resin as a result, It is improved with the compatibility of other ingredients, furthermore it is possible to obtain to inhibit resin combination gas generated caused by heating Object.As the silane compound, for example,：γ-glycidoxypropyltrime,hoxysilane, the third oxygen of γ-epoxy Base propyl-triethoxysilicane, β-(3,4- epoxycyclohexyls) ethyl trimethoxy silane, γ-glycidoxypropyl two The silane coupling agents such as Ethoxysilane and γ-glycidoxypropyl dimethoxysilane.
The content of silane compound is for example relative to 100 mass parts of polyarylene sulfide resin, preferably 0.01~10 mass parts Range, the even more preferably range for 0.1~5 mass parts.By making the content of silane compound within the above range, energy The compatibility for enough obtaining polyarylene sulfide resin and aforementioned other ingredients improves such effect.
The polyarylene sulfide resin composition of present embodiment can contain releasing agent, colorant, heat-resisting stabilizing agent, ultraviolet light Other additives such as stabilizer, foaming agent, antirust agent, fire retardant and lubricant.The content of drug is added for example relative to polyarylphosphorus 100 mass parts of ether resin, the preferably range of 1~10 mass parts.
Polyarylene sulfide resin composition can by will utilize polyarylene sulfide resin obtained by the above method with it is aforementioned other Components fuse be kneaded method, such as the compound by partical in the form of obtain.The temperature of melting mixing is for example preferably 250 ~350 DEG C of range is even more preferably 290~330 DEG C of range.Melting mixing can use double screw extruder etc. into Row.
The polyarylene sulfide resin composition of present embodiment can lead to individually or with the combinations of materials such as aforementioned other ingredients It crosses the various melt-processed methods of injection moulding, extrusion molding, compression molding and blow molding etc and is processed into heat resistance, forming The excellent formed products such as processability, dimensional stability.When the polyarylene sulfide resin composition of present embodiment is due to being heated It is gas generated few, so the formed products of high-quality can be easily manufactured.
When the polyarylene sulfide resin composition of present embodiment is used for electric-vehicle part, can reduce is caused by heating It is gas generated.Therefore, it is possible to reduce the metal materials such as the gas componant i.e. low molecular weight compound of sulfur atom-containing and copper Contact can inhibit trees (tree as a result, can inhibit the reaction of the two in the case where applying high voltage repeatedly The depredation of smectic) generation, progress, improve resistance to electric trace.
In this way, the polyarylene sulfide resin composition of the present invention can be suitably used for hybrid vehicle (HV), electronic vapour The electric vehicle field for having lithium rechargeable battery and especially requiring high security of vehicle (EV) etc.Originally accordingly, with respect to general Electric-vehicle part obtained from the polyarylene sulfide resin composition forming of invention, such as can enumerate for accommodating power mould Block, current transformer, condenser, insulator, engine terminal box, battery, motor compressor, battery current sensor, junction block etc. Shell.The formed products are particularly suitable for the ignition coil shell as DLI systems.
Embodiment
The present invention is further elaborated with hereinafter, enumerating embodiment.But the present invention is not limited to these implementations Example.
1. evaluation assessment
[flexural property]
Standard test method ... ASTMD-790
Test film ... 3.2mm (thickness) × 12.7mm (width) × 127mm (length)
Test result ... tests the average value of number n=10
[hot water resistance]
Test film is immersed in 95 DEG C of hot water, investigates the ongoing change of bending strength.
Test film ... 3.2mm (thickness) × 12.7mm (width) × 127mm (length)
Test method ... the ASTM D-790 of bending strength
Conservation rate of bending strength of the assessment item ... after 1000 hours, 3000 hours relative to initial strength
Test result ... tests the average value of number n=5
[metal dhering strength]
Polyarylene sulfide resin of the injection with size quantity on the sheet metal (SUS304) for 4 × 10 × 49mm for being placed in mold Composition, and make its forming is implemented to stretch examination chuck between the formed products under conditions of 20mm, tensile speed 1mm/ minutes It tests, measures metal dhering strength.
