CN104650584A - Polyphenylene sulfide resin composition and molded product thereof - Google Patents
Polyphenylene sulfide resin composition and molded product thereof Download PDFInfo
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- CN104650584A CN104650584A CN201310371312.9A CN201310371312A CN104650584A CN 104650584 A CN104650584 A CN 104650584A CN 201310371312 A CN201310371312 A CN 201310371312A CN 104650584 A CN104650584 A CN 104650584A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/02—Polythioethers; Polythioether-ethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention provides a polyphenylene sulfide resin composition which comprises polyphenylene sulfide resin, special-shaped section glass fiber and amorphous resin with its glass-transition temperature being more than 100 DEG C. Chlorinity of the polyphenylene sulfide resin composition is below 1000 ppm. The polyphenylene sulfide resin composition has excellent fluidity, toughness and rigidity. The invention also provides framework forming products of a portable computer, a mobile phone and a portable electronic apparatus, wherein the framework forming products are prepared from the above polyphenylene sulfide resin composition.
Description
Technical field
The present invention relates to polymeric material field, be specifically related to have polyphenyl thioether resin composition and products formed thereof that superior fluidity and toughness have good rigidity concurrently simultaneously.
Background technology
Polyphenylene sulfide (PPS resin) has excellent mobility, high temperature resistant, corrosion-resistant, fire-retardant, balanced physical and mechanical properties and the feature such as fabulous dimensional stability and excellent electrical property, is widely used in electrically, the field such as electronic component or automobile component.
Because PPS molecular backbone chain is made up of a large amount of phenyl ring repeating units, compared with Other Engineering plastics, the good rigidly of PPS resin and poor toughness.In addition, a trend of the development of present electronic industry is goods thin-walled properties, so the polyphenyl thioether resin composition that exploitation has superior fluidity and excellent toughness is significant in electron trade simultaneously.Patent Document 1 discloses and in fiberglass reinforced polyphenylens sulfide resin, add resistant, toughened dose of A-663 can effectively improve resin toughness, by notched Izod impact strength from 7 ~ 9kJ/m
2bring up to 10 ~ 12kJ/m
2, maintain other performances of material, its modulus in flexure (rigidity) about 10GPa, it does not mention the improvement in mobility simultaneously.Patent documentation 2 discloses and in fiberglass reinforced polyphenylene sulfide, adds nanometer butadiene-styrene-vinyl rubber carry out toughness reinforcing, and notched Izod impact strength is brought up to 9 ~ 11kJ/m from 8
2, mobility aspect does not provide related data.The toughness improving fiberglass reinforced polyphenylene sulfide with the blend of Hydrogenated SBS or EPDM-g-St and ethylene-methyl methacrylate glycidyl ester announced by patent documentation 3, and its notched Izod impact strength is 8 ~ 11.5kJ/m
2but when its numerical value is 11.5, modulus in flexure is down to 9.7GPa, is difficult to keep higher toughness and rigidity simultaneously, and does not mention the improvement in mobility.Patent documentation 4 discloses and adopts PA6 to carry out toughness reinforcing to fiberglass reinforced polyphenylene sulfide, and the toughening effect of 10%PA6 is best, and notched Izod impact strength can be made to reach 13kJ/m
2, but modulus in flexure is down to 13.5GPa from 14.5.
Patent documentation 1, publication number CN102807753A;
Patent documentation 2, publication number CN1462771A;
Patent documentation 3, notification number CN1314762C;
Patent documentation 4, publication number CN101130633A.
Summary of the invention
The object of the invention is to: obtain the polyphenyl thioether resin composition that mobility, toughness and rigidity are excellent especially.
The invention provides a kind of polyphenyl thioether resin composition, described polyphenyl thioether resin composition comprises: (A) polyphenylene sulfide, (B) special crosssection glass fibre and (C) second-order transition temperature are the noncrystalline resin of more than 100 DEG C, and the cl content of described polyphenyl thioether resin composition is below 1000ppm.
In polyphenyl thioether resin composition of the present invention, relative to (A) polyphenylene sulfide of 100 weight parts, (B) special crosssection glass fibre is preferably 50-200 weight part, and (C) second-order transition temperature is that the noncrystalline resin of more than 100 DEG C is preferably 1.5-35 weight part.From the viewpoint of rigidity and mobility two, relative to (A) polyphenylene sulfide of 100 weight parts, profiled-cross-section glass fibre is 60-180 weight part more preferably; Further be preferably 85-135 weight part; In order to improve toughness to a greater extent and ensure mobility, (C) second-order transition temperature is that the noncrystalline resin of more than 100 DEG C is relative to (A) polyphenylene sulfides of 100 weight parts, more preferably 2-25 weight part, is further preferably 4-15 weight part.
(A) polyphenylene sulfide:
(A) polyphenylene sulfide used in the present invention is the polymkeric substance with the repeating unit shown in following structural formula (I),
From the view point of thermotolerance, above-mentioned (I) repeating unit accounts for more than 70 % by mole of (A) polyphenylens sulfide resin unit, is more preferably more than 90 % by mole.Wherein, when (I) repeating unit accounts for more than 70 % by mole of (A) polyphenylene sulfide unit, in (A) polyphenylene sulfide unit remaining less than 30 % by mole unit can by have the repeating unit (II) of following structure or (III) or (IV) or (V) or (VI) or (VII) or (VIII) any one or more than one form.Further when (I) repeating unit accounts for more than 90 % by mole of (A) polyphenylene sulfide unit, in (A) polyphenylene sulfide unit remaining less than 10 % by mole unit can by have the repeating unit (II) of following structure or (III) or (IV) or (V) or (VI) or (VII) or (VIII) any one or more than one form.
