CN1048268C - Rubber-modified polystyrene resin compounds - Google Patents
Rubber-modified polystyrene resin compounds Download PDFInfo
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- CN1048268C CN1048268C CN95118216A CN95118216A CN1048268C CN 1048268 C CN1048268 C CN 1048268C CN 95118216 A CN95118216 A CN 95118216A CN 95118216 A CN95118216 A CN 95118216A CN 1048268 C CN1048268 C CN 1048268C
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Abstract
The present invention relates to a styrene series resin composition with high ball falling impact strength, glossiness and tensile strength without odour of formed products, which is modified by rubber. The residual quantity of styrene series monomers in the composition is below 1500 ppm, and the residual quantity of butadiene dimer is below 150 ppm. The average particle diameters of a rubber quantity in resins are from 0.08 to 0.35 mu m, wherein the rubber particles of which the particle diameters are below 0.1 mu m, from 0.1 to 0.25 mu m and above 0.25 mu m respectively account for 19.5 to 99, 0.5 to 60 and 0.5 to 80 of the total of the rubber particles by quantity percentage.
Description
The present invention is relevant a kind of rubber-modified styrene resin composite, is meant that especially a kind of composition that makes has the resin combination of excellent ball falling impact intensity, high-tensile, good gloss degree, the no stink of moulding product.
The personage who is familiar with this technical field knows that all styrene resin composite is to be dispersed in the matrix of styrene based copolymer with rubber like graft copolymer, made a kind of impact resistant resin composition.On using, family's shell of electrical article and this used resinous materials of automobile moulding must possess shock-resistant and characteristic such as high gloss simultaneously, and ABS resin is exactly the typical representative styrene resin composite material that can meet above-mentioned requirements, so be widely adopted for many years.
But, the common shock-resistance high resin of healing, tensile strength and glossiness are lower; Opposite, tensile strength and the glossiness high resin of healing, shock-resistance is just relatively poor; This is because the shock-resistance of resin, tensile strength and glossiness are simultaneously relevant with rubber content or rubber size in the resin.From in the past research as can be known, heal height or rubber size of the rubber content in resin is bigger, and shock-resistance is just better; Rubber content in resin heal low or rubber size littler, tensile strength and glossiness are just higher.Therefore, how to make the resin combination that different rubber sizes distribute, and possesses the resin material of impact strength, high-tensile and good gloss degree simultaneously, it is problem for having studied since a good while, nearest again ejection formation industry is on producing, based on the position that the beyond the region of objective existence that reduces cost and pay attention to being shaped is seen, the tendency that forming temperature is significantly increased.
General phenylethylene resin series in the past is in the course of processing of high temperature ejection formation or extrusion moulding, the moulding product can produce stink, above-mentioned stink source is general suspects it is because styrene resin adds mercaptan (mercatan) and produces as molecular weight regulator in polymerization process, because of the mercaptan tool hangs down boiling characteristics, remains in the resin easily; In order to improve aforementioned disappearance, once mentioned in No. 3951932 patent case of U.S.'s patent of invention, with tert-butyl mercaptan (tertiary butyl mercaptan) as molecular weight regulator, and remove residual mercaptan with coupling vacuum stripping, can reduce in the styrene resin processing and the stink on the forming composition, but its improved effect is unsatisfactory, though in the manufacturing of phenylethylene resin series, the residual of comfortable molecular weight regulator do not come in the source of stink completely.
Because in the known technology, when making the thermoplastic styrene resin, be difficult for obtaining simultaneously good ball falling impact intensity, high-tensile, high glossiness, with can't improve the shortcoming that the moulding product can produce stink when the moulding, be to concentrate on studies to develop a kind of resin combination of novelty, to improve aforementioned disappearance.
For this reason, the present invention seeks to provide a kind of have good ball falling impact intensity, high-tensile, high gloss intensity, no stink moulding product (be meant odorless not or stink considerably less, below also with) rubber-modified styrene resin composite.
Feature of the present invention is: rubber-modified styrene resin composite system comprises by acrylic monomer and/or methacrylate ester monomer, styrenic monomers, optionally can add the matrix phase of the vinylbenzene one propenyl based copolymer that other copolymerizable unsaturated ethylene alkene monomers are constituted and be dispersed in butadiene-based rubber particle in this matrix; In resin combination, the styrenic monomers residual quantity is below 1500ppm, and the butadiene dimer residual quantity is below 150ppm, and this butadiene-based dipolymer is a 4-vinyl cyclohexene; And the rubber quantity average particle diameter in the resin combination is at 0.08～0.35 μ m, wherein, the rubber particles of particle diameter below 0.1 μ m accounts for rubber particles sum 19.5～99 quantity per-cents, particle diameter accounts for rubber sum 0.5～60 quantity per-cent at the rubber particles of 0.1 μ m～0.25 μ m, and the above rubber particles of particle diameter 0.25 μ m accounts for rubber sum 0.5～80 quantity per-cent.
The matrix of styrene resin composite of the present invention is styrene-propene base system multipolymer, it is by styrenic monomers 50～90wt%, acrylic monomer and/or the monomeric propylene base system of methacrylate ester monomer 10～50wt%, 0～40wt% constitutes with other copolymerizable monomer, its molecular-weight average is 40, between 000 to 300,000, be preferably 60, between 00 to 250,000; Wherein:
Styrenic monomers can be: vinylbenzene, alpha-methyl styrene, α-chloro-styrene, p-trimethylphenylmethane ethene, p-vinyl toluene, o-chloro-styrene, p-chloro-styrene, 2,5-dichlorostyrene, 3,4-dichlorostyrene, 2,4,6-tribromo-benzene ethene and 2,5-Dowspray 9, Vinylstyrene etc., wherein comparatively preferred with vinylbenzene or alpha-methyl styrene.
The acrylic monomer can be: vinyl cyanide, methacrylonitrile, and wherein preferable with vinyl cyanide; (methyl) acrylic ester monomer then can be: (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) vinylformic acid benzene methyl, (methyl) Ethyl acrylate, (methyl) cyclohexyl acrylate, (methyl) dodecyl acrylate, (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) glycidyl acrylate, γ-(methyl) vinylformic acid-hydroxypropyl-Trimethoxy silane (γ-methacryl hydroxypropyl tri-methoxy silane), (methyl) dimethylaminoethyl acrylate etc., wherein preferable with methyl methacrylate.