[epoxy resin dhering strength]
The test film for shaping 3mm (thickness) × 25mm (width) × 75mm (length), on test film with bond area for 25mm × The mode of 10mm is with 40~50 μm of epoxy resin coating (host agents of thickness：EPICLON850 (Dainippon Ink Chemicals's manufacture)/titanium dioxide Silicon (50 mass % of filling rate), curing agent：Hexahydrophthalic anhydride, host agent/curing agent=100/30 (mass ratio)).By it Fixed with fixture after, heated at 85 DEG C 3 hours, then heat 3 hours at 150 DEG C, then Slow cooling, to make ring Oxygen resin solidification.Then, tensile shear strength was measured with 5mm/ minutes tensile speeds, records real load.
[die cavity balance]
Using the gasket mould with 40 die cavitys, understand in the die cavity (C1) near the position of a sprue gate With minimum molding condition by PPS compound injection mouldings under conditions of full packing.Molding condition is 75 tons of forming machines, barrel temperature Degree 320 DEG C, 140 DEG C of mold temperature, without pressurize.
By the filling of die cavity after molding (C1) and the die cavity (C10) farthest away from a sprue gate in identical runner Degree is compared.Compactedness (quality %) is asked by the formed products of die cavity (C10) relative to the mass ratio of the formed products of die cavity (C1) Go out.It may be said that the compactedness of die cavity (C10) is higher, die cavity balance is more excellent.According to compactedness, judged using benchmark below each The die cavity of composition balances.
AA：The range of 100~90 mass %
A：The range of 89~80 mass %
B：The range of 79~70 mass %
C：The range of 69~60 mass %
D：59% mass range below
[gas generated]
Using gas chromatography-mass spectrum device, by the sample of polyarylene sulfide resin or the specified amount of resin combination at 325 DEG C Lower heating 15 minutes, at this time gas generated is quantified in the form of quality %.
[resistance to electricity trace]
The test film for shaping 2mm (thickness) × 50mm (width) × 100mm (length), by the method according to ASTMD3638, along tree Fat flow direction measures, and by breakdown voltage and number mapping is added dropwise, reads the voltage of 50 drops.
2. the synthesis of polyphenylene sulfide (PPS resin)
(synthesis example 1：The synthesis of PPS-1)
By paradiiodobenzene (Tokyo is melted into Co., Ltd., 98.0% or more paradiiodobenzene purity) 300.0g, the solid sulfur (Northeast Chemical Co., Ltd. manufacture, sulphur (powder)) 27.00g, 4,4 '-two thiobis benzoic acid (Wako Pure Chemical Industries, Ltd.'s systems Making, 4,4 '-two thiobis benzoic acid, Technical Grade) 2.0g heats at 180 DEG C, they are dissolved under a nitrogen, Mixing.Then, 220 DEG C are warming up to, absolute pressure 26.6kPa is decompressed to.For obtained molten mixture, at 320 DEG C The mode that absolute pressure reaches 133Pa periodically changes temperature and pressure, carries out 8 hours melt polymerizations.After reaction, add Enter NMP200g, the heating stirring at 220 DEG C is filtered gained dissolved matter.It is added in dissolved matter after filtration NMP320g carries out filter cake cleaning filtering.Ion exchange water 1L is added in the obtained filter cake containing NMP, in autoclave, It is stirred 10 minutes in 200 DEG C.Then, filter cake is filtered, 70 DEG C of ion exchange water 1L is added in filter cake after filtration, is filtered Cake cleans.Ion exchange water 1L is added in the aqueous filter cake of gained, stirs 10 minutes.Then, filter cake, filter after filtration are filtered 70 DEG C of ion exchange water 1L is added in cake, carries out filter cake cleaning.After repeating the operation again, filter cake is done at 120 DEG C Dry 4 hours, obtain PPS resin (PPS-1) 91g.
