CN1055099C

CN1055099C - Styrene resin composition

Info

Publication number: CN1055099C
Application number: CN97112118A
Authority: CN
Inventors: 盛培华; 薛东弼
Original assignee: Chi Mei Corp
Current assignee: Chi Mei Corp
Priority date: 1997-06-02
Filing date: 1997-06-02
Publication date: 2000-08-02
Anticipated expiration: 2017-06-02
Also published as: CN1201052A

Abstract

The invention discloses a styrene resin composition, which comprises the following components: (1)100 parts by weight of a styrene resin comprising a rubber-like graft copolymer A5-100% by weight and a styrene copolymer B0-95% by weight; (2) 0.01-2 parts by weight of a product C obtained by carrying out a butylation reaction on p-cresol and dicyclopentadiene; (3)0.01 to 0.8 parts by weight of a phosphorus antioxidant D and/or a thioether antioxidant E; the total content of dipolymer or tripolymer formed by styrene monomer and/or acrylonitrile monomer contained in the styrene resin composition is less than 25,000ppm, and the residual styrene monomer is less than 2,000 ppm.

Description

Styrene-series resin compositions

The invention relates to a kind of styrene-series resin compositions, be meant especially a kind ofly to add few, the low odor of cigarette amount in man-hour, and the resin combination of good thermal stability.

Being familiar with this operator all knows, rubber like graft copolymer is scattered in the styrene based copolymer, prepared product is a kind of impact resistance phenylethylene resin series constituent, and this kind resin combination can be used in ejection formation, extrusion moulding, vacuum forming, blow aspects such as prolonging moulding or thermoforming; And in order to make styrene-series resin compositions have the value of practicality, on making, need in resin, add the antioxidant that is used for improving thermostability usually, and because the resin work in-process can produce free radical and superoxide, these two kinds of compositions are to cause reaction process cracked principal element, therefore, in the manufacturing processed of styrene-series resin compositions, can add two kinds of antioxidants usually and come stabilized radical and superoxide respectively; Generally speaking, sterically hindered phenol is that antioxidant mostly is used to stablize the free radical that produces in the course of processing, and sulfo-distearyl acyl group dipropionate (Distearyl thio dipropionate for example, abbreviation DSTDP) thioether is an antioxidant, perhaps trinonylphengl phosphite (Tris nonylphenylphosphite, abbreviation TNPP) phosphorous antioxidant generally is used to the stable peroxide thing, improves the thermostability of resin by this; But being in the antioxidant, thioether has the composition of sulphur, therefore, use this type of excessive antioxidant to make and produce heavier stink in manufacturing processed or the finished product, use excessive phosphorous antioxidant then can produce and add cigarette amount in man-hour disappearance on the high side, therefore, how when having good thermal stability, make resin possess few, the low odor of cigarette amount man-hour adding, be to demand the problem that breaks through for a long time urgently for being familiar with this technical field personage.

Therefore, main purpose of the present invention is to add few, the low odor of cigarette amount in man-hour providing a kind of, and the styrene-series resin compositions of good thermal stability.

Above-mentioned purpose of the present invention is achieved in that a kind of styrene-series resin compositions mainly comprises:

The phenylethylene resin series of (1) 100 weight part, it is by rubber like graft copolymer A5～100

Weight %, styrene based copolymer B0～95 weight % form; Wherein, rubber-like connects

Graft copolymer A is in the presence of diene series rubber, with styrenic monomers, acrylic list

Body and optionally and the choosing the copolymerizable monomer graft copolymerization and get;

The product C that (2) 0.01～2 weight parts are got through the butylation reaction by p-Cresol and dicyclopentadiene;

The phosphorous antioxidant D of (3) 0.01～0.8 weight parts and/or thioether are antioxidant E:

Dipolymer or trimeric total content that styrenic monomers that above-mentioned styrene-series resin compositions is contained and/or acrylic monomer are become are lower than 25,000ppm, and residual styrenic monomers is 2, below the 000ppm; Above-mentioned composition is after fusion, and it is few to make a kind of low odor, cigarette amount that can be applicable to any moulding, processing method, and the good styrene-series resin compositions of thermostability.

Rubber like graft copolymer A of the present invention is by diene series rubber 40～90 weight parts, and by the styrenic monomers of 50～90 weight %, the acrylic monomer of 10～50 weight %, 0～40 weight % optionally and monomer mixture 10～60 weight parts formed of copolymerizable monomer of choosing, can be via dividing other bulk, solution, suspension or emulsion polymerization method and make, also can make via the combination of these polymerizations, as emulsification one bulk or bulk-suspension polymerization, be preferably emulsion polymerization method, block polymerization and solution polymerization process are best especially with the emulsion polymerization method.

Emulsion polymerization and rubber like graft copolymer A be preferably in the butadiene-based rubber emulsion and exist down, with the styrenic monomers of 50～90 weight %, the acrylic monomer of 10～50 weight %, and the copolymerizable monomer graft polymerization of 0～40 weight % and weight average particle diameter be the emulsion of the rubber like graft copolymer A of 0.05～0.8 μ m, thereafter through condense, dehydration, drying and other steps, make powder granulous rubber like graft copolymer A; Above-mentioned butadiene-based rubber emulsion comprises the conjugate diene monomer of 60～100 weight %, and the unit unsaturated monomer of 0～40 weight % is formed with first polymkeric substance or its multipolymer, and above-mentioned conjugate diene monomer can followingly be represented:

Wherein, R can be hydrogen, methyl or chloro etc., and the unit unsaturated monomer can be styrenic monomers, acrylic monomer and (methyl) acrylic ester monomer.