When have in (A) polyphenylene sulfide unit above-mentioned repeating unit (II) or (III) or (IV) or (V) or (VI) or (VII) or (VIII) any one or more than one time, (A) fusing point of polyphenylene sulfide is lower, from the view point of shaping, be favourable.
To (A) polyphenylene sulfide used in the present invention, from obtaining superior fluidity, preferably there is high fusion index further.Such as preferred more than 200g/10 minute, preferred more than 500g/10 minute further, about the upper limit, from the view point of obtaining excellent toughness, be preferably less than 5000g/10 minute.
The method of calculation of melting index are: reference standard ISO1133-2005, use Toyo Seiki MeltIndexer F-B01 at 315 DEG C, under 2.16Kg load, calculate and obtain from the weight grams of the resin of kapillary outflow in 10 seconds.
The kind of (A) polyphenylene sulfide in the present invention is not particularly limited, it can be more than a kind or a kind, 1000ppm is less than, preferably the mixture of 2 kinds or two or more polyphenylene sulfide in order to regulate and control the mobility of polyphenyl thioether resin composition, toughness, rigidity and its cl content better.
The present invention is not particularly limited for the manufacture method of (A) polyphenylene sulfide, as long as can obtain (A) polyphenylene sulfide of said structure.Prepared by the method for the acquisition larger molecular weight polymkeric substance that the method for the acquisition relatively small molecular weight polymkeric substance that Japanese Patent Publication 45-3368 publication can be selected to record or Japanese Patent Publication 52-12240 publication etc. are recorded.The difference of the former with the latter is whether there is reagent and additive in polymerization alkali metal carboxylate in polymerization system.The former does not add alkali metal carboxylate in polymerization system, and therefore the polymerization degree is not high, molecular weight, thus mobility is just high, and the latter gives resin high toughness compared with high energy due to molecular weight.So the polyphenylene sulfide can prepared by two kinds of methods is combinationally used, mobility and the toughness of polyphenylene sulfide can be balanced.
(B) profiled-cross-section glass fibre:
(B) special crosssection glass fibre described in the present invention refers to the non-circular glass fibre of the section of individual glass fibers, and when adopting (B) special crosssection glass fibre, resin combination can obtain better mobility and mechanical strength.
In order to coordinate polyphenylene sulfide to obtain better mobility, described (B) profiled-cross-section glass fibre, its flat ratio is preferably greater than or equal to 1.5.Flat ratio refers to the ratio of the long and short diameter of glass fibre section.Described (B) profiled-cross-section glass fibre, the area of its cut surface is preferably 100-500 μm
2/ root, more preferably 110-300 μm
2/ root.
(C) second-order transition temperature is the noncrystalline resin of more than 100 DEG C:
From obtaining all excellent viewpoint of toughness and rigidity, in polyphenyl thioether resin composition of the present invention, add the noncrystalline resin (C) that second-order transition temperature is more than 100 DEG C.
Second-order transition temperature is that the noncrystalline resin (C) of more than 100 DEG C is selected from: one or more in cyclic olefin polymer, cyclic olefine copolymer, polycarbonate, polyphenylene oxide, amorphous polyarylester, polysulfones, polyethersulfone, polyetherimide, polyamidoimide, polyimide or its multipolymer.Wherein, from the viewpoint of thermotolerance and consistency, one or more in optimization polycarbonate, polyphenylene oxide, amorphous polyarylester, polysulfones, polyethersulfone, polyetherimide, polyamidoimide, polyimide or its multipolymer.
Consider from obtaining excellent mobility, polyphenyl thioether resin composition of the present invention is at 315 DEG C of down cut speed 1000s
-1capillary rheometer melt viscosity will lower than 180Pas, more preferably below 150Pas, about lower limit, from the view point of obtaining excellent toughness, be preferably more than 80Pas.Testing tool is the machine-processed 140-SAS-2002 of peace field essence.
From the impact reduced environment, the cl content of the polyphenyl thioether resin composition in the present invention is less than 1000ppm.From polymkeric substance, the cl content of (A) polyphenylene sulfide is less than 2000ppm.The mensuration of cl content is with reference to European standard EN14582:2007.
Polyphenylens sulfide resin composition of the present invention, while having original the had excellent rigidity of (A) polyphenylene sulfide, has excellent toughness.In order to realize this characteristic, (C) second-order transition temperature be the noncrystalline resin of more than 100 DEG C more preferably: noncrystalline resin formed in polyphenyl thioether resin composition " island " shape dispersion, the average area of these " island " shape things is less than 1 μm
2/.Further be preferably: noncrystalline resin forms the dispersion of " island " shape in polyphenyl thioether resin composition, and the average area of these " island " shape things is less than 0.5 μm
2/.If (C) second-order transition temperature is that the average area of these " island " shape things that the noncrystalline resin of more than 100 DEG C is formed is greater than 1 μm
2/, then toughness raising effect may be impaired.
In addition, the average area of these " island " shape things mentioned here is that following method obtains.Namely, polyphenyl thioether resin composition ejection formation is become standard batten (batten forming mould is wide 10mm × thick 4mm), the section ruthenium of batten is dyeed, cut into the thin slice under 0.1 μm, observe under transmission electron microscope, observe (C) second-order transition temperature be more than 100 DEG C noncrystalline resin become " island " shape be scattered in polyphenyl thioether resin composition, these " island " average area of shape thing can carry software by instrument and carry out automatic area meter calculation, with the area obtained divided by these " island " number of shape thing just obtains the average area of these " island " shape things.During actual computation, measure arbitrarily the area of 100 " island " shape things, it is arranged from big to small, counts a1, a2, a3 ... .a100, the area of these 80 " island " shape things of a11 to a90 is made arithmetical mean, and the numerical value obtained just counts the average area of these " island " shape things.