The aforesaid propylene nitrile is monomer and the monomeric usage ratio of (methyl) acrylic ester and without particular limitation, if pay attention to the shock strength and the oil-proofness of resin, the vinyl cyanide usage quantity is bigger, if pay attention to the surface hardness and the light transmission of resin, (methyl) acrylic ester monomer, particularly the consumption of methyl methacrylate is bigger, should look the requirement of rerum natura and use respectively.
Suitable copolymerizable monomer comprises that maleimide is a monomer, for example: maleimide, N-methyl maleimide, N-sec.-propyl maleimide, the N-butyl maleimide, the basic maleimide of N-, N-octyl group maleimide, N-dodecyl maleimide, N-cyclohexyl maleimide, N-phenylmaleimide, N-2,3-tolyl maleimide, N-2,4-tolyl maleimide, N-2,3-ethylbenzene base maleimide, N-2,4-ethylbenzene base maleimide, N-2,3-butylbenzene base maleimide, N-2,4-butylbenzene base maleimide, N-2,6-tolyl maleimide, N-2,3-chloro-phenyl-maleimide, N-2,4-chloro-phenyl-maleimide, N-2,3-bromophenyl Malaysia imide, N-2,4-bromophenyl Malaysia imide.
Other copolymerizable monomer still have: (methyl) acrylic monomer, Maleic Acid, Anhydrous, anhydrous methyne Succinic Acid, anhydrous methyl-maleic acid, the unsaturated carboxylic acid based compound and the ester thereof of anhydrous neocerotic acid are monomer, ethene, propylene, 1-butylene, the 1-amylene, 4-methyl-1-pentene, ethylene chloride, vinylidene chloride, tetrafluoroethylene again, one chlorine three is fluoridized ethene, the hexafluoro propylene, divinyl, propenyl amine, isobutenyl amine, vinyl acetate between to for plastic, ethyl-vinyl ether, methyl-vinyl ketone etc.
The butadiene-based rubber particle that is dispersed in the styrene-propene base system copolymer matrix is a rubber like graft copolymer, and above-mentioned butadiene-based rubber is by: 1,3-butadiene 100～50wt% and has CH
2Copolymerizable monomer 0～the 50wt% of=C＜base constitutes; Divinyl-the aromatic vinyl copolymer of polyhutadiene, butadiene-styrene, divinyl-vinyl toluene copolymer and so on for example, the divinyl of perbutan, divinyl-methacrylonitrile copolymers and so on-unsaturated nitrile based compound multipolymer; The butadiene-acrylic acid alkyl ester copolymer of butadiene-acrylic acid methyl terpolymer, butadiene-acrylic acid ethyl ester multipolymer, butadiene-acrylic acid butyl ester multipolymer, divinyl-2-ethyl acrylate copolymer and so on; The divinyl of divinyl-methylmethacrylate copolymer, divinyl-ethyl methacrylate copolymers and so on-alkyl methacrylate multipolymer etc. and the terpolymer of butadiene content more than 50 weight %.
Aforementioned butadiene-based rubber can prepare by emulsion polymerization method, the rubber latex that monomer directly can be synthesized 0.05～0.35 μ m during preparation with emulsion polymerization method, when the particle diameter of rubber latex during greater than 0.35 μ m, the problem that the meeting frowziness is not easy to remove produces, after also monomer can being made the small particle size rubber latex of 0.05～0.20 μ m with emulsion polymerization method, again with freezing loose method or mechanical loose method or the loose method of additive with the loose rubber latex that becomes 0.22～0.35 μ m of above-mentioned small particle size rubber, in order to further carrying out graft copolymerization.Wherein, employed additive can be in the loose method of additive: acidic substance such as acetic anhydride, hydrogenchloride, sulfuric acid, or: salt-base substances such as sodium-chlor, Repone K, calcium chloride, magnesium chloride, sal epsom, and metha crylic-acrylic copolymer (as: methacrylic acid-butyl acrylate copolymer) etc. contains the acidic group polymer coagulant.
The preparation of butadiene-based rubber emulsion of the present invention.Can be by the change of emulsifying agent addition manner, temperature of reaction, speed of reaction and monomer conversion, make the rubber latex of the size distribution of wanting, need not use loose method especially, but in order to reduce the content of contained butadiene dimer in the butadiene-based rubber emulsion, the alleged butadiene dimer system of the present invention specially refers to 4 vinyl cyclohexene (4-vinyl cyclohexene), after stripping (stripping) is handled, in the effect that removes butadiene dimer better performance is arranged with the rubber latex of hypertrophy manufacturing than rubber latex without the hypertrophy method.
Employed divinyl of polymerization butadiene-based rubber and copolymerizable monomer, can adopt once add, mode such as interpolation in batches or continuously, wherein can more effectively remove butadiene dimer with continuous interpolation again.
Above-mentioned rubber-like polymer can be partial cross-linked, the addition of its linking agent is with respect to the polymeric 0～2wt% of rubber, the linking agent that is fit to has: divinylbenzene (Divinyl benzene), diallyl maleate ester (Diallyl maleate), diallyl fumarate (Diallyl fumarate), diallyl acetic ester (Dially acetate), allyl acrylate (allyl acrylate), glycol dimethacrylate (tetra ethylene glycol dimethacrylae) etc., the glue containing ratio of aforementioned butadiene-based rubber emulsion is without particular limitation, usually at 30～90% optimums, and be the best with 20～60 with benzene in the glue swelling capacity that is solvent.
This rubber like graft copolymer is by butadiene-based rubber and styrenic monomers 50～90w t%, acrylic monomer and/or methacrylate ester monomer 10～50wt% again, carrying out graft polymerization with other copolymerizable monomer 0～40wt% forms, the preparation of graft copolymer is normally in the presence of the rubber-like polymer, carry out the grafting rubbers polyreaction with monomer mixture, utilize the combination of chemical or at least a styrene-propene base system of grafting multipolymer on the rubber-like polymer; Factors such as the speed that the polymeric ratio of above-mentioned monomer and rubber-like, polymerizing condition, the polymeric chemical property of rubber-like, size of particles, monomer add, chain transfer agent all can influence its grafted degree; The manufacture method of rubber graft copolymer of the present invention can adopt emulsion polymerization method, the block polymerization of emulsification, emulsification suspension polymerization etc., is good with emulsion polymerization method wherein.