Above-mentioned butadiene-based rubber emulsion can be divinyl-styrol copolymer, divinyl-acrylonitrile copolymer and divinyl-methylmethacrylate copolymer etc., it can above-mentioned monomer direct polymerization becomes weight average particle diameter is the polymkeric substance of 0.05～0.8 μ m, or after can aggregating into the small particle size rubber latex of 0.05～0.18 μ m in advance, with the loose method of traditional rubber, the small particle size rubber latex hypertrophy of 0.05～0.18 μ m is become the rubber latex of 0.2～0.8 μ m again.The loose method of above-mentioned rubber comprises: add organic acid, metal-salt or contain the chemical loose method of carboxylic acid group's polymer coagulant, the loose method of churned mechanically machinery or for freezing loose method etc., wherein, chemical loose method for example can use butyl acrylate-Sipacril 2739OF as polymer coagulant.

Aforementioned emulsion process polymerization and rubber like graft copolymer A have unimodal formula size distribution, median size is 0.05～0.8 μ m, or has the double-peak type size distribution, median size is respectively 0.05～0.18 μ m and 0.2～0.8 μ m.

And bulk or solution polymerization process polymerization and the manufacture method of rubber like graft copolymer A, be with diene series rubber be dissolved in advance monomer mixture and optionally and the choosing solvent in, this monomer mixture comprises the styrenic monomers of 50～90 weight %, the acrylic monomer of 10～50 weight %, and the copolymerizable monomer of 0～40 weight %, then gained solution is pumped in the reactive tank, under mixing, carry out graft polymerization reaction.Can add an amount of chain transfer agent between the reaction period according to circumstances, for example: uncle's lauryl mercaptan, with the molecular weight of controlling polymers, and reactive tank can be combined by multiple-grooved, is preferably the still type reactive tank with strong mixer.

Above-mentioned diene series rubber is preferable such as be divinyl rubber, isoprene rubber, neoprene etc.; Wherein, divinyl rubber has the branch of high-cis (Hi-Cis) content and low cis (Low-Cis) content; In the high-cis rubber, the typical weight of its cis (Cis)/vinyl (Vinyl) consists of 94～98%/1～5%, and all the other consist of trans (Trans) structure; Its Mooney (Mooney) viscosity is at 20～120, and molecular weight ranges is with 100,000～800, and 000 is good; In the low cis rubber, the typical weight of cis/vinyl consists of 20～40%/1～20%, and all the other are transconfiguration, and its Mooney viscosity is at 20～120; Other elastomeric materials that are fit to still have: acrylic-nitrile rubber, styrene/butadiene rubbers, or the mixing of above-mentioned different rubber, and the SBR that promptly is commonly called as of styrene/butadiene rubbers; Be suitable for phenylethylene/butadiene copolymerization rubber of the present invention, its polymerization pattern can be two-section type (di-block) multipolymer, syllogic (tri-block) copolymerization, Random copolymer RCP (random) or star formula copolymerization (star-type).And the part by weight scope of styrene/butadiene rubbers is preferably 5/100 to 80/20, and molecular weight ranges is preferably 50,000～600,000; Be applicable to that rubber of the present invention is good with divinyl rubber and styrene/butadiene rubbers, wherein again with divinyl rubber for better.

By bulk or solution polymerization process polymerization and rubber like graft copolymer A, its rubber weight average particle diameter generally between 0.6～10 μ m, is preferably 1.0～7.0 μ m.

Rubber like graft copolymer A of the present invention be except using above-mentioned emulsification graft copolymer or bulk (or solution) graft copolymerization beyond the region of objective existence respectively, also can be with said two devices and usefulness, to form size distribution bimodal or three peak formulas, wherein:

The double-peak type person as:

(1) median size 0.2～0.8 μ m (emulsification)

Median size 0.6～10 μ m (bulk or solution),

Or

(2) median size 0.05～0.18 μ m (emulsification)

Median size 0.6～10 μ m (bulk or solution).

Three peak formula persons as:

(3) median size 0.05～0.18 μ m (emulsification)

Median size 0.2～0.8 μ m (emulsification)

Median size 0.6～10 μ m (bulk or solution)

Styrenic monomers used in the present invention can be selected from vinylbenzene, alpha-methyl styrene, α-chloro-styrene, right-t-butyl styrene, p-methylstyrene, neighbour-chloro-styrene, right-chloro-styrene, 2,5-dichlorostyrene, 3,4-dichlorostyrene, 2,4,6-tribromo-benzene ethene, 2,5-Dowspray 9 etc., wherein, preferable with vinylbenzene or alpha-methyl styrene.