In addition, in the scope not damaging effect of the present invention, elastomerics can being added in polyphenyl thioether resin composition of the present invention, by adding elastomerics, can work in coordination with noncrystalline resin the toughness improving polyphenylene sulfide.
Elastomeric example has: ethylene series elastomerics, modified olefin based elastomers or phenylethylene elastomerics etc.Wherein ethylene series elastomer is if any: independent alpha-olefins such as ethene, propylene, 1-butylene, 1-amylene, 4-methyl-1-pentene or iso-butylene or two or more to be polymerized the polymkeric substance or multipolymer that obtain, the α such as alpha-olefin and vinylformic acid, methyl acrylate, ethyl propenoate, butyl acrylate, methacrylic acid, methyl methacrylate, β-dimethyl-aminoethylmethacrylate or butyl methacrylate, the multipolymer etc. of beta-unsaturated acid and alkyl ester thereof.The elastomeric object lesson of ethylene series has: polyethylene, polypropylene, ethylene/propene copolymer ("/" represents copolymerization, identical below), Ethylene/1-butene multipolymer, ethylene/methyl acrylate copolymer, ethylene/ethyl acrylate multipolymer, ethylene/butylacrylate copolymer, ethylene/methacrylic acid methyl terpolymer, ethylene/methacrylic acid methacrylate copolymers, ethylene/methacrylic acid acrylate copolymer, propylene/copolymer-maleic anhydride or iso-butylene/copolymer-maleic anhydride etc.
Modified olefin based elastomers has the monomer component (composition containing functional group) of the functional groups such as epoxy group(ing), anhydride group or iolon by importing in above-mentioned ethylene series elastomerics and obtains.The example of the composition of this functional group has: maleic anhydride, itaconic anhydride, citraconic anhydride, interior dicyclo (2,2,1) 5-heptene-2,3-dicarboxylic acid or interior dicyclo (2,2,1) 5-heptene-2, the monomer containing anhydride group such as 3-dicarboxylic anhydride, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itoconate or citraconic acid glycidyl ester etc. are containing the monomer of epoxy group(ing), or carboxylic acid metal complex waits the monomer containing iolon.
These methods containing the composition of functional group of importing are not particularly limited, can following methods be adopted: when being above-mentioned ethylene series (be total to) the polymkeric substance copolymerization same as the composition of ethylene series elastomerics use, make its copolymerization with it; Or use radical initiator to the method for ethylene series (being total to) polymer graft importing etc.Relative to the whole monomers forming uncommon (be total to) polymkeric substance of modified olefin, be appropriate containing the import volume of the composition of functional group the scope of 0.001-40 % by mole, preferred 0.01-35 % by mole.
Import to olefin polymer kind and there is epoxy group(ing), anhydride group, or the monomer component of functional group such as iolon and the object lesson of useful especially ethylene series (being total to) polymkeric substance obtained have: ethylene/propene-g-glycidyl methacrylate copolymer (" g " represents grafting, identical below), Ethylene/1-butene-g-glycidyl methacrylate copolymer, ethylene/acrylic acid glycidyl ester copolymer, ethylene/methacrylic acid glycidyl ester copolymer, ethylene/methyl acrylate/glycidyl methacrylate copolymer, ethylene/methacrylic acid methyl esters/glycidyl methacrylate copolymer, ethylene/propene-g-copolymer-maleic anhydride, Ethylene/1-butene-g-copolymer-maleic anhydride, ethylene/methyl acrylate-g-copolymer-maleic anhydride, ethylene/ethyl acrylate-g-copolymer-maleic anhydride, ethylene/methacrylic acid methyl esters-g-copolymer-maleic anhydride, ethylene/methacrylic acid ethyl ester-g-copolymer-maleic anhydride, the zinc complex of ethylene/methacrylic acid, the magnesium complex of ethylene/methacrylic acid, or the sodium complex etc. of ethylene/methacrylic acid.
Have from the preferred example of the viewpoint of consistency: ethylene/methacrylic acid glycidyl ester copolymer, ethylene/methyl acrylate/glycidyl methacrylate copolymer, ethylene/methacrylic acid methyl esters/glycidyl methacrylate copolymer, Ethylene/1-butene-g-copolymer-maleic anhydride or ethylene/ethyl acrylate-g-copolymer-maleic anhydride etc.
Especially preferred example has: ethylene/methacrylic acid glycidyl ester copolymer, ethylene/methyl acrylate/glycidyl methacrylate copolymer or ethylene/methacrylic acid methyl esters/glycidyl methacrylate copolymer etc.
On the other hand, the object lesson of styrene series elastomer has: styrene/butadiene copolymers, styrene/ethylene/butadienecopolymer, styrene/ethylene/propylene copolymer or styrene/isoprene multipolymer etc., from consistency optimization styrene/butadienecopolymer.The epoxide of further optimization styrene/butadienecopolymer.
Elastomeric weight part is 0.5-20 weight part relative to 100 weight part polyphenylene sulfides (A), preferred 0.8-10 weight part, more preferably 1-6 weight part, from the viewpoint of mobility and toughness two, elastomeric weight part suitably can regulate according to elastomeric kind, other condition.In order to obtain excellent toughness and mobility, 2 kinds or two or more can be combined by above-mentioned elastomerics.