The initiator that aforementioned graft polymerization reaction added usually in the scope of 0.01～5.0 weight % of polymerisable monomer, is preferably between 0.1～3.0 weight %; Its addition according to monomer and institute must polyreaction and decide, graft polymerization reaction is easier to carry out in order to make, but aforementioned initiator increment adding; The molecular weight size of graft copolymer again, temperature in the time of can be by graft reaction is controlled, perhaps cooperate the molecular weight regulator of commonly using on a small quantity, can also merge temperature control and molecular weight regulator controls, above-mentioned molecular weight regulator can be mercaptan, fontanelle compound and terpenes etc., its comparatively concrete example has: just-and lauryl mercaptan, the 3rd (dodecyl) mercaptan, carbon tetrabromide, anthracene terpinolene, α-Jia Jibenyixierjuwu, and 2,4-phenylbenzene-4-methyl-1-pentene etc.
Graft polymerization reaction of the present invention can utilize monomer mixture to add in the polyreaction with continuous or increment ground, preferably simultaneously continuously or the adding initiator of increment; Aforementioned initiator can use various known emulsification Raolical polymerizable initiators, and for example: superoxide (peroxy) and azo-compound, its addition manner can adopt once and to add or continuously or increment ground adding etc.; Suitable superoxide initiator is for example: alkali metal peroxide, persulphate, perborate, peracetate, percarbonate, hydrogen peroxide etc.; In addition, also can use the oil soluble initiator, for example: ditertiary butyl peroxide (di-tert-butyl-peroxide), dibenzoyl superoxide (benzoyl peroxide), lauroyl superoxide (lauroyl peroxide), octadecanoyl superoxide (oleylperoxide), hydrogen phosphide cumene (cumene hydroperoxide), tertbutyl peroxide (tert-butyl hydroperoxide); In addition, there is the free radical catalyst of other modes also can be used, for example: actinic radiation.
The graft polymerization reaction of aforementioned rubber latex and monomer mixture is to stir under 20～100 ℃, rare gas element, also can be pressurized to 0～100 P.S.I.G., and polymerization time needs 2～10 hours usually, and is good with 4～9 hours.
This case contriver studies the result in great detail, usually rubber-modified phenylethylene resin series is when higher mold temperature and shaping speed, styrenic monomers and butadiene dimer are free easily, and the gasification rate of the contained residual benzene vinyl monomer of rubber-modified phenylethylene resin series increases, volatilization has the effect that multiplies each other in the time of to butadiene dimer, and the stink on ejection formation or the moulding product should come from this by inference.
For obtaining the good manufacture method of resin combination of the present invention, it is the stripping that in proper temperature and vacuum, carries out the graftomer emulsion, or condense with high-temperature water vapor, also can adopt high-temperature water vapor under the decompression situation, to carry out stripping, to reduce part residual benzene vinyl monomer and butadiene dimer, washing with the graftomer high-temperature water after above the condensing, and it is dry under vacuum, the water content of common dry thing is controlled at below 3%, and with below 1% for good: another preferable mode is without vacuum drying treatment, graftomer after will condensing is after water washing, dewater to water-content below 40% with centrifugal drier, with forcing machine moisture content is removed again, add the fusion of styrene-propene base system multipolymer simultaneously and mix and extrude.
According to the present invention, wish to get the rubber-modified styrene resin composite that odorless comes, its residual styrenic monomers is below 1500ppm, and residual butadiene dimer is below 150ppm, be preferably styrenic monomers below 850ppm, butadiene dimer is below 100ppm.
When the rubber particles in the polymkeric substance is small-particle, be easier to reduce the amount of butadiene dimer, so among the present invention, the rubber particles that is dispersed in the matrix is on the high side with small-particle, the size distribution of rubber particles is that the rubber particles of particle diameter below 0.1 μ m accounts for rubber particles sum 19.5～99 quantity per-cents, is preferable with 50～98 quantity per-cents especially; And the rubber particles of particle diameter 0.1～0.25 μ m accounts for 0.5～60 quantity per-cent of rubber particles sum, is preferable with 1～40 quantity per-cent especially; The above rubber particles of particle diameter 0.25 μ m accounts for 0.5～80 quantity per-cent of rubber particles sum, is preferable with 1～70 quantity per-cent especially; When the quantity per-cent of these size distribution was beyond aforementioned range, the ball falling impact intensity of resin and the balance of glossiness were not good; Between 0.08～0.35 μ m, and is good with 0.09～0.14 μ m according to rubber quantity average particle diameter of the present invention, and when average rubber particle size during less than 0.08 μ m, ball falling impact intensity is not good; Otherwise average rubber particle size surpasses at 0.35 o'clock, and the glossiness of moulding product is not good, and anti-Zhang Du is variation also.
Particularly, it is with resin combination that the present invention puies forward rubber quantity median size, with perosmic anhydride (OsO
4) dye after after the section, show the emblem mirror with penetration (TEM) electronics and take a picture that to obtain enlargement ratio be that 50000 times electronics shows emblem mirror photograph, measuring the rubber grain on 12 centimeters * 12 centimeters area calculates, the branch rate fi algorithm of particle diameter di particle: (∑ fi di)/∑ fi, the mensuration of each rubber size is benchmark with particle (maximum diameter length+minimum diameter length)/2.
Size distribution of the present invention is with resin slicer, and take a picture with aforesaid method, show emblem mirror magnification on the photograph of 25000 times (rubber particles is more than 2000) at the infiltration type electronics, obtain the different-size particles number respectively, the population of particle diameter below 0.1 μ m is n
1, the population between particle diameter 0.1～0.25 μ m is n
2, the above population of particle diameter 0.25 μ m is n
3, N=n
1+ n
2+ n
3The time, then the following population size distribution of 0.1 μ m is (n
1/ N) * 100 (represent, below also with) with %, the grain that 0.1～0.25 μ m is above directly to distribute be (n
2/ N) * 100,0.25 the above size distribution of μ m is (n
3/ N) * 100.
The rubber composition accounts for 15～80 weight % in the rubber like graft copolymer used herein, with 45～75 weight % is good, and the ratio that is grafted on the styrene-propene base system multipolymer on the rubber is exactly a percentage of grafting, with rubber weight be benchmark at 20～150 weight %, be good with 25～80 weight % especially; In order to adjust the benzene mixed ethylene-propylene base system multipolymer that rubber content in the resin combination of the present invention should be optionally suitable.
In rubber like graft copolymer and styrene-propene base system multipolymer blended mixture, the ratio of rubber composition is at 2～50 weight %, with 7～35 weight % is good, especially with 10～25 weight % for better, when the rubber composition ratio in the rubber like graft copolymer is in this scope, the ratio of mixture of styrene-propene base system multipolymer can be 0%, does not use also passable.
The styrene-propene base system multipolymer that forms matrix be form on the rubber graft copolymer unbound state not graft phenylethene-propenyl based copolymer and aforementioned be to adjust rubber content blended styrene-propene base system multipolymer.