The copolymerizable monomer of using among the rubber like graft copolymer A of the present invention can be selected from (methyl) acrylic ester monomer, maleimide is monomer, vinylformic acid, Maleic Acid, Anhydrous and glycolmethacrylate; Wherein, (methyl) acrylic ester monomer can be: methyl acrylate, ethyl propenoate, butyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, methacrylic acid benzene methyl, N-Hexyl methacrylate, cyclohexyl methacrylate, lauryl methacrylate, methacrylic acid 2-hydroxyl ethyl ester, glycidyl methacrylate and Dimethylaminoethyl Methacrylate etc. are preferable with methyl methacrylate wherein.

Maleimide is that monomer can be selected from N-methyl maleimide, N-sec.-propyl maleimide, the N-butyl maleimide, N-hexyl maleimide, 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 imides etc. wherein, are best with the N-phenylmaleimide.

Styrene based copolymer B used in the present invention is by the styrenic monomers of 80～50 weight parts, the acrylic monomer of 20～50 weight parts, and optionally select the copolymerizable monomer polymerization of 0～40 weight part and get, above-mentioned styrenic monomers, acrylic monomer and copolymerizable monomer are identical with employed monomer explanation among the rubber like graft copolymer A; Aforementioned styrene based copolymer B can also bulk, solution, suspension or emulsion polymerization method make, and is preferable with bulk and solution polymerization process.Its weight average molecular weight scope is at 60,000 to 400,000, and the number molecular-weight average is at 30,000 to 200,000, when molecular weight too Gao Shihui cause processing to be difficult for, if the too low then shock-resistance of molecular weight is not good.

The product C (Butylated reaction product of p-cresol and dicyclopentadiene) that gets through the butylation reaction by p-Cresol and dicyclopentadiene in the styrene-series resin compositions of the present invention, it is meant following formula: compound:

Its molecular weight=500～2000, n is the integer of non-O.

Because when phenylethylene resin series uses phosphorous antioxidant, can produce the cigarette amount man-hour adding, using thioether is then meeting frowziness in manufacturing processed or finished product of antioxidant, but product C then can reduce phosphorus system significantly and/or thioether is the usage quantity of antioxidant if add in manufacturing processed, is adding disappearances such as the cigarette amount that produces man-hour and stink and can effectively improve resin.

The usage quantity of above-mentioned product C is between 0.01～2 weight part, be preferably 0.02～1 weight part, when usage quantity is lower than 0.01 weight part, can make the thermostability variation of styrene-series resin compositions of the present invention, no practical value, if usage quantity then can cause the raising of manufacturing cost when being higher than 2 weight parts, does not meet economic benefit.

Phosphorous antioxidant D in the resin combination of the present invention and/or thioether are antioxidant E, and its usage quantity is preferably 0.02～0.6 weight part between 0.01～0.8 weight part; Wherein, thioether is that the representative person of antioxidant E has: sulfo-distearyl acyl group dipropionate, sulfo-two palmitoyl dipropionates, five tetrahydroxybutanes-four-(β-ten dimethyl-sulphur propionic ester), two dodecyl thioether, double tridecyl thioether, two tetradecyl thioether and two octadecyl thioethers etc.; And phosphorous antioxidant D can be phosphorous acid ester is antioxidant, its representative person has: trinonylphengl phosphite, 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 esters.Other phosphorous antioxidant can be for example: four (2, the 4-tert-butyl-phenyl)-4,4 '-stretch xenyl phosphoric acid ester and 9,10-dihydro-9-oxy-10-phosphoric acid phenanthrene-10-oxygen support etc.; Above-mentioned phosphorous antioxidant D and/or thioether are that the consumption of antioxidant E is when being lower than 0.01 weight part, can cause the thermostability of resin not good, the consumption of phosphorous antioxidant D is higher than 0.8 weight part, then the processing cigarette amount of resin can't be improved, thioether be the consumption of antioxidant E be higher than 0.8 weight part then the stink of resin can't eliminate.

Resin combination of the present invention is because butylation product C and phosphorous antioxidant D and/or thioether are antioxidant E and usefulness, not only can improve the thermostability of resin combination significantly, and only need a spot of antioxidant can reach above-mentioned effect, add excessive disappearance so also can not produce antioxidant, for example: the cigarette amount is many, stink etc.

Alleged styrenic monomers and/or acrylic monomer are become among the present invention dipolymer or trimer, wherein, this dipolymer comprises: styrene-acrylonitrile SA, vinyl cyanide-vinyl cyanide AA, vinylbenzene-vinylbenzene SS, and trimer includes: vinyl cyanide-vinyl cyanide-vinyl cyanide AAA, vinylbenzene-vinylbenzene-vinylbenzene SSS, vinyl cyanide-acrylonitrile-styrene AAS, vinylbenzene-styrene-acrylonitrile SSA etc.

Monomeric dipolymer of styrenic monomers and/or acrylic or trimeric total content are 25 in the constituent of the present invention, below the 000ppm, and with 20,000ppm is following to be good, and residual styrenic monomers is 2, below the 000ppm, again with 1,500ppm is following to be preferable, and when above-mentioned content was higher than this scope, the stink of resin can't effectively be eliminated.

Styrene-series resin compositions of the present invention can add the additive that uses other according to need, for example: sequestrant, plasticizer, processing aid, ultra-violet stabilizer, UV light absorber, weighting agent, reinforcer, colorant, lubricant, charged preventor, incombustible agent, difficult combustion auxiliary agent, thermo-stabilizer, thermo-color prevent agent, coupler or other additives etc., above-mentioned additive can be in polyreaction, after the polyreaction, condense preceding or extrude in the process of mixing and add.