In addition, in the scope not damaging effect of the present invention, silane compound, titanate ester can be added in polyphenyl thioether resin composition of the present invention as compatilizer.
Silane compound such as has epoxy radicals silicone hydride compound, amino silane compounds, ureido silane compound or isocynate silane compound, in addition, can also use various silane compound.The object lesson of this silane compound has: γ-glycidoxypropyltrimethoxy silane, γ-epoxypropoxy triethoxyl silane, or the alkoxysilane compound containing trialkylsilyl group in molecular structure containing epoxy group(ing) such as β-(3,4-expoxycyclohexyl) ethyl trimethoxy silane, γ mercaptopropyitrimethoxy silane, the alkoxysilane compound containing trialkylsilyl group in molecular structure containing sulfydryl such as γ-mercaptopropyi methyl dimethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureido-propyl Trimethoxy silane, or the alkoxysilane compound containing trialkylsilyl group in molecular structure containing urea groups such as γ-(2-urea groups ethyl) TSL 8330, γ-isocyanate group propyl-triethoxysilicane, γ-isocyanate group propyl trimethoxy silicane, γ-isocyanate group hydroxypropyl methyl dimethoxysilane, γ-isocyanate group hydroxypropyl methyl diethoxy silane, γ-isocyanate group ethyl dimethoxysilane, γ-isocyanate group ethyl diethoxy silane, or the alkoxysilane compound containing trialkylsilyl group in molecular structure containing isocyanate group such as γ-isocyanate group propyltrichlorosilan, γ-(2-amino-ethyl) amino propyl methyl dimethoxysilane, γ-(2-amino-ethyl) amino propyl methyl Trimethoxy silane, gamma-amino propyl trimethoxy silicanes etc. are containing amino alkoxysilane compound containing trialkylsilyl group in molecular structure, and γ-hydroxypropyl Trimethoxy silane, or the alkoxysilane compound containing trialkylsilyl group in molecular structure etc. of the hydroxyl such as γ-hydroxypropyl triethoxyl silane.
The example of titanate ester has: the compound of sec.-propyl two oleic acid acyloxy (dioctyl phosphoric acid acyloxy) titanic acid ester, sec.-propyl three oleic acid acyloxy titanic acid ester, three Unimac 5680 isopropyl titanates, three Unimac 5680 isopropyl titanates, Di(dioctylpyrophosphato) ethylene titanate or tetra isopropyl two (dioctyl phosphito acyloxy) titanic acid ester etc.
The weight part of silane compound is 0.01-3 weight part relative to 100 weight part polyphenylene sulfides (A), preferred 0.05-2 weight part, more preferably 0.1-1 weight part, by adding such silane compound, the mechanical strength toughening effect improving polyphenyl thioether resin composition well can be balanced.The weight part ratio 0.01 of silane compound is few, then possibly cannot play the effect of compatilizer, in addition, large than 3, then when may be attended by reduction and the ejection formation of mobility, gas increases.In addition, also 2 kinds or of more than two kinds above-mentioned silane compounds can be combinationally used.
In addition, in the scope not damaging effect of the present invention, in polyphenyl thioether resin composition of the present invention, can antioxidant be added, thermotolerance and the thermostability of resin combination can be improved further.Antioxidant is preferably containing the antioxidant of more than a kind or a kind chosen from phenol antioxidant and phosphorus antioxidants.When also with phenol antioxidant and phosphorus antioxidants, thermotolerance and thermostability can be kept especially efficiently, therefore preferably.
As phenol antioxidant, preferably use hindered phenol compound.Concrete example has: triglycol two (the 3-tertiary butyl-(5-methyl-4-hydroxybenzyl) propionic ester), N, N '-hexa-methylene two (3, 5-di-t-butyl-4-hydroxy-hydrocineamide), four (methylene radical-3-(3 ', 5 '-di-t-butyl-4 '-hydroxybenzyl) propionic ester) methane, tetramethylolmethane four (3-(3 ', 5 '-di-t-butyl)-4 '-hydroxybenzyl) propionic ester), 1, 3, 5-tri-(3, 5-di-tert-butyl-4-hydroxyl benzyl)-s-triazine-2, 4, 6-(1H, 3H, 5H)-triketone, 1, 1, 3-tri-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 4, 4 '-butylidene two (3-methyl-6-tert butyl phenyl), Octadecane base-3-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester, 3, 9-bis-(2-(3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy)-1, 1-dimethyl ethyl)-2, 4, 8, 10-tetra-oxaspiro (5, 5) undecane, or 1, 3, 5-trimethylammonium-2, 4, 6-tri--(3, 5-di-tert-butyl-4-hydroxyl benzyl) benzene etc.Wherein preferred ester type polymer hindered phenol type, preferably use four (methylene radical-3-(3 ' particularly, 5 '-di-t-butyl-4 '-hydroxybenzyl) propionic ester) methane, tetramethylolmethane four (3-(3 ', 5 '-di-t-butyl)-4 '-hydroxybenzyl) propionic ester) or 3,9-bis-(2-(3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy)-1,1-dimethyl ethyl)-2,4,8,10-tetra-oxaspiro (5,5) undecane etc.