(synthesis example 2：The synthesis of PPS-2)
" 2- Iodoanilines (Tokyo be melted into Co., Ltd. manufacture) " replacements " 4,4 '-two thiobis benzoic acid " is used, removes this it Outside, it is operated in the same manner as synthesis example 1, obtains PPS resin (PPS-2) 91g.
(synthesis example 3：The synthesis of PPS-3)
" diphenyl disulfide (Sumitomo Seika Co., Ltd, DPDS) " replacement " 4,4 '-two thiobis benzoic acid " is used, this is removed Except, it is operated in the same manner as synthesis example 1, obtains PPS resin (PPS-3) 91g.
(synthesis example 4：The synthesis of PPS-4)
N-Methyl pyrrolidone 600g and five hydrated sodium sulfide 336.3g (2.0mol) is put into the autoclave of 2L, in nitrogen 200 DEG C are warming up under gas atmosphere, water removal-NMP mixtures are removed in thus distillation.Then, it is added into the system by o-dichlorobenzene 292.53g (1.99mol) and 2,5- dichloroanilines 1.62g (0.01mol) are dissolved in the solution of gained in NMP230g, in nitrogen It under atmosphere, reacts 5 hours in 220 DEG C, and then is reacted 2 hours in 240 DEG C.From content, sampling after reaction vessel taking-up cooling A part, with gas chromatograph to unreacted 2,5- dichloroanilines are quantified.In addition, remaining slurry is cleaned with hot water several It is secondary, leaching polymer cake.The filter cake is dried under reduced pressure at 80 DEG C, obtains the polyphenylene sulfide containing amino (PPS-4) of powder.
The character of the PPS-1~PPS-4 obtained in synthesis example 1~4 is shown in table 1.
[table 1]
3. polyphenyl thioether resin composition (PPS compounds)
[raw material]
In order to prepare PPS resin composition, prepare following material.
(thermoplastic elastomer (TPE))
ELA：The copolymer of ethylene/methacrylic acid ethylene oxidic ester (3 mass %)/methyl acrylate (27 mass %) (Sumitomo Chemical Company Ltd's manufacture, " BONDFAST7L ")
(silane coupling agent)
Epoxy silane：γ-glycidoxypropyltrime,hoxysilane
(inorganic filler)
GF：Fiberglas chopped strand (10 μm of fibre diameter, length 3mm)
[making and evaluation of compound]
Machine is mixed according to formula composition shown in table 2, using bucket uniformly to mix each raw material, is then squeezed using twin-screw mixer Go out machine (TEM-35B, toshiba machine) and carry out melting mixing at 300 DEG C, obtains granular compound.The compound that will be obtained Carry out injection moulding under conditions of 300 DEG C of barrel temperature, 140 DEG C of mold temperature, make flexural property, metal dhering strength, The test film used in die cavity balance and hot water resistance experiment, carries out various evaluations.In addition, for individual PPS resin and again It is gas generated to close object measurement.It will be evaluation result is shown in table 2.
[table 1]
As shown in Table 2 the result shows that, (bending strength, bend fracture are stretched in mechanical property by PPS-1, PPS-2 and PPS-3 Long rate), the side of metal dhering strength, epoxy resin dhering strength, die cavity balance, hot water resistance, gas generated, resistance to electric trace Face is better than PPS-4.

Claims (25)

1. a kind of electric-vehicle part polyarylene sulfide resin composition, contains：
Polyarylene sulfide resin；With
Selected from by inorganic filler, the thermoplastic resin in addition to the polyarylene sulfide resin, elastomer and with 2 to submit At least one kind of other ingredients in the group of the crosslinkable resin composition of Lian Xing functional groups,
It includes making diiodo- aromatic compound, elemental sulfur and polymerization inhibitor comprising diiodo- virtue that the polyarylene sulfide resin, which utilizes, The method reacted in the molten mixture of fragrant compounds of group, the elemental sulfur and the polymerization inhibitor obtains,
The polyarylene sulfide resin has from the polymerization inhibitor in the group that the salt by amino, carboxyl and carboxyl forms At least one group, the polymerization inhibitor has above-mentioned functional group, or can generate above-mentioned functional group.