Be applicable to that sequestrant addition of the present invention is good with 0.001～2.0 weight %, its representative person is 2, the 2-oxalamide is two-sodium salt of [ethyl-3-(3, the 5-tertiary butyl-4-hydroxyphenyl) propionic ester], phenyl phenacyl ketone and diethylamine four acetic acid etc.

Be applicable to that the representative person of lubricant of the present invention has: calcium stearate, Magnesium Stearate, metallic soaps such as lithium stearate, ethylene distearyl acid amides, methylene distearyl acid amides, palmitic amide, butyl stearate, stearic acid palm ester, poly-propionic acid alcohol tristearate, behenic acid, the compound of stearic acid etc., and polyethylene wax, octocosoic acid wax, carnauba wax (Carnuba wax), petroleum wax etc., but not with the aforementioned limit that is exemplified as: the addition of lubricant is with respect to 0.03～5.0 weight % of the common total of total styrene-series resin compositions, also can in constituent of the present invention, for example add: the processing aid of methyl methacrylate system, with extrusion moulding and the hot formability that improves resin.

The use of UV light absorber and ultra-violet stabilizer, then can improve resin the irradiation of weathering resistance, UV resistant the rerum natura deterioration of the variable color that produces or resin, wherein, the representative person of UV light absorber who is suitable for has: benzotriazole based compound, benzophenone based compound, cyanogen acrylic acid series compound, but not as limit; And the ultra-violet stabilizer that is suitable for has: the retardance amine compound, and be that ultra-violet stabilizer and cyanogen acrylic acid series UV light absorber are good merge to use retardance amine, for example: the Uvinul 4050H of BASF AG (0.02～1.0 weight %)/Uvinul 3035 (0.02～1.0 weight %), during use also not with the above-mentioned limit that is exemplified as; As the total addition level of above-mentioned substance 0.02～2.0 weight % of styrene-series resin compositions.

Be applicable to charged preventor of the present invention, its representative person has: the low molecule based compound of tertiary amine based compound, quarternary ammonium salt based compound etc., or the polymeric amide polyethers, be the macromolecular material of permanent charged preventing property, but not as limit as epichlorohydrin polymer etc.

Weighting agent representative person have: lime carbonate, tripoli and mica.And the representative person of reinforcer has: glass fibre, carbon fiber, various brilliant silk (whisker) class.Colorant representative person have: titanium oxide, ferric oxide, graphite, phthalein mountain valley with clumps of trees and bamboo dyestuff.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 and expansile graphite etc.Stablizer representative person have: dibutyl tin maleate, alkali magnalium hydroxyl carbonate etc.; And thermo-color prevents that agent from can be low-molecular-weight vinylbenzene-Maleic Acid, Anhydrous multipolymer, and its addition is with respect to styrene-series resin compositions of the present invention 0.1～1.0 weight % of total amount usually.Coupler representative person have: silane system, phthalate, germanic acid ester based compound etc.

In styrene-series resin compositions of the present invention for modification, can suitably use the additive of polymerization system, the rubber-modified phenylethylene resin series that for example adopts emulsion polymerization method mode in addition to make, for example: acrylonitrile-butadiene-styrene resin, use butadiene-based rubber rubber in addition, for example: EPDM, come the AES resin of modification with butyl acrylate rubber, 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 %, styrene-acrylonitrile-Maleic Acid, Anhydrous multipolymer through the aniline imidization, there is not grafted bridge formation rubber, for example: acrylonitrile-butadiene rubber, ethylene chloride resin, the poly-phenyl ether of stretching, polymethylmethacrylate, polycarbonate resin, polyamide resin, poly-terephthalic acid butene esters, the polystyrene thermoplastic elastomer, and various phase solvations etc., its usage quantity is with respect to 3～200 parts of weights of 100 weight parts styrene-series resin compositions of the present invention.

For further describing the present invention in detail, be described as follows with embodiment and physical property measurement again, the composition unless specifically stated otherwise of following constituent, otherwise all represent with weight part.

Below enumerate embodiment and describe the present invention in detail, but scope of the present invention is not exceeded with these embodiment.

＜preparation example

＜preparation example I-1〉manufacturing of rubber like graft copolymer (A-1):

Following raw materials according is inserted in the reactive tank with whipping appts, heating unit and material feeding tube.

The composition weight part

1,3-butadiene 95.0

Vinyl cyanide 5.0

Potassium persulfate solution (1%) 15.0

Trisodium phosphate 3.0

Potassium oleate 1.5

Distilled water 140.0

Uncle-lauryl mercaptan 0.2

Fill a prescription in 65 ℃ of thermotonuses 12 hours according to above-mentioned, can obtain transformation efficiency and be 94%, solids content is about 40%, the synthetic rubber latex of weight average particle diameter 0.1 μ m.

In addition, the polymer coagulant that contains the carboxylic acid group with following composition manufacturing:

The composition weight part

N-butyl acrylate 85.0

Methacrylic acid 15.0

Uncle-lauryl mercaptan 0.3

Potassium oleate 2.0

Dioctyl sodium sulphosuccinate 1.0

Isopropyl benzene hydrogen peroxidase 10 .4

Sodium formaldehyde sulphoxylate 0.3

Distilled water 200.0

Fill a prescription in 75 ℃ of thermotonuses 5 hours according to above-mentioned, can obtain the polymer coagulant that contains the carboxylic acid group of transformation efficiency 95%, pH value 6.0.