As phosphorus antioxidants; two (2 can be listed; 6-di-t-butyl-4-aminomethyl phenyl) tetramethylolmethane-diphosphites, two (2; 4-di-tert-butyl-phenyl) tetramethylolmethane-diphosphites, two (2; 4-dicumylphenyl) tetramethylolmethane-diphosphites, three (2; 4-di-tert-butyl-phenyl) phosphorous acid ester, four (2; 4-di-tert-butyl-phenyl)-4; 4 '-bis-phenylene phosphorous acid ester, distearyl acyl group tetramethylolmethane-diphosphites, triphenyl phosphite or 3,5-dibutyl-4-hydroxybenzyl phosphate ester diethyl ester etc.
Wherein, in polyphenyl thioether resin composition, less to volatilize Sum decomposition to make antioxidant, the antioxidant that preferred fusing point is high, preferably use two (2 particularly, 6-di-t-butyl-4-aminomethyl phenyl) tetramethylolmethane-diphosphites, two (2,4-di-tert-butyl-phenyl) tetramethylolmethane-diphosphites or two (2,4-dicumylphenyl) tetramethylolmethane-diphosphites etc.
The weight part of antioxidant is 0.01-3 weight part relative to 100 weight part polyphenylene sulfides (A), from the gaseous constituent aspect produced time shaping, 2 kinds or two or more antioxidant combination can also be used by preferred 0.05-2 weight part, more preferably 0.1-1 weight part.
In addition, in the scope not damaging effect of the present invention, in polyphenyl thioether resin composition of the present invention, other composition can be added, such as filler (quartz, calcium carbonate, clay, kaolin, two fluidisation molybdenums, wollastonite, aluminum oxide, graphite, metal powder, carbon dust, carbon nanotube, polyacrylonitrile based or pitch-based carbon fiber, or mica etc., wherein from protection against corrosion, lubrication, the effect of giving electroconductibility is set out, preferred calcium carbonate, or silicon-dioxide), releasing agent (montanic acid and metal-salt thereof, its ester, its half ester, hard ester alcohol, stearylamide, polyamide-based, hydrazo-dicarbonamide or polyethylene wax etc., wherein produce gas from when reducing shaping, preferred polyamide class), pigment (Cadmium Sulfide, phthalocyanine, or color black masterbatch etc.), dyestuff (nigrosine etc.), crystal seed agent (talcum powder, titanium dioxide, kaolin, clay, or polyether-ether-ketone etc.), softening agent (P-hydroxybenzoic acid monooctyl ester, or N-butylbenzenesulfonamide etc.), static inhibitor (alkyl sulphate type negatively charged ion system static inhibitor, quaternary ammonium salt cationic system static inhibitor, the nonionic system static inhibitor such as polyoxyethylene sorbitol acid anhydride single-hard ester acid ester, or trimethyl-glycine system both sexes static inhibitor etc.), fire retardant (such as red phosphorus, phosphoric acid ester, trimeric cyanamide hydrogen urea hydrochlorate, magnesium hydroxide, the oxyhydroxide such as aluminium hydroxide, ammonium polyphosphate, brominated Polystyrene, brominated polyphenylether, brominated polycarbonate, the combination etc. of brominated epoxy resin or these bromide fire retardants and antimonous oxide), or other polymkeric substance.
Polyphenyl thioether resin composition of the present invention can be prepared by known method.Namely, the above polyphenylene sulfide (A), special crosssection glass fibre (B) and the noncrystalline resin of second-order transition temperature more than 100 DEG C (C) are main component, the compositions such as any selection elastomerics, silane compound, antioxidant, filler, heat-resisting stabilizing agent, weather agent, releasing agent, pigment, fuel, crystal seed agent, softening agent, static inhibitor or fire retardant, with mentioned component premix, or do not carry out premix and just supply forcing machine etc., melting in this forcing machine, simultaneously fully mixing, be prepared thus.In addition, about special crosssection glass fibre, bat wool to the feed of forcing machine, lose in order to fibrous when suppressing melting mixing, filler beyond preferred polyphenylene sulfide, elastomerics, silane compound, antioxidant, threadiness, weather agent, releasing agent, pigment, fuel, crystal seed agent, softening agent, static inhibitor or fire retardant etc. are fed intake by the original inlet of forcing machine, and special crosssection glass fibre or bat wool use side spout feed.
Can obtain mobility, toughness and rigidity polyphenyl thioether resin composition excellent especially by the present invention, it is specially adapted to thin-wall part ejection formation, is particularly useful for the basket formation goods of ejection formation portable computer, mobile phone, portable electronic appliance.
Therefore the present invention also provides the basket of a kind of portable computer, mobile phone, portable electronic appliance to form goods, uses above-mentioned polyphenyl thioether resin composition to obtain.
The present invention also provides a kind of products formed obtained by above-mentioned polyphenyl thioether resin composition.
Above-mentioned products formed, thin segment thickness is below 1.5mm.
Embodiment
Further illustrate the present invention below by specific embodiment, following examples premised on technical solution of the present invention under implement, give detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
The material given by following (1)-(4) is selected from for the polyphenylene sulfide of the embodiment of following explanation and comparative example, special crosssection glass fibre, noncrystalline resin and other non-essential additives.
(1) polyphenylene sulfide (hereinafter referred to as PPS)
The manufacture of a.PPS-1 resin
To with in 20 liters of autoclaves of agitator and bottom valve, load 2383g (20.0 moles) 47% Sodium sulfhydrate, the sodium hydroxide of 836g (20.1 moles) 96%, 3960g (40.0 moles) METHYLPYRROLIDONE (NMP), 313g (3.81 moles) sodium-acetate and 3000g deionized water, nitrogen is passed under normal pressure, and 225 DEG C were slowly heated in 3 hours, after distillating 4200g water and 80g NMP, by reactor cooling to 160 DEG C.