When the polymkeric substance fusion, in order to reduce the residual quantity of styrenic monomers and butadiene dimer simultaneously, more concrete mode is to use the forcing machine with a plurality of degassing mouths, shift out residual vinyl aromatic monomers and butadiene dimer by the method for notch portion that outgas again with reduced vacuum, preferable mode is to adopt the forcing machine with degassing mouth more than 2, and gas clean-up is removed the effect of volatile matter with increase; Again extrude add when mixing entry or just-hexane, just-volatile organic solvents such as octane, can strengthen removing styrenic monomers and butadiene dimer; Add fashionablely at water or volatile organic solvent,, can strengthen the effusion of aforementioned volatile matter by the boiling characteristics of water or solvent; Generally speaking, relatively at the resin combination of 100 weight parts, the addition of this water or organic solvent is between 0.1～15 weight part, especially being good between 0.5～10 weight part.
The method of adding devolatilization auxiliary agents such as aforementioned water or organic solvent can be when the resin fusion, in the forcing machine fusion process of mixing, by the cylinder feeding end (loading hopper) of forcing machine and the inlet between the degassing mouth, perhaps the inlet between two degassing mouths is pressed into interpolation, and selected extrusion condition is easily to remove volatile matter.
In the resin combination of the present invention in order to reduce the residual quantity of styrenic monomers and butadiene-based dipolymer, can following record means for it, the selection of the relevant size distribution in the loose chemical industry journey of the butadiene-based rubber particle during as the polymerization stage of butadiene-based rubber grain, post-processing stages, graft polymerization, what of devolatilization auxiliary agent the ridity of graft copolymer, forcing machine add, the vacuum outgas mouth is provided with what, can adopt a plurality of suitable means to cooperate during enforcement and reach desired result of the present invention.
Rubber-modified styrene resin composite of the present invention can add the material that uses other according to need, for example: antioxidant, plasticizer, processing aid, lubrication prescription, UV light absorber, ultraviolet tranquilizer, charged preventor, weighting agent, reinforcer, tinting material, incombustible agent, difficult combustion auxiliary agent, thermal stabilizer, coupler or other additives etc., above-mentioned additive can be after polyreaction, polyreactions, condense preceding or extrude in the process of mixing and add.
It is that antioxidant, thioether are materials such as antioxidant, phosphorous antioxidant, chela agent that antioxidant should use usually as phenol; Is good and phenol is the addition of antioxidant with 0.005～2.0 weight %, representative person has: octadecyl (3,5-di-t-butyl-4-hydroxyphenyl) propionic ester, triethylene glycol two (3-(the 3-tertiary butyl-5-methyl-4-hydroxyphenyl) propionic ester), (3-(3 for five moss alcohol four, 5-di-t-butyl-4-hydroxyphenyl) propionic ester), the 2-tertiary butyl-6-(the 3-tertiary butyl-2-hydroxyl-6-methylbenzene methyl)-4-aminomethyl phenyl acrylate, 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol) and 2,2 '-sulphur two (4-methyl-6-tert butyl phenol), 2,2 '-sulfo--diethylene base-two (3 (3,5-dual-tert-butyl-4-hydroxyl-phenyl) propionic ester), 2,2 '-oxalamide-two (ethyl-3-(3,5-di-t-butyl-4-hydroxyl-phenyl) propionic ester) etc.
Thioether is that the addition of antioxidant is good with 0.005～2.0 weight %, and representative person has: distearyl thiodipropionic acid ester, two palmityl thiodipropionic acid esters, alcohol-four-(β-ten dimethyl-sulphur propionic ester), two octadecyl thioethers etc.
Phosphorous antioxidant is that phosphorous acid ester is antioxidant or phosphoric acid ester antioxidant, its addition is good with 0.015～2.0 weight %, representative person has: three (nonyl phenyl) phosphorous acid ester, dodecyl phosphorous acid ester, ring-type neopentane tetralyl two (octadecyl phosphorous acid ester), 4,4 '-butylidene two (3-methyl-6-tert butyl phenyl-double tridecyl phosphorous acid ester), three (2, the 4-tert-butyl-phenyl) phosphorous acid ester or four (2, the 4-tert-butyl-phenyl)-4,4 '-stretch xenyl phosphoric acid ester, 9,10-dihydro-9-oxy-10-phosphoric acid phenanthrene-10-oxygen support etc.
The addition of chela agent is good with 0.001～2.0 weight %, and representative person has: the sodium salt of phenyl phenacyl ketone, diethylamine four acetic acid etc.
The addition of aforementioned antioxidant is generally at rubber-modified styrene resin composite relatively and adds up to 0.03～2.0 weight %.
Lubrication prescription representative person have: the compound of the metallic soaps of calcium stearate, Magnesium Stearate, lithium stearate etc., ethylene distearyl acid amides, methylene distearyl acid amides, palmitic amide, butyl stearate, stearic acid palm ester, poly-propionic acid alcohol tristearate, behenic acid, stearic acid etc., polyethylene wax, carnauba wax (Carnuba wax), petroleum wax etc.; The addition of lubrication prescription is with respect to 0.03～5.0 weight % of the common total of rubber modified styrene resin composite.In order to improve extrusion moulding, hot formability, also can add processing aid again as methyl methacrylate system; UV light absorber is representative to be had: benzotriazole based compound, benzophenone based compound, and ultraviolet tranquilizer representative person have: the retardance amine compound; The addition of aforementioned substances is with respect to the rubber modified styrene resin composite of the present invention 0.02～2.0 weight % of total amount usually.
Charged preventor representative person have: the low molecule based compound of tertiary amine based compound, quaternary ammonium salt based compound etc., or the polymeric amide polyethers, as the macromolecular material of polymeric permanent charged the preventing property of epichlorohydrin.
Weighting agent representative person have: lime carbonate, tripoli, mica.
Reinforcer representative person have: glass fibre, carbon fiber, various brilliant silk (whisker) class.
Tinting material representative person have: titanium oxide, ferric oxide, graphite, phthalocyanine pigment.
Incombustible agent or the representative person of difficult combustion auxiliary agent have: decabrominated dipheny base ether, tetrabromo-bisphenol, brominated Polystyrene oligomerization zoarium, brominated epoxy resin, hexabromocyclododecane, chlorinatedpolyethylene, triphenyl phosphoric acid, red phosphorus, weisspiessglanz, aluminium hydroxide, magnesium hydroxide, zinc borate, trimeric cyanamide, isocyanide amine salt, silica powder, polytetrafluorethylepowder powder, expansile graphite etc.