Afterwards, the polymer coagulant (dry weight) that utilizes 3 weight parts to contain the carboxylic acid group comes the synthetic rubber latex (dry weight) of loose 100 weight parts, and the pH value of resulting enlarged rubber emulsion is 8.5, and weight average particle diameter is 0.31 μ m.

At last, carry out graft polymerization reaction with the enlarged rubber emulsion according to following prescription again, to make rubber like graft copolymer (A-1):

The composition weight part

Enlarged rubber emulsion (dry weight) 100.0

Vinylbenzene 25.0

Vinyl cyanide 8.3

Potassium oleate 1.2

Uncle-lauryl mercaptan 0.2

Isopropyl benzene hydrogen peroxidase 10 .5

Copperas solution (0.2%) 3.0

Formaldehyde sodium sulfoxylate solution (10%) 3.0

Ethylene dinitrilotetra-acetic acid solution (0.25%) 20.0

Distilled water 200.0

Prepared grafting rubbers emulsion is with calcium chloride (CaCl ₂) condense after, just can make the rubber like graft copolymer of wanting required for the present invention (A-1), its rubber content 75 weight %, weight average particle diameter 0.31 μ m.＜preparation example I-2〉manufacturing of rubber like graft copolymer (A-2):

With＜preparation example I-1〉prepared synthetic rubber latex (rubber weight average particle diameter 0.1 μ m), direct and following table prescription carries out graft polymerization reaction, to make rubber like graft copolymer (A-2).

The composition weight part

Synthetic rubber latex (0.1 μ m) (dry weight) 100.0

Vinylbenzene 32.4

Vinyl cyanide 12.6

Potassium oleate 1.6

Uncle-lauryl mercaptan 0.27

Isopropyl benzene hydrogen peroxidase 10 .67

Copperas solution (0.2%) 4.0

Formaldehyde sodium sulfoxylate solution (10%) 4.0

Ethylene dinitrilotetra-acetic acid solution (0.25%) 27.0

Distilled water 200.0

Comply with the prepared grafting rubbers emulsion of above-mentioned prescription again with calcium chloride (CaCl ₂) condense, just can make the rubber like graft copolymer of wanting required for the present invention (A-2), its rubber content 69 weight %, weight average particle diameter 0.1 μ m.

＜preparation example I-3〉manufacturing of rubber like graft copolymer (A-3):

With the benzoyl peroxide of the uncle-lauryl mercaptan of 0.1 weight part and 0.07 weight part as initiator, polyhutadiene (company of Asahi Chemical Industry product with 6.6 weight parts, trade(brand)name Asadene 55AS) is dissolved in fully in the ethylbenzene of the vinyl cyanide of vinylbenzene, 25.6 weight parts of 74.4 weight parts and 30 weight parts, to form feedstock solution.Afterwards feedstock solution is sent into continuously volume and be in 45 liters first reactor, temperature of reaction is 100 ℃, configuration is provided with the screw mixer of refrigeration cycle pipe in the reactor, its stir speed (S.S.) is 300rpm, will through behind first reactor reaction mixture take out continuously and send in regular turn in second reactor, the device of this second reactor is identical with first reactor, the transformation efficiency of mixture of waiting reaches at 60% o'clock, the mixture taking-up is sent in the devolatilization device, remove unreacted monomer and volatile matter, afterwards with its extrusion granulator, promptly make rubber like graft copolymer (A-3), the weight average particle diameter of its rubber particles is 1.1 μ mm, and rubber content is 11 weight %.

＜preparation example II-1〉styrene based copolymer (B-1):

The raw material of vinylbenzene 70 weight %, vinyl cyanide 30 weight % is mixed, again with ethylene distearyl acid amides 0.025 weight %, uncle-lauryl mercaptan, and fugitive constituent formed recovery liquid after condensation that following reaction is removed merges as feeding feeding, remain on the continous way still type reactor with agitator of 45 liters of 145 ℃ and volumes with temperature in being fed into, and make the toluene ratio in the reaction solution remain on 15%, and percent polymerization remain on 56%.

When reaction solution is removed the volatilization composition by the devolatilization device after, can obtain the particle of vinylbenzene-acrylonitrile copolymer; On the other hand, the volatilization composition of being removed is condensing as reclaiming liquid with condenser, and re-use it with the aforementioned base materials mixed solution continuously, by the consumption of adjusting uncle-lauryl mercaptan, can make melt flow index and be 3.2 polystyrene (vinylbenzene-vinyl cyanide) multipolymer (B-1).＜preparation example II-2〉preparation of styrene based copolymer (B-2):

The raw material of vinylbenzene 70 weight %, vinyl cyanide 30 weight % is mixed, again with ethylene distearyl acid amides 0.025 weight %, benzoyl peroxide, uncle-lauryl mercaptan, and fugitive constituent formed recovery liquid after condensation that following reaction is removed merges as feeding feeding, remain on the continous way still type reactor with agitator of 45 liters of 108 ℃ and volumes with temperature in being fed into, and make the toluene ratio in the reaction solution remain on 15%, and percent polymerization remain on 55%.