2. electric-vehicle part polyarylene sulfide resin composition according to claim 1, wherein the poly arylidene thio-ester tree Fat has at least one of the group for selecting the salt of free carboxyl group and carboxyl to form from polymerization inhibitor group.
3. electric-vehicle part polyarylene sulfide resin composition according to claim 1, wherein the poly arylidene thio-ester tree Fat is to include in main chain with the polyarylene sulfide resin of disulfide bond shown in the following general formula (20) and with relative to the poly arylidene thio-ester Resin is the mixture that the ratio of the range of 0.01~10000ppm includes iodine atom,
4. electric-vehicle part polyarylene sulfide resin composition according to claim 1, wherein the poly arylidene thio-ester tree Fat is the mixture for including iodine atom with the ratio relative to the range that the polyarylene sulfide resin is 0.01~5000ppm.
5. electric-vehicle part polyarylene sulfide resin composition according to claim 2, wherein the poly arylidene thio-ester tree Fat is the mixture for including iodine atom with the ratio relative to the range that the polyarylene sulfide resin is 0.01~5000ppm.
6. electric-vehicle part polyarylene sulfide resin composition according to claim 3, wherein the poly arylidene thio-ester tree Fat is the mixture for including iodine atom with the ratio relative to the range that the polyarylene sulfide resin is 0.01~5000ppm.
7. the electric-vehicle part polyarylene sulfide resin composition according to any one of claim 3~6, wherein main Polyarylene sulfide resin with disulfide bond shown in the following general formula (20) in chain is in end with one shown in the following general formula (1-1) Univalent perssad shown in valence group or the following general formula (2-1),
In formula (1-1), Y be hydroxyl or amino,
8. the electric-vehicle part polyarylene sulfide resin composition according to any one of claim 3~6, wherein main Polyarylene sulfide resin with disulfide bond shown in the following general formula (20) in chain is in end with monovalence shown in the following general formula (a) Univalent perssad shown in univalent perssad or the following general formula (c) shown in group, the following general formula (b),
Wherein, the X in general formula (a)~(c) is hydrogen atom or alkali metal atom, in general formula (b), R10Indicate carbon atom number 1~6 Alkyl, in general formula (c), R11Indicate hydrogen atom or the alkyl of carbon atom number 1~3, R12Indicate the alkyl of carbon atom number 1~5.
9. according to electric-vehicle part polyarylene sulfide resin composition according to any one of claims 1 to 6, wherein institute Stating polyarylene sulfide resin has 0.80~1.70 Mw/Mtop,
The Mw and Mtop is the weight average molecular weight measured using gel permeation chromatography and peak molecular weight respectively.
10. electric-vehicle part polyarylene sulfide resin composition according to claim 7, wherein the poly arylidene thio-ester Resin has 0.80~1.70 Mw/Mtop,
The Mw and Mtop is the weight average molecular weight measured using gel permeation chromatography and peak molecular weight respectively.
11. electric-vehicle part polyarylene sulfide resin composition according to claim 8, wherein the poly arylidene thio-ester Resin has 0.80~1.70 Mw/Mtop,
The Mw and Mtop is the weight average molecular weight measured using gel permeation chromatography and peak molecular weight respectively.
12. according to electric-vehicle part polyarylene sulfide resin composition according to any one of claims 1 to 6, wherein institute State polyarylene sulfide resin at 300 DEG C 0.95~1.75 non-newtonian index and 0.80~1.70 Mw/Mtop,
The Mw and Mtop is the weight average molecular weight measured using gel permeation chromatography and peak molecular weight respectively.