Then, add the santochlor of 3031g (20.6 moles), 1515g (15.3 moles) NMP, sealed by reaction vessel under a nitrogen, under 400rpm stirs, 0.8 DEG C/min is warming up to 225 DEG C from 200 DEG C, keeps 30 minutes.Then 0.3 DEG C/min is warming up to 274 DEG C, keeps 40 minutes.Then 282 DEG C are warming up to.Opened by autoclave bottom valve, nitrogen pressurization is by mixture flash distillation in container extremely with in the container of agitator, and 250 DEG C are stirred for a moment, remove most of NMP, reclaim the solid matter comprising PPS and salt.
To with the solid matter and the 15000g deionized water that add gained in the autoclave of agitator, clean 30 minutes at 70 DEG C, filter, deionized water wash, obtains filter cake.
The filter cake of gained and 12000g deionized water are joined in the autoclave with agitator, with the air of nitrogen replacement autoclave, is then warming up to 192 DEG C, keep 30 minutes, then cool autoclave, take out thing in still.Being filtered, is first the solution washing of 33% acetic acid by mass concentration, filters, and then obtains filter cake with deionized water wash.To filter cake warm air drying 1 hour at 80 DEG C, then vacuum-drying 24 hours at 120 DEG C, obtain dry PPS resin, the melting index of the PPS-1 resin of gained is 760g/10 minute, and cl content is 1400ppm.Here the method for calculation of melting index are: reference standard ISO1133-2005, use Toyo Seiki Melt Indexer F-B01 at 315 DEG C, under 2.16Kg load, calculate and obtain from the weight grams of the resin of kapillary outflow in 10 seconds.The mensuration of cl content is with reference to European standard EN14582:2007.
The manufacture of b.PPS-2 resin
To with in 20 liters of autoclaves of agitator and bottom valve, load 2383g (20.0 moles) 47% Sodium sulfhydrate, the sodium hydroxide of 831g (19.9 moles) 96%, 3960g (40.0 moles) METHYLPYRROLIDONE (NMP) and 3000g deionized water, nitrogen is passed under normal pressure, and 225 DEG C were slowly heated in 3 hours, after distillating 4200g water and 80g NMP, by reactor cooling to 160 DEG C.
Then, add the santochlor of 4410g (30 moles), 1515g (15.3 moles) NMP, sealed by reaction vessel under a nitrogen, under 400rpm stirs, 0.8 DEG C/min is warming up to 225 DEG C from 200 DEG C, keeps 30 minutes.Then 0.3 DEG C/min is warming up to 274 DEG C, keeps 30 minutes.Then 282 DEG C are warming up to.Opened by autoclave bottom valve, nitrogen pressurization is by mixture flash distillation in container extremely with in the container of agitator, and 250 DEG C are stirred for a moment, remove most of NMP, reclaim the solid matter comprising PPS and salt.
To with the solid matter and the 16000g deionized water that add gained in the autoclave of agitator, clean 30 minutes at 70 DEG C, filter, deionized water wash, obtains filter cake.
The filter cake of gained and 12000g deionized water are joined in the autoclave with agitator, with the air of nitrogen replacement autoclave, is then warming up to 192 DEG C, keep 30 minutes, then cool autoclave, take out thing in still.Being filtered, is first the solution washing of 50% acetic acid by mass concentration, filters, and then obtains filter cake with deionized water wash.To filter cake warm air drying 1 hour at 80 DEG C, then vacuum-drying 24 hours at 120 DEG C, obtain dry PPS resin, the melting index of the PPS-1 resin of gained is 4500g/10 minute, and cl content is 2200ppm.Here the method for calculation of melting index are: reference standard ISO1133-2005, use Toyo Seiki Melt Indexer F-B01 at 315 DEG C, under 2.16Kg load, calculate and obtain from the weight grams of the resin of kapillary outflow in 10 seconds.The mensuration of cl content is with reference to European standard EN14582:2007.
(2) profiled-cross-section glass fibre be day east spin the special crosssection glass fibre that the flat ratio made is 4 or 2; Rounded section glass fibre is as a comparison case manufactured by NEC glass society, its single fiber diameter 10.5 μm.
(3) second-order transition temperature is the noncrystalline resin of more than 100 DEG C
Polycarbonate (Tg=145 DEG C), Idemitsu A1900;
Polyphenylene oxide powder (Tg=211 DEG C), Aldrich;
Amorphous polyarylester (Tg=195 DEG C), Unitika U-100;
Polysulfones (Tg=190 DEG C), Solvay P-1700;
Polyethersulfone 4800P (Tg=220 DEG C), Sumitomo Chemical;
Polyetherimide (Tg=215 DEG C), Sabic Ultem1010;
Polyamidoimide (Tg=250-300 DEG C), Toray TI-5000;
Polyimide (Tg=265 DEG C), Mitsui Chemicals E-2021;
Polystyrene Mw 350000 (Tg=95 DEG C), Aldrich;
Second-order transition temperature data refer is from Polymer Handbook, and the 4th edition, J.Brandrup etc. are outstanding, and Wiley-Interscience publishes, and 1999.
(4) high density polyethylene(HDPE), Lanzhou Petrochemical 5000s; The crystalline resins used as a comparison case;
(5) silane compound, Shin-Etsu Chemical; Titanic acid ester, the excellent general chemical industry in Nanjing;
Polypropylene-g-maleic anhydride, poly-(iso-butylene-alt-maleic anhydride) and poly-(ethene co-propylene), Aldrich;
Poly-(ethene-co-glycidyl methacrylate), Sumitomo Chemical;
Calcium carbonate, Calfine Jin Ping workshop;
Tetramethylolmethane four (3-(3 ', 5 '-di-t-butyl)-4 '-hydroxybenzyl) propionic ester), traditional Chinese medicines chemistry;
Oxidic polyethylene cured (1160H), Mitsui Chemicals;
Black masterbatch (flame retardant grade), general auspicious Dehua work.