When reaction solution is removed the volatilization composition by the devolatilization device after, can obtain the particle of vinylbenzene-acrylonitrile copolymer; On the other hand, the volatilization composition of being removed is condensing as reclaiming liquid with condenser, and re-use it with the aforementioned base materials mixed solution continuously, this method is adjusted speed of response by the consumption of benzoyl peroxide, or adjust the consumption of uncle-lauryl mercaptan, can make melt flow index and be 3.0 polystyrene (vinylbenzene-vinyl cyanide) multipolymer (B-2).

＜preparation example II-3〉styrene based copolymer (B-3):

The raw material of vinylbenzene 70 weight %, vinyl cyanide 30 weight % is mixed, again with ethylene distearyl acid amides 0.025 weight %, uncle-lauryl mercaptan, and fugitive constituent formed recovery liquid after condensation that following reaction is removed merges as feeding feeding, remain on the continous way still type reactor with agitator of 45 liters of 155 ℃ and volumes with temperature in being fed into, and make the toluene ratio in the reaction solution remain on 15%, and percent polymerization remain on 57%.

When reaction solution is removed the volatilization composition by the devolatilization device after, can obtain the particle of vinylbenzene-acrylonitrile copolymer; On the other hand, the volatilization composition of being removed is condensing as reclaiming liquid with condenser, and re-use it with the aforementioned base materials mixed solution continuously, by the consumption of adjusting uncle-lauryl mercaptan, can make melt flow index and be 3.35 polystyrene (vinylbenzene-vinyl cyanide) multipolymer (B-3).

The physical property measurement standard of the embodiment of the invention and the obtained resin combination of comparative example is as follows:

One, the dipolymer or the trimeric total content that are become of styrenic monomers and/or acrylic monomer:

Resin combination is dissolved in the acetone, re-uses the gas chromatograph of the numbering 5890A of Hewlett Packard (Hewlett-Packard) company, resin solution is performed an analysis with flame ionic detector.

Two, residual styrenic monomers content:

Resin combination is dissolved in the acetone, re-uses the gas chromatograph of the numbering 5890A of Hewlett Packard company, resin solution is performed an analysis with flame ionic detector.

Three, thermostability:

Resin combination is of a size of the test piece of 4in * 4in * 1/8in (long * wide * thick) through ejection formation, and placing 180 ℃ oven for baking after 60 minutes the test piece, the thermostability of observing the lower expression resin combination of its foxy (Δ YI), Δ YI value is better.

Four, stink:

The styrene-series resin compositions that makes is extruded through a twin screw extruder, under the gas situation that does not detach the generation of die head place, assess the taste of its generation, gone through continuously 1 hour by the above evaluation group that forms of three people (containing), whether the assessment taste can be accepted, and the amenity under the prolonged operation, unanimous being chosen as is recorded as " ◎ " in the time of can accepting, still be recorded as in the time of can accepting " zero ",, then be assessed as " * " as if having a people not feel well or thinking that taste is not good.

Five, cigarette amount:

Testing method and stink are roughly the same, and promptly unanimous being assessed as is recorded as " ◎ " when hanging down the cigarette amount, be " zero " secondly, and the many persons of cigarette amount are recorded as " * ".

＜embodiment 〉

＜embodiment 1 〉

Use is by＜preparation example I-1〉prepared rubber like graft copolymer (A-1) 35 weight %, and by＜preparation example II-1〉phenylethylene resin series 100 weight parts formed of prepared polystyrene (monomer weight ratio of styrene/acrylonitrile is 30/70) multipolymer (B-1) 65 weight %, and add 0.2 weight part by right-cresols and dicyclopentadiene through the butylation reaction and product C (Goodyear company manufacturing, commodity are called Wingstay-L), and the trinonylphengl phosphite TNPP of 0.4 weight part, make it form a homogeneous melt; This melt is squeezed into strip and cuts into particulate state, dipolymer or trimeric total content that styrenic monomers in its resin combination and/or acrylic monomer are become are 15,000ppm, residual styrenic monomers content is 1,200ppm, and assess at stink, cigarette amount and the thermostability of constituent, the result is stated from the subordinate list one.

＜embodiment 2 〉

Repeat the step of embodiment 1, in addition the addition with product C (i.e. the product that is got through the butylation reaction by right-cresols and dicyclopentadiene) changes 3.0 weight parts into, and the every rerum natura that records is stated from subordinate list one.

＜embodiment 3 〉

Repeat the step of embodiment 1, in addition use by＜preparation example II-2 prepared styrene based copolymer (B-2), making dipolymer or the trimeric total content that styrenic monomers in the resin and/or acrylic monomer become is 8,200ppm, residual styrenic monomers content is 650ppm, and assess at stink, cigarette amount and the thermostability of constituent, its physical property measurement is the result be stated from the subordinate list one.

＜embodiment 4 〉

Repeat the step of embodiment 1, in addition with product C (by right-cresols and dicyclopentadiene through the butylation reaction and product) addition change 0.1 weight part into, and add the IRGANOX-1076[octadecyl-3-(3 of 0.3 weight part, 5-two-tertiary butyl-4-carboxyl-phenyl)-and propionic ester], the every rerum natura that records also is stated from subordinate list one.