Thermal stabilizer representative person have: dibutyl tin maleate, alkali magnalium hydroxyl carbonate etc.; Again, thermo-color prevents that agent from can be low-molecular-weight vinylbenzene-Maleic Acid, Anhydrous multipolymer, and its addition is with respect to rubber modified styrene resin composite of the present invention, usually 0.1～1.0 weight % of total amount.
Coupler representative person have: silane system, phthalate, germanic acid ester based compound.
In styrene resin composite of the present invention for upgrading, can suitably use the additive of polymerization system, for example block polymerization, solution polymerization process, block outstanding turbid polymerization etc., just can adopt emulsion polymerization method mode in addition to make, rubber-modified phenylethylene resin series, acrylonitrile-butadiene-styrene resin for example, use butadiene-based rubber rubber such as EPDM in addition, butyl acrylate rubber comes the AES resin of upgrading, phenylethylene resin series such as AAS resin, Maleic Acid, Anhydrous-styrol copolymer, vinylbenzene-maleimide copolymer, the maleimide amine content surpasses styrene-acrylonitrile-Maleic Acid, Anhydrous multipolymer of 40 weight %, come the styrene-acrylonitrile-Maleic Acid, Anhydrous multipolymer of imidization with aniline, there are not grafted bridge formation rubber such as acrylonitrile-butadiene rubber, ethylene chloride resin, polymethylmethacrylate, polycarbonate resin, polyamide resin, poly-terephthalic acid butene esters, the polystyrene thermoplastic elastomer, various phase solvations etc., 3～200 weight parts of the styrene resin composite that its usage quantity is rubber modified with respect to 100 weight part the present invention.
Below enumerate embodiment the present invention is described, but scope of the present invention is not exceeded with these embodiment.＜Production Example〉(I-1) manufacturing of butadiene-based rubber emulsion (A1):
Following raw materials according is inserted in the reactive tank with whipping appts, heating unit and material feeding tube.
The composition weight part
Divinyl 100.0
Three-lauryl mercaptan 0.2
Pyrophosphate salt 3.0
Potassium oleate 1.5
Potassium Persulphate 0.3
Deionized water 140.0
45 ℃ of beginnings, along with the increase of transformation efficiency, temperature of reaction also edges up and high reaches 50 hours up to reaction behind the pan feeding; The prepared rubber latex transformation efficiency in reaction back is more than 90%, and the unreacted divinyl was removed with steam distillation after polymerization ended, and the solid in the latex is 41%, and the rubber quantity median size in the emulsion is 0.14 μ m, is designated hereinafter simply as A1.(I-2) manufacturing of butadiene-based rubber emulsion (A2) "
Following raw materials according is inserted with stirring in the reactive tank that blocks device, heating unit and material feeding tube.
The composition weight part
Divinyl 93.0
Vinylbenzene 7.0
31 lauryl mercaptans 0.2
Pyrophosphate salt 3.0
Potassium oleate 1.5
Potassium Persulphate 0.15
Deionized water 140.0
React at 70 ℃ behind the pan feeding, continue after 12 hours, make its cooling just can reach the reaction termination; The prepared rubber latex transformation efficiency in reaction back is more than 92%, and the unreacted divinyl was removed with steam distillation after polymerization ended, and the solid content in the latex is 40%, and the rubber quantity median size in the emulsion is 0.06 μ m, is designated hereinafter simply as A2.(I-3) manufacturing of butadiene-based rubber emulsion (A3):
Formula ratio as (I-2), total monomer amount with 20% and 20% potassium oleate, persulfate aqueous solution, react with the while addition manner, all the other 80% total monomer amounts and 80% potassium oleate, persulfate aqueous solution, with continuous 5 hours addition manners and 65 ℃ carry out 9 hours after, make its cooling just can reach the reaction termination, the prepared rubber latex transformation efficiency in reaction back is more than 85%, the unreacted divinyl was removed with steam distillation after polymerization ended, solid amount in the latex is 39%, rubber quantity median size in the emulsion is 0.07 μ m, is designated hereinafter simply as A3.
What (II) the tool hypertrophy turned usefulness into contains the synthetic of acidic group copolymer emulsion; Its composition such as following cited person.
The composition weight part
N-ethyl propenoate 85.0
Vinylformic acid 15.0
Three-lauryl mercaptan 0.3
Potassium oleate 2.0
Dioctyl sodium sulphosuccinate 1.0
Hydrogen phosphide cumene 0.4
Sodium formaldehyde sulphoxylate 0.3
Water 200.0
Aforementioned composition is seated in the poly-unit,, just can makes: transformation efficiency more than 98%, pH value 6.1, quantity median size 0.07 μ m latex with 70 ℃ of polymerizations four hours.(III-1) manufacturing of enlarged rubber emulsion (C1):
In butadiene-based rubber emulsion (A2) dry weight is in 100 weight parts, while stir, add with five seconds, acidic group copolymer emulsion (II) dry weight that contains that the tool hypertrophy turns usefulness into is 1.5 weight parts and inorganic electrolyte Na
2SO
4, continuously stirring 30 minutes just can make: the enlarged rubber emulsion of quantity median size 0.38 μ m, and hereinafter to be referred as C1.(III-2) manufacturing of enlarged rubber emulsion (C2):
In butadiene-based rubber emulsion (A2) dry weight is in 100 weight parts, while stir, add with five seconds, acidic group copolymer emulsion (II) dry weight that contains that the tool hypertrophy turns usefulness into is 1.8 weight parts and inorganic electrolyte Na
2SO
4, continuously stirring 30 minutes just can make: the enlarged rubber emulsion of quantity median size 0.45 μ m, and hereinafter to be referred as C2.(III-3) manufacturing of enlarged rubber emulsion (C3):
In butadiene-based rubber emulsion (A3) dry weight is in 100 weight parts, takes the hypertrophy processing identical with (III-2), can get the enlarged rubber emulsion of quantity median size 0.43 μ m, hereinafter to be referred as C3.