After raw material high-speed mixer being dry mixed according to the ratio shown in table 1, adopt biaxial extruder (L/D=45.5) granulation of JSW society TEX30 α type, forcing machine has 13 heating zone, have two cuff measuring instruments feeding device and with vacuum-pumping equipment.After granulation completes, the polyphenyl thioether resin composition particle obtained after dry 3h, is injection molded into iso standard batten and carries out performance test in the baking oven of 130 DEG C.
Form is observed:
In polyphenyl thioether resin composition, (C) amorphous resin is dispersed in wherein.
By polyphenyl thioether resin composition ejection formation (forming mould is wide 10mm × thick 4mm), the section ruthenium of products formed is dyeed, cut into the thin slice under 0.1 μm, observe under transmission electron microscope, observe (C) second-order transition temperature be more than 100 DEG C noncrystalline resin become " island " shape be scattered in polyphenyl thioether resin composition, these " island " average area of shape thing can carry software by instrument and carry out automatic area meter calculation, with the area obtained divided by these " island " number of shape thing just obtains these " island " average area of shape thing.(with mentioned above)
Capillary viscosity is tested:
Be 1000s by dried polyphenyl thioether resin composition particle 315 DEG C of down cut speed
-1capillary rheometer on carry out fluidity testing, measure melt viscosity value.
Rigidity and toughness properties test:
Modulus in flexure and bending moment (breaking point displacement), the standard batten good with injection moulding measures by standard ISO 178, and bending speed 2mm/min, often organizes 5 and average;
Charpy notched Izod impact strength, the standard batten good with injection moulding measures by standard ISO 179, often organizes 5 and averages.
Modulus in flexure reflects the rigidity of material, and modulus is large, and rigidity is large, otherwise rigidity is little;
Charpy notched Izod impact strength reflects toughness when material is subject to temporary impact, and intensity is larger, and illustrative material impact resistance is strong, and bending moment is the deformation quantity produced when external force slowly acts on material, and it more reflects the ductility of material.If notched Izod impact strength and bending moment increase simultaneously, can think that toughness of material is improved.
Embodiment 1-10:
Raw material is as shown in table 1.Except glass fibre, after other raw materials mix in high-speed mixer, add from extruder main spout, glass fibre adds from extruding pusher side spout, extruder temperature is set as 200 DEG C-330 DEG C, through melting, extrude, cool, pelletizing obtains granular polyphenyl thioether resin composition; This saccharoid after dry 3h, is injection molded into standard batten (batten die size is wide 10mm × thick 4mm), carries out performance test by above-mentioned testing method in the baking oven of 130 DEG C.The batten performance measurement result that each embodiment obtains is shown, the result of the average area of " island " shape thing that noncrystalline resin is formed in each sample in table 2.
Comparative example 1-3:
Preparation method is identical with embodiment 1, and raw material is as shown in table 1.Results of property is as shown in table 2, mobility is very poor, the melt viscosity of capillary rheometer higher than 180Pas, when being the noncrystalline resin of more than 100 DEG C when not adopting second-order transition temperature, bending moment more than 2.0mm, can not be difficult to meet mobility, rigidity and toughness all excellent simultaneously.
In addition, also carried out the batten ejection formation of 1.5mm, found that each embodiment moulding process is convenient, from mobility, toughness combination rigidity, preferred embodiment 2, implements 3, implement 4, implement 5, implement 6, implement 9, implement 10, preferably implement 2 further, implement 3, implement 4, implement 5, above-mentioned preferred embodiment carries out 1.5mm batten ejection formation, and the shaping spline surfaces obtained is smooth, full (batten is of a size of long 125mm × wide 13mm × thick 1.5mm).And comparative example 1-3 is shaping more difficult, forming pressure is more than 150MPa, and in ejection formation process, forming machine has abnormal sound, and shaping batten all can not be made.Thus, implement 2, implement 3, implement 4, implement the ejection formation that 5 have carried out again 1mm plastic, the shaping spline surfaces obtained is smooth, full (batten is of a size of long 125mm × wide 13mm × thick 1mm).
Polyphenyl thioether resin composition of the present invention has excellent mobility, toughness and rigidity simultaneously, therefore with the obvious advantage when ejection formation thin-gage goods, be particularly useful for the basket formation goods of frivolous, the solid portable computer of ejection formation, mobile phone, portable electronic appliance.
Table 1
Table 1(continues)
Table 2
Claims (10)
1. a polyphenyl thioether resin composition, it is characterized in that: described polyphenyl thioether resin composition comprises: (A) polyphenylene sulfide, (B) special crosssection glass fibre and (C) second-order transition temperature are the noncrystalline resin of more than 100 DEG C, and the cl content of described polyphenyl thioether resin composition is below 1000ppm.
2. polyphenyl thioether resin composition according to claim 1, it is characterized in that: relative to (A) polyphenylene sulfide of 100 weight parts, (B) special crosssection glass fibre is 50-200 weight part, and (C) second-order transition temperature is the noncrystalline resin of more than 100 DEG C is 1.5-35 weight part.
3. polyphenyl thioether resin composition according to claim 1 and 2, is characterized in that: the flat ratio of (B) special crosssection glass fibre is more than or equal to 1.5.