＜embodiment 5 〉

Repeat the step of embodiment 1, but do not add trinonylphengl phosphite, and change the sulfo-distearyl acyl group dipropionate (DSTDP) that adds 0.4 weight part, the rerum natura that records is stated from the subordinate list one.

＜embodiment 6 〉

Repeat the step of embodiment 1, in addition use 38 weight % by＜preparation example I-2〉prepared rubber like graft copolymer (A-2), and 62 weight % by＜preparation example II-1 phenylethylene resin series 100 weight parts formed of prepared styrene based copolymer (B-1), making dipolymer or the trimeric total content that styrenic monomers in the resin and/or acrylic monomer become is 14,400ppm, residual styrenic monomers content is 1,200ppm, and at the stink of constituent, cigarette amount and thermostability are assessed, and its physical property measurement is the result be stated from the subordinate list one.

＜embodiment 7 〉

Repeat the step of embodiment 1, and use the antioxidant of identical composition and weight part, in addition use 33 weight % by＜preparation example I-2〉prepared rubber like graft copolymer (A-2), and 30 weight % by＜preparation example I-3 prepared rubber like graft copolymer (A-3), and 37 weight % by＜preparation example II-1 phenylethylene resin series 100 weight parts formed of prepared styrene based copolymer (B-1), the constituent that makes is surveyed dipolymer or the trimeric total content that its styrenic monomers and/or acrylic monomer are become equally, residual styrenic monomers content, and every physical property test, the result is stated from subordinate list one.

＜embodiment 8 〉

Repeat the step of embodiment 1, and use the antioxidant of identical composition and weight part, in addition use 18 weight % by＜preparation example I-1〉prepared rubber like graft copolymer (A-1), 15 weight % are by＜preparation example I-2〉prepared rubber like graft copolymer (A-2), 20 weight % are by＜preparation example I-3〉prepared rubber like graft copolymer (A-3), and 47 weight % by＜preparation example II-1 phenylethylene resin series 100 weight parts formed of prepared styrene based copolymer (B-1), the constituent that makes is surveyed dipolymer or the trimeric total content that its styrenic monomers and/or acrylic monomer are become equally, residual styrenic monomers content, and every physical property test, the result is stated from the subordinate list one.

＜comparative example 1 〉

Depend on the contained prescription of table one, former and deputy material is mixed the back carry out the physical property measurement of product and stink, cigarette amount, thermal stability evaluation, result such as subordinate list one with embodiment 1.

＜comparative example 2 〉

Repeat comparative example 1, but do not add trinonylphengl phosphite (TNPP), and change the sulfo-distearyl acyl group dipropionate (DSTDP) that adds 1 weight part, result such as subordinate list one.

＜comparative example 3 〉

Operational condition with embodiment 1, difference is: use instead by＜preparation example II-3〉prepared styrene based copolymer (B-3), dipolymer or trimeric total content that styrenic monomers during it is formed and/or acrylic monomer are become are 31,000ppm, residual styrenic monomers content is 2,500ppm, result also are stated from subordinate list one.

＜comparative example 4 〉

Depend on the contained prescription of table one, after former and deputy material is mixed, carry out the physical property measurement of product with embodiment 1, and stink, cigarette amount, thermal stability evaluation, result such as subordinate list one.

Test-results by subordinate list one shows as can be known, in styrene-series resin compositions and with the phosphorous antioxidant D of the trinonylphengl phosphite of 1 weight part and the Irganox-1076 of 0.4 weight part, though the stink test-results is good, but make cigarette amount showed increased, and thermostability (Δ YI) is still not good, and this is by the test-results susceptible of proof of comparative example 1; And show by comparative example 2, the antioxidant of styrene-series resin compositions and the sulfo-distearyl acyl group dipropionate that is with 1 weight part thioether, though and the cigarette amount is few during the Irganox-1076 of 0.4 weight part, obviously produces stink, and thermostability is improved still obviously not enough; Show by comparative example 3 again, contained styrenic monomers and/or the monomeric dipolymer of acrylic and trimer total content are higher than 25 in styrene-series resin compositions, 000ppm, and residual styrenic monomers is higher than 2, during 000ppm, its stink and cigarette amount all obviously increase; Experimental result by comparative example 4 shows, add the antioxidant DSTDP (E) of 1.6 weight parts and the Irganox-1076 of 0.5 weight part, its thermostability is suitable with the present invention reluctantly, but the extremely dense stink of deriving, and the cost height of antioxidant, heavy addition does not also meet economic benefit.

Review embodiment 1～8, via and be antioxidant E with butylation reaction product C and phosphorous antioxidant D and/or thioether, only need a spot of antioxidant can reach good thermostability, and employed antioxidant amounting is few, so can not produce tangible stink and the cigarette amount waits disappearance more; So the present invention is through aforementioned each composition and use quantitative limitation, can obtain adding few, the low odor of cigarette amount in man-hour, and the styrene-series resin compositions of good thermal stability.

The above only is several preferable possible embodiments of the present invention, is familiar with this technology personage such as, and it all should be included in the technical scheme of the present invention according to equivalent modifications or change that technical solution of the present invention is done.