The manufacturing of " embodiment 1 " (one) graft copolymer:
In with the reactor after the nitrogen displacement, butadiene-based rubber emulsion (A1) 100 weight parts (dry weight) of adding shown in subordinate list one, chain-transfer agent three-lauryl mercaptan (TDM) 0.2 weight part shown in subordinate list one, with hydrogen phosphide cumene 0.32 weight part, sodium formaldehyde sulfoxylate 0.2 weight part, potassium oleate 2 weight parts, water 200 weight parts, after the interpolation vinylbenzene 70 weight parts and vinyl cyanide 30 weight parts are mixed back adding continuously, under 60 ℃ of temperature of reaction, carry out 8.5 hours graft polymerization reaction, can get the graft copolymer of transformation efficiency 94%, the size distribution of rubber and quantity median size are shown in subordinate list two.(2) manufacturing of resin combination:
Aqueous sulfuric acid with 5% adds in the above-mentioned graft copolymer emulsion, and stirring is after 10 minutes down at 90 ℃, and the curding out slurries are with 112 ℃, 4kg/cm
2Water vapor stripping after 60 minutes, again after the hot water washing of dehydration and 80 ℃, and after 1 hour, obtain the graft copolymer powder at 80 ℃, 120Torr drying; (it forms weight ratio: vinyl cyanide/benzene alkene=30/70 with the styrene-acrylonitrile resin of aforementioned graft copolymer more afterwards, molecular weight is 12,000) with respect to 2 of the resin combination of 100wt%, 6-two-tertiary butyl-4-sylvan (0.1wt%), three (nonyl phenyl) phosphorous acid ester (0.1wt%), ethene bis-stearamides (2.0wt%) etc., mix into the mixture of total rubber content 19wt% with above-mentioned graft copolymer powder mixes, with Werner ﹠amp made in Germany; Pfleiderer ZSK-35 type biaxial extruder is extruded under 240 ℃, and the vacuum tightness of forcing machine first degassing mouthful (V1) and second degassing mouthful (V2) is respectively 150Torr and 60Torr, and take off between mouthful (V1) at feeding mouth and first, with first and second degassing mouthful (V1, V2) inlet between, contained as subordinate list three respectively, add devolatilization auxiliary agent normal hexane, add-on is respectively with respect to 2.5 weight parts of 100 parts by weight resin compositions and 1.8 weight parts.
" embodiment 2～7 "
Use the same treatment mode with embodiment 1, different persons are to use various different graft copolymers or its mixture shown in subordinate list two, and above-mentioned each graft copolymer and title, consumption are stated from subordinate list one first hurdle; Its graft copolymer the condense subsequent disposal such as the subordinate list three of slurries are adjusted different stripping, drying and extrusion condition and are obtained final resin combination.
" embodiment 8 "
(1) graft copolymer manufacturing:
In with the reactor after the nitrogen displacement, add butadiene-based rubber emulsion (A1) 200 weight parts (dry weight), chain-transfer agent α-Jia Jibenyixierjuwu 0.2 weight part, tertbutyl peroxide 0.32 weight part, sodium formaldehyde sulfoxylate 0.2 weight part, potassium oleate 2 weight parts, in the water 200 weight part injecting reactors, after the interpolation vinylbenzene 70 weight parts and vinyl cyanide 30 weight parts are mixed back adding continuously, under 60 ℃, carry out 8.5 hours graft polymerization reaction, can get the graft copolymer of transformation efficiency 93.6%, and the quantity median size of rubber is 0.14 μ m, and its size distribution is to account for 62.4% below the 0.1 μ m, 0.1～0.25 μ m accounts for 32.4%, 0.25 account for 5.2% more than the μ m.(2) manufacturing of resin combination:
5% aqueous sulfuric acid is added in the above graft copolymer emulsion, and 90 ℃ stir 10 minutes down after the curding out slurries, after the water of dehydration and 40 ℃ is washed, obtain the graft copolymer powder of water ratio 31.2% again; (it forms weight ratio: vinyl cyanide/vinylbenzene/N-phenylmaleimide=22/70/8 with styrene-acrylonitrile-N-phenylmaleimide multipolymer afterwards, molecular weight is 108,000) with 2 of relative resin combination at 100wt%, 6-two-tertiary butyl-4-sylvan (0.1wt%), three (nonyl phenyl) phosphorous acid esters (0.1wt%), ethene bis-stearamides (2.0wt%) etc., mix into the mixture of total rubber content 19wt% with above-mentioned graft copolymer powder mixes, biaxial extruder with day system Toshiba TEM-35 type is extruded under 240 ℃, (V1, vacuum tightness V2) is respectively 90Torr and 20Torr to first and second degassing mouth.
The manufacturing of " embodiment 9 " (one) graft copolymer:
In the presence of nitrogen, add butadiene-based rubber emulsion (A1) 200 weight parts (dry weight), chain-transfer agent TDM0.2 weight part, tertbutyl peroxide 0.32 weight part, sodium formaldehyde sulfoxylate 0.2 weight part, potassium oleate 2 weight parts, water 200 weight parts, after the interpolation vinylbenzene 70 weight parts and vinyl cyanide 30 weight parts are mixed back adding continuously, under 40 ℃ of temperature of reaction, carry out 8.5 hours graft polymerization reaction, can get the graft copolymer of transformation efficiency 94.2%, the quantity median size of rubber particles is 0.14 μ m, and its size distribution is to account for 62.3% below the 0.1 μ m, 0.1～0.25 μ m accounts for 32.4%, 0.25 account for 5.3% more than the μ m.(2) manufacturing of resin combination:
5% aqueous sulfuric acid is added in the above graft copolymer emulsion, and 90 ℃ stir 10 minutes down after the curding out slurries with 112 ℃, 4kg/cm
2Water vapor stripping after 90 minutes, after the dehydration washing, obtain the graft copolymer powder of water ratio 29.8% again; (it forms weight ratio: vinyl cyanide/vinylbenzene=30/70 with styrene-acrylonitrile resin afterwards, molecular weight is 120,000) with 2 of relative resin combination at 100wt%, 6-two-tertiary butyl-4-sylvan (0.1wt%), three (nonyl phenyl) phosphorous acid esters (0.1wt%), ethene bis-stearamides (2.0wt%) etc., mix into the mixture of total rubber content 19wt% with above-mentioned graft copolymer powder mixes: the biaxial extruder with day system ToshibaTEM-35 type is extruded under 240 ℃, first and second degassing mouthful (V1, V2) vacuum tightness is respectively 150Torr and 60Torr, and at feeding mouth, inlet between V1 and the V2 (two degassing mouthful), be pressed into respectively addition with respect to resin combination 100 weight parts just-hexane 2.5 weight parts and 1.8 weight parts.