13. electric-vehicle part polyarylene sulfide resin composition according to claim 7, wherein the poly arylidene thio-ester Resin has the Mw/Mtop of 0.95~1.75 non-newtonian index and 0.80~1.70 at 300 DEG C,
The Mw and Mtop is the weight average molecular weight measured using gel permeation chromatography and peak molecular weight respectively.
14. electric-vehicle part polyarylene sulfide resin composition according to claim 8, wherein the poly arylidene thio-ester Resin has the Mw/Mtop of 0.95~1.75 non-newtonian index and 0.80~1.70 at 300 DEG C,
The Mw and Mtop is the weight average molecular weight measured using gel permeation chromatography and peak molecular weight respectively.
15. electric-vehicle part polyarylene sulfide resin composition according to claim 9, wherein the poly arylidene thio-ester Resin has the Mw/Mtop of 0.95~1.75 non-newtonian index and 0.80~1.70 at 300 DEG C,
The Mw and Mtop is the weight average molecular weight measured using gel permeation chromatography and peak molecular weight respectively.
16. electric-vehicle part polyarylene sulfide resin composition according to claim 10, wherein the poly arylidene thio-ester Resin has the Mw/Mtop of 0.95~1.75 non-newtonian index and 0.80~1.70 at 300 DEG C,
The Mw and Mtop is the weight average molecular weight measured using gel permeation chromatography and peak molecular weight respectively.
17. electric-vehicle part polyarylene sulfide resin composition according to claim 11, wherein the poly arylidene thio-ester Resin has the Mw/Mtop of 0.95~1.75 non-newtonian index and 0.80~1.70 at 300 DEG C,
The Mw and Mtop is the weight average molecular weight measured using gel permeation chromatography and peak molecular weight respectively.
18. a kind of electric-vehicle part formed products are by the polyarylene sulfide resin described in any one of claim 1~17 Obtained from composition forming.
19. a kind of electric-vehicle part has the formed products described in claim 18.
20. a kind of manufacturing method of electric-vehicle part polyarylene sulfide resin composition, which is characterized in that by poly arylidene thio-ester tree Fat with selected from by inorganic filler, the thermoplastic resin in addition to the polyarylene sulfide resin, elastomer and with 2 to submit At least one kind of other components fuses in the group of the crosslinkable resin composition of Lian Xing functional groups are kneaded,
It includes making diiodo- aromatic compound, elemental sulfur and polymerization inhibitor comprising diiodo- virtue that the polyarylene sulfide resin, which utilizes, The method reacted in the molten mixture of fragrant compounds of group, the elemental sulfur and the polymerization inhibitor obtains,
The polyarylene sulfide resin has from the polymerization inhibitor in the group that the salt by amino, carboxyl and carboxyl forms At least one group, the polymerization inhibitor has above-mentioned functional group, or can generate above-mentioned functional group.
21. the manufacturing method of electric-vehicle part polyarylene sulfide resin composition according to claim 20, wherein institute State at least one of the group for selecting the salt of free carboxyl group and carboxyl to form that polyarylene sulfide resin has from polymerization inhibitor base Group.
22. the manufacturing method of electric-vehicle part polyarylene sulfide resin composition according to claim 20, wherein institute Stating polyarylene sulfide resin has 0.80~1.70 Mw/Mtop,
The Mw and Mtop is the weight average molecular weight measured using gel permeation chromatography and peak molecular weight respectively.
23. the manufacturing method of electric-vehicle part polyarylene sulfide resin composition according to claim 20, wherein institute State polyarylene sulfide resin at 300 DEG C 0.95~1.75 non-newtonian index and 0.80~1.70 Mw/Mtop,
The Mw and Mtop is the weight average molecular weight measured using gel permeation chromatography and peak molecular weight respectively.
24. the manufacturing method of electric-vehicle part polyarylene sulfide resin composition according to claim 20, wherein institute State polymerization inhibitor be the following general formula (1) or the following general formula (2) compound represented,
In formula, Y is hydroxyl or amino.