Subordinate list one: the composition of various embodiments of the present invention and comparative example, consumption and test-results.

Subordinate list one

Experiment numbers			Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4	Embodiment 5	Embodiment 6	Embodiment 7	Embodiment 8	Comparative example 1	Comparative example 2	Comparative example 3	Comparative example 4
Experiment numbers			Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4	Embodiment 5	Embodiment 6	Embodiment 7	Embodiment 8	Comparative example 1	Comparative example 2	Comparative example 3	Comparative example 4	Use composition	Graft copolymer A (weight part)	A-1	35	35	35	35	35	-	-	18	35	35	35	35
A-2	-	-	-	-	-	38	33	15	-	-	-	-					A-1	35	35	35	35	35	-	-	18	35	35	35	35
A-2	-	-	-	-	-	38	33	15	-	-	-	-	A-3	-			-	-	-	-	-	30	20	-	-	-	-
Styrene based copolymer B (weight part)	B-1	65	65	-	65	65	62	37	47	65	65	-	A-3	-			-	-	-	-	-	30	20	-	-	-	-	65
	B-1	65	65	-	65	65	62	37	47	65	65	-	B-2	-		-	65	-	-	-	-	-	-	-	-	-		65
	B-3	-	-	-	-	-	-	-	-	-	-	65	B-2	-		-	65	-	-	-	-	-	-	-	-	-	-
	B-3	-	-	-	-	-	-	-	-	-	-	65	Irganox-1076 (weight part)			-	-	-	0.3	-	-	-	-	0.4	0.4	-	-	0.5
Winstay-L C (weight part)		0.2	0.3	0.2	0.1	0.2	0.2	0.2	0.2	-	-	0.2	Irganox-1076 (weight part)			-	-	-	0.3	-	-	-	-	0.4	0.4	-	-	0.5
Winstay-L C (weight part)		0.2	0.3	0.2	0.1	0.2	0.2	0.2	0.2	-	-	0.2	TNPP D (weight part)			0.4	0.4	0.4	0.4	-	0.3	0.4	0.4	1	-	0.4	-	-
DSTDP E (weight part)		-	-	-	-	0.4	0.1	-	-	-	1	-	TNPP D (weight part)			0.4	0.4	0.4	0.4	-	0.3	0.4	0.4	1	-	0.4	1.6	-
DSTDP E (weight part)		-	-	-	-	0.4	0.1	-	-	-	1	-	Test subject	SM is that monomer and/or AN are dipolymer or the trimer (ppm) that monomer becomes		15000	15300	8200	14800	15100	14400	16200	14200	15600	15500	31000	1.6	15200
Residual SM monomer (ppm)		1200	1220	650	1180	1200	1200	1320	1150	1420	1380	2500				15000	15300	8200	14800	15100	14400	16200	14200	15600	15500	31000	1230	15200
Residual SM monomer (ppm)		1200	1220	650	1180	1200	1200	1320	1150	1420	1380	2500		Stink		○	○	◎	○	○	○	○	○	○	×	×	1230	××
The cigarette amount		○	○	◎	○	○	○	○	○	×	○	×		Stink		○	○	◎	○	○	○	○	○	○	×	×	○	××
The cigarette amount		○	○	◎	○	○	○	○	○	×	○	×		Thermostability (Δ YI)		31.0	27.0	30.2	47.5	32.4	29.5	32.1	30.7	60.0	57.5	33.5	○	38.2

Annotate: 1Irganox-1076 is octadecyl-3-(3,5-two-tertiary butyl-4-hydroxy-phenyl)-propionic ester.

2Winstay-L is for reacting the product C that gets by p-Cresol and dicyclopentadiene through butylation.

(Butylated reaction product of p-cresol and dicyclopentadiene)。

3TNPP is trinonylphengl phosphite (Tris nonylphenyl phosphite).

4DSTDP is sulfo-distearyl acyl group dipropionate (Di stearyl thio dipropionate).

5SM is a vinylbenzene.

6AN is a vinyl cyanide.

7 Δ YI are that the test piece with resin places 180 ℃ baking box observed foxy after 50 minutes.

Claims

1. styrene-series resin compositions is characterized in that composition comprises:

The phenylethylene resin series of (1) 100 weight part, it is made up of rubber like graft copolymer A5～100 weight %, styrene based copolymer B0～95 weight %; Wherein, rubber like graft copolymer A is in the presence of diene series rubber, gets with the copolymerizable monomer graft copolymerization of styrenic monomers, acrylic monomer and 0～40 weight %;

Dipolymer or trimeric total content that styrenic monomers that above-mentioned styrene-series resin compositions is contained and/or acrylic monomer are become are lower than 25,000ppm, and residual styrenic monomers is 2, below the 000ppm.

2, styrene-series resin compositions according to claim 1 is characterized in that: dipolymer that styrenic monomers and/or acrylic monomer are become in the constituent or trimer total content are 20, below the 000ppm.

3, styrene-series resin compositions according to claim 1 is characterized in that: contained residual benzene vinyl monomer is 1, below the 500ppm in the constituent.

4, styrene-series resin compositions according to claim 1 is characterized in that: constituent is 0.02～1 weight part by the usage quantity of the product C that p-Cresol and dicyclopentadiene get through the butylation reaction.