" embodiment 10 "
(1) manufacturing of graft copolymer:
In the presence of nitrogen, add butadiene-based rubber emulsion (A1) 300 weight parts (dry weight), chain-transfer agent α-Jia Jibenyixierjuwu 0.2 weight part, hydrogen phosphide cumene 0.32 weight part, sodium formaldehyde sulfoxylate 0.2 weight part, potassium oleate 2 weight parts, water 200 weight parts, after the interpolation with vinylbenzene 60 weight parts, alpha-methyl styrene 10 weight parts, methyl methacrylate 2 weight parts and vinyl cyanide 28 weight parts mix the back and add continuously, at 60 ℃ of graft polymerization reactions that move 8.5 hours down, can get the graft copolymer of transformation efficiency 93.6%, the quantity median size of rubber particles is 0.14 μ m, and its size distribution is to account for 62.0% below the 0.1 μ m, 0.1～0.25 μ m accounts for 33.6%, 0.25 account for 4.4% more than the μ m.
(2) manufacturing of resin combination:
5% aqueous sulfuric acid is added in the above graft copolymer emulsion, and 90 ℃ stir 10 minutes down after the curding out slurries with 112 ℃, 4kg/cm
2Water vapor stripping after 60 minutes, after the hot water of dehydration and 80 ℃ is washed, obtain the graft copolymer powder of water ratio 29.2% again; (it forms weight ratio: vinyl cyanide/vinylbenzene/alpha-methyl styrene/methyl methacrylate=28/50/18/4 with styrene--vinyl cyanide-methyl-methacrylate resin, molecular weight is 132,000) with respect to 2 of 100wt% resin combination, 6-two-tertiary butyl-4-sylvan (0.1wt%), three (nonyl phenyl) phosphorous acid esters (0.1wt%), ethene bis-stearamides (2.0wt%) etc., mix into the mixture of rubber content 19wt% with above-mentioned graft copolymer powder mixes, biaxial extruder with day system Toshiba TEM-35 type is extruded under 240 ℃, (V1, vacuum tightness V2) is respectively 120Torr and 40Torr to first and second degassing mouth.
" comparative example 1～4 "
Use identical treatment process with embodiment 1, difference is to use various different graft copolymers or its mixture shown in subordinate list two, its graft copolymer the condense subsequent disposal of slurries such as subordinate list three and adjust different strippings, drying and extrusion condition and obtain final resin combination.
The resin combination of aforementioned each embodiment and comparative example gained makes test film, and in order to physical propertiess such as test ball falling impact intensity, surface gloss and tensile strength and residual monomer, stinks, result such as subordinate list four, testing method is as follows:
One. ball falling impact intensity:
With the circular test board of Jet forming machine ejaculation radius 50mm thickness 3mm, under 23 ℃ temperature,, obtain the peak power of rupture test plate with 5 kilograms steel ball impact test plate central authorities, unit is kg/cm.
Two. the gloss on surface:
Respectively under 280 ℃ of mold temperatures, penetrate the tabular forming composition of 50mm (wide) * 90mm (length) * 3mm (thick) with Jet forming machine; The molding plate mean values of glossmeter with 60 ° of input angles mensuration five composition templates, unit is %.
Three. tensile strength:
According to the test of ASTM D-638 method, its unit is: kg/cm
2
Four. the residual quantity of styrenic monomers and 4 vinyl cyclohexene:
Styrenic monomers that the present invention carried and 4 vinyl cyclohexene composition, be resin combination to be dissolved in dimethyl formamide (Dimethyl formamide, be called for short DMF) and resin combination solution re-uses the gas chromatograph of the numbering 5890A of Hewl-ettpackard company and performs an analysis with the ionic flame test set.
Five. the test of molding stink:
The resin combination that makes according to experiment is to make spherical micelle after extruding pelletizing, getting the 150g micelle puts in the sealing glass jar after cooling, open glass pot by ten persons of having a sharp sense of smell and test its stink degree, and comply with and assert that number number frowzy decides its grade, and with following symbology.
Assert that number frowzy indicates
The following ◎ of 2 people
2-4 people zero
4-8 people △
More than 8 people *
" conclusion "
Result by subordinate list four shows as can be known, rubber-modified styrene resin composite of the present invention, via regulating and control residual styrenic monomers below 1500ppm, residual 4 vinyl cyclohexene is below 150ppm, and median size and the size distribution of adjusting suitable rubber particles can have excellent high ball falling impact intensity, high-tensile, have the good gloss degree simultaneously, more can when being shaped, significantly reduce the shaping stink, obtain the moulding product of no stink character by this; Its composition is not only novel, has more the utility value on the industry.
Only the above only is a preferable possible embodiments of the present invention, is familiar with this technology personage such as, and it all ought to be included in the application's claim according to modification or change that the present invention's spirit category is done.
Subordinate list one
The polymerizing condition of graft copolymer
Note: 1.TDM is three-lauryl mercaptan.
| The numbering of graft copolymer | G1 | G2 | G3 | G4 | G5 | G6 | G7 | G8 | |
| The kind of butadiene-based rubber emulsion | A1 | A1 | A2 | A3 | C1 | C1 | C2 | C3 | |
| Graft polymerization chain-transfer agent (weight part) | T D M | 0.2 | - | 0.2 | 0.2 | 0.2 | - | 0.2 | 0.2 |
| α-Methyl Styrene Dimer | - | 0.2 | - | - | - | 0.2 | - | - | |
| The monomer conversion of graft polymerization (%) | 94.0 | 93.2 | 94.5 | 94.2 | 93.6 | 92.8 | 93.8 | 94.0 | |
2. α-Methyl styrene Dimer is a α-Jia Jibenyixierjuwu.
Subordinate list two
The median size of graft copolymer or its mixture and size distribution
| Experiment numbers | Embodiment | Comparative example | ||||||||||
| The graft copolymerization species | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 1 | 2 | 3 | 4 | |
| G1 | G2 G5 | G3 G5 | G3 G6 | G3 G7 | G3 G7 | G4 G8 | G1 | G1 | G2 | G3 | ||
| The size distribution % of rubber particles | 0.1 below the μ m | 62.4 | 68.5 | 76.4 | 75.2 | 74.2 | 52.5 | 78.2 | 62.4 | 62.4 | 62.4 | 96.4 |
| 0.1～0.25μm | 32.4 | 27.5 | 20.8 | 22.0 | 14.0 | 13.0 | 19.6 | 32.4 | 32.4 | 32.4 | 3.2 | |
| 0.25 more than the μ m | 5.2 | 4.0 | 2.8 | 2.8 | 11.8 | 34.5 | 2.2 | 5.2 | 5.2 | 5.2 | 0.4 | |
| Quantity median size (μ m) | 0.14 | 0.12 | 0.11 | 0.11 | 0.13 | 0.23 | 0.11 | 0.14 | 0.14 | 0.14 | 0.075 | |
Subordinate list three
Graft copolymer is with continuous reason after the liquid
Annotate: * 1:V
1And V
2Be the degassing of first and second on forcing machine mouth.