4. polyphenyl thioether resin composition according to claim 1 and 2, is characterized in that: described polyphenyl thioether resin composition is at 315 DEG C of down cut speed 1000s
-1capillary rheometer melt viscosity lower than 180Pas.
5. polyphenyl thioether resin composition according to claim 1 and 2, is characterized in that: (C) second-order transition temperature is that the noncrystalline resin of more than 100 DEG C is selected from: one or more in polycarbonate, polyphenylene oxide, amorphous polyarylester, polysulfones, polyethersulfone, polyetherimide, polyamidoimide, polyimide or its multipolymer.
6. polyphenyl thioether resin composition according to claim 1 and 2, it is characterized in that: (C) second-order transition temperature is that the noncrystalline resin of more than 100 DEG C forms the dispersion of " island " shape in polyphenyl thioether resin composition, and the average area of these " island " shape things is less than 1 μm
2/.
7. the basket of portable computer, mobile phone, portable electronic appliance forms goods, it is characterized in that: use the polyphenyl thioether resin composition described in claim 1 or 2 to obtain.
8. the products formed obtained by the polyphenyl thioether resin composition described in claim 1 or 2.
9. products formed according to claim 8, is characterized in that: thin segment thickness is below 1.5mm.
10. the basket of the portable computer obtained by products formed according to claim 8, mobile phone, portable electronic appliance forms goods.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
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| CN201310371312.9A CN104650584A (en) | 2013-08-22 | 2013-08-22 | Polyphenylene sulfide resin composition and molded product thereof |
| CN201480032766.6A CN105377991B (en) | 2013-08-22 | 2014-08-05 | The manufacture method of polyphenyl thioether resin composition and its products formed and its products formed |
| US14/912,859 US10370522B2 (en) | 2013-08-22 | 2014-08-05 | Polyphenylene sulfide resin composition, and moulding and manufacturing process for moulding thereof |
| PCT/CN2014/083723 WO2015024439A1 (en) | 2013-08-22 | 2014-08-05 | Polyphenylene sulfide resin composition, and moulding and manufacturing process for moulding thereof |
| KR1020167005810A KR102157022B1 (en) | 2013-08-22 | 2014-08-05 | Polyphenylene sulfide resin composition, and moulding and manufacturing process for moulding thereof |
| JP2016535318A JP6394700B2 (en) | 2013-08-22 | 2014-08-05 | Polyphenylene sulfide resin composition, molded product thereof and method for producing the molded product |
| EP14837825.0A EP3037480B1 (en) | 2013-08-22 | 2014-08-05 | Polyphenylene sulfide resin composition, and moulding and manufacturing process for moulding thereof |
| TW103128609A TWI640575B (en) | 2013-08-22 | 2014-08-20 | Polyphenylene sulfide resin composition, molded articles therefrom and a method for manufacturing the molded articles |
| PH12016500344A PH12016500344A1 (en) | 2013-08-22 | 2016-02-19 | Polyphenylene sulfide resin composition, and moulding and manufacturing process for moulding thereof |
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| CN109233278A (en) * | 2018-08-16 | 2019-01-18 | 金发科技股份有限公司 | A kind of polyphenyl thioether composite material and preparation method thereof |
| CN109912973A (en) * | 2019-01-25 | 2019-06-21 | 深圳市高科塑化有限公司 | A kind of glass fiber reinforcement PPS-CNT conducing composite material and preparation method thereof |
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| CN115491034A (en) * | 2022-11-03 | 2022-12-20 | 南京真宸科技有限公司 | Rapid crystalline polyphenylene sulfide composite material and preparation method thereof |
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| US11118053B2 (en) | 2018-03-09 | 2021-09-14 | Ticona Llc | Polyaryletherketone/polyarylene sulfide composition |
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| CN109233278A (en) * | 2018-08-16 | 2019-01-18 | 金发科技股份有限公司 | A kind of polyphenyl thioether composite material and preparation method thereof |
| CN109912973A (en) * | 2019-01-25 | 2019-06-21 | 深圳市高科塑化有限公司 | A kind of glass fiber reinforcement PPS-CNT conducing composite material and preparation method thereof |
| CN111849162A (en) * | 2019-04-24 | 2020-10-30 | 旭化成株式会社 | Thin-walled component and container |
| CN112239602A (en) * | 2019-07-17 | 2021-01-19 | 财团法人纺织产业综合研究所 | Thermoplastic composition and process for producing the same |
| CN111117245A (en) * | 2019-12-19 | 2020-05-08 | 上海普利特伴泰材料科技有限公司 | Nano modified PPS plastic for pen power shell and preparation method thereof |
| CN112280302A (en) * | 2020-11-13 | 2021-01-29 | 苏州纳磐新材料科技有限公司 | Warp-resistant high-strength high-toughness PPS composite material and preparation method thereof |
| CN112280302B (en) * | 2020-11-13 | 2022-11-25 | 苏州纳磐新材料科技有限公司 | Warp-resistant high-strength high-toughness PPS composite material and preparation method thereof |
| CN115491034A (en) * | 2022-11-03 | 2022-12-20 | 南京真宸科技有限公司 | Rapid crystalline polyphenylene sulfide composite material and preparation method thereof |
| CN116285352A (en) * | 2023-03-15 | 2023-06-23 | 青岛中宝塑业有限公司 | High-performance modified PPS plastic, preparation method and application thereof |
| CN116285352B (en) * | 2023-03-15 | 2023-12-19 | 青岛中宝塑业有限公司 | High-performance modified PPS plastic, preparation method and application thereof |
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