25. the manufacturing method of electric-vehicle part polyarylene sulfide resin composition according to claim 20, wherein institute It includes the following general formula (3), (4) or (5) compound represented to state polymerization inhibitor,
In formula, in general formula (3), R1And R2Separately indicate hydrogen atom or the following general formula (a), (b) or (c) shown in one Valence group, R1Or R2In at least either be general formula (a), (b) or (c) shown in univalent perssad, in general formula (4), Z indicates iodine Atom or sulfydryl, R3Indicate the following general formula (a), (b) or (c) shown in univalent perssad, in general formula (5), R4Expression general formula (a), (b) or (c) univalent perssad shown in,
Wherein, the X in general formula (a)~(c) is hydrogen atom or alkali metal atom, in general formula (b), R10Indicate carbon atom number 1~6 Alkyl, in general formula (c), R11Indicate hydrogen atom or the alkyl of carbon atom number 1~3, R12Indicate the alkyl of carbon atom number 1~5.
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Families Citing this family (8)

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KR102300453B1 (en) * 2015-05-14 2021-09-09 에스케이케미칼 주식회사 Polyarylene sulfide composition having improved adhesion to metal
EP3381968B1 (en) 2015-11-23 2021-10-27 SK Chemicals Co., Ltd. Polyarylene sulfide resin and method for preparing same
JP7100222B2 (en) * 2015-11-23 2022-07-13 エスケー ケミカルズ カンパニー リミテッド Polyarylene sulfide resin composition and molded product
JP6742109B2 (en) * 2016-02-23 2020-08-19 帝人株式会社 Resin composition
JP6885096B2 (en) * 2016-02-26 2021-06-09 東レ株式会社 Polyphenylene sulfide resin composition and molded article
CN109705346A (en) * 2018-12-29 2019-05-03 重庆晟淦新材料科技有限公司 Polyphenylene sulfide and the preparation method and application thereof without lithium chloride and additive
WO2021100277A1 (en) * 2019-11-19 2021-05-27 Dic株式会社 Biaxially stretched laminated film, laminate, and methods for producing same
KR20210100814A (en) * 2020-02-07 2021-08-18 에스케이케미칼 주식회사 Polymerization inhibitor for a polyarylene sulfide resin

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102325826A (en) * 2008-12-23 2012-01-18 Sk化学株式会社 Method for preparing polyarylene sulfide
CN102762638A (en) * 2010-02-01 2012-10-31 Sk化学株式会社 Method for preparing polyarylene sulfide having a lower content of iodine
CN102791773A (en) * 2010-03-09 2012-11-21 Sk化学株式会社 Reusable polyarylene sulfide and method for preparing same
US20130115438A1 (en) * 2010-05-12 2013-05-09 Sk Chemical Co., Ltd. Polyarylene sulfide having excellent processability and preparation method thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4269198B2 (en) 1998-07-30 2009-05-27 Ｄｉｃ株式会社 Polyarylene sulfide resin composition
KR101554010B1 (en) * 2008-12-31 2015-09-18 에스케이케미칼 주식회사 Process for preparing polyarylene sulfide having lower content of isolated iodine
KR101944898B1 (en) * 2012-06-11 2019-02-01 에스케이케미칼 주식회사 Polyarylene sulfide resin composition and a preparation method thereof
JP2015030779A (en) * 2013-08-01 2015-02-16 帝人株式会社 Resin composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102325826A (en) * 2008-12-23 2012-01-18 Sk化学株式会社 Method for preparing polyarylene sulfide
CN102762638A (en) * 2010-02-01 2012-10-31 Sk化学株式会社 Method for preparing polyarylene sulfide having a lower content of iodine
CN102791773A (en) * 2010-03-09 2012-11-21 Sk化学株式会社 Reusable polyarylene sulfide and method for preparing same
US20130115438A1 (en) * 2010-05-12 2013-05-09 Sk Chemical Co., Ltd. Polyarylene sulfide having excellent processability and preparation method thereof

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