| Experiment numbers | Embodiment | Comparative example | ||||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 1 | 2 | 3 | 4 | ||
| The stripping of slurries condenses | Have | Do not have | Have | Do not have | Do not have | Do not have | Do not have | Have | Do not have | Do not have | Have | |
| Dry back graft copolymer water content (%) | 0.1 | 0.3 | 0.5 | 0.3 | 0.3 | 0.6 | 0.2 | 1 | 0.5 | 0.5 | 0.3 | |
| The forcing machine degassing mouthful vacuum tightness (Torr) | V1(*1) | 150 | 180 | 80 | 240 | 170 | 180 | 240 | Open and close | 760 | 150 | 300 |
| V2(*1) | 60 | 70 | 45 | 120 | 80 | 100 | 20 | 380 | 180 | 80 | 140 | |
| Addition-the normal hexane of devolatilization auxiliary agent (weight part) | Between feeding mouth and V1 | 2.5 | 2.2 | 4 | 1.8 | 1.8 | 1.8 ** | 1.8 | - | 1.8 | - | 1.8 |
| Between V1 and V2 | 1.8 | 1.8 | - | - | - | - | - | - | - | - | - | |
* 2: the devolatilization agent makes water.
Subordinate list four
Rerum natura value of commenting of resin combination
| The test number test subject | Embodiment | Comparative example | ||||||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 1 | 2 | 3 | 4 | |
| Total rubber content (weight %) | 19 | 19 | 19 | 19 | 19 | 19 | 19 | 19 | 19 | 19 | 19 | 19 | 19 | 19 |
| Ball falling impact intensity (cm) | 400 | 390 | 390 | 390 | 380 | 410 | 390 | 370 | 400 | 390 | 400 | 400 | 400 | 220 |
| Gloss (%) | 92 | 92 | 94 | 94 | 94 | 90 | 94 | 91 | 92 | 93 | 92 | 92 | 93 | 96 |
| Tensile strength (kg/cm 2) | 414 | 418 | 420 | 420 | 422 | 410 | 416 | 403 | 415 | 412 | 414 | 416 | 418 | 485 |
| Residual benzene vinyl monomer (ppm) | 520 | 580 | 480 | 690 | 645 | 630 | 702 | 720 | 582 | 642 | 1860 | 860 | 620 | 890 |
| Residual 4 vinyl cyclohexene (ppm) | 45 | 62 | 52 | 60 | 58 | 110 | 65 | 100 | 70 | 86 | 380 | 272 | 184 | 62 |
| Stink | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ◎ | ○ | ◎ | ◎ | × | × | × | ◎ |
Claims (5)
1. rubber-modified styrene resin composite, it is made up of matrix phase of styrene-propene base system multipolymer and the butadiene-based rubber particle that is dispersed in the matrix phase; Above-mentioned styrene-propene base system multipolymer is made of acrylic monomer and/or metha crylic monomer, styrenic monomers and other copolymerizable unsaturated ethylene alkene monomers that can optionally add;
It is characterized in that: the styrenic monomers residual quantity in the resin combination is below 1500ppm, and the butadiene dimer residual quantity is below 150ppm, and this butadiene dimer is a 4 vinyl cyclohexene; And rubber quantity median size is 0.08～0.35 μ m in the resin combination, the rubber particles of particle diameter below 0.1 μ m accounts for 19.5 of rubber particles sum～9 9 quantity per-cents, the rubber particles of particle diameter between 0.1～0.25 μ m accounts for 0.5～60 quantity per-cent of rubber particles sum, and the rubber particles of particle diameter more than 0.25 μ m accounts for 0.5～80 quantity per-cent of rubber particles sum.
2. rubber-modified styrene resin composite as claimed in claim 1; Wherein, the rubber particles of particle diameter below 0.1 μ m accounts for 50～98 quantity per-cents of rubber particles sum, the rubber particles of particle diameter between 0.1～0.25 μ m accounts for 1～40 quantity per-cent of rubber particles sum, and the rubber particles of particle diameter more than 0.25 μ m accounts for 1～70 quantity per-cent of rubber particles sum.
3. rubber-modified styrene resin composite as claimed in claim 1; Wherein, rubber quantity average particle diameter is between 0.09～0.14 μ m.
4. rubber-modified styrene resin composite as claimed in claim 1; Wherein, the styrenic monomers residual quantity is below 850ppm.
5. rubber-modified styrene resin composite as claimed in claim 1; Wherein, the 4 vinyl cyclohexene residual quantity is below 100ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95118216A CN1048268C (en) | 1995-10-10 | 1995-10-10 | Rubber-modified polystyrene resin compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95118216A CN1048268C (en) | 1995-10-10 | 1995-10-10 | Rubber-modified polystyrene resin compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1147529A CN1147529A (en) | 1997-04-16 |
| CN1048268C true CN1048268C (en) | 2000-01-12 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95118216A Expired - Lifetime CN1048268C (en) | 1995-10-10 | 1995-10-10 | Rubber-modified polystyrene resin compounds |
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| EP1537977B1 (en) * | 2002-07-31 | 2018-11-21 | Shikoku Kakoki Co., Ltd. | Resin sheet for cold forming and cold formed article |
| US8541078B2 (en) * | 2004-08-06 | 2013-09-24 | Societe Bic | Fuel supplies for fuel cells |
| TWI418590B (en) * | 2011-11-07 | 2013-12-11 | Chi Mei Corp | Transparent Rubber Modified Styrene Resin |
| TWI453247B (en) * | 2012-12-28 | 2014-09-21 | Chi Mei Corp | Rubber-modified styrene-based resin composition |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6320735A (en) * | 1986-07-12 | 1988-01-28 | Fuji Elelctrochem Co Ltd | Optical head |
| JPH0790159A (en) * | 1993-09-22 | 1995-04-04 | Idemitsu Petrochem Co Ltd | Rubber-modified styrene resin composition |
-
1995
- 1995-10-10 CN CN95118216A patent/CN1048268C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6320735A (en) * | 1986-07-12 | 1988-01-28 | Fuji Elelctrochem Co Ltd | Optical head |
| JPH0790159A (en) * | 1993-09-22 | 1995-04-04 | Idemitsu Petrochem Co Ltd | Rubber-modified styrene resin composition |
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| CN1147529A (en) | 1997-04-16 |
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