CN1239601C - Serial thermoplastic polystyrene resin compositions - Google Patents

Abstract

The present invention discloses a thermoplastic styrene series resin composition which comprises a thermoplastic styrene series copolymer (A). The thermoplastic styrene series copolymer (A) is composed of (i-1) 15 to 100 parts by weight of styrene series monomer derivatives, (i-2) 0 to 45 parts by weight of cyanide vinyl series monomer derivatives, (i-3) 0 to 40 parts by weight of other vinyl series monomer derivatives which are used for copolymerization and 0.0005 to 1.0 parts by weight of multifunctional maleimide series monomer derivatives, wherein the total of (i-1) to (i-3) is 100 parts by weight. The thermoplastic styrene series resin composition is a thermoplastic styrene series resin composition which simultaneously has the advantages of forming machining performance, such as good flowability, vacuum forming performance, etc., and good hue.

Description

Thermoplastic styrene resin composition

Affiliated technical field

The present invention provides a kind of modified rubber thermoplastic styrene resin composition that contains the thermoplastic styrene constituent of specific thermoplastic styrene multipolymer (A) and contain this multipolymer (A) and rubber particles.This thermoplastic styrene constituent and modified rubber thermoplastic styrene resin composition have high workability, the forming process characteristic of excellent vacuum formability etc.

Background technology

General thermoplastic styrene resin, because of all there is good evaluation its processing forming, mechanicalness aspect, the big characteristic of one especially on the good appearance of moulding product and the glossiness especially is so be widely used on electronics, electrical appliance and the auto parts.

Generally speaking, the thermoplastically styrene resin can ejection formation, extrusion moulding, blow forming methods such as prolonging moulding and process.When the particular process moulding,, after then need be extruded into tabular (sheet) earlier with above-mentioned resin, make needed moulding product in the vacuum forming mode more in addition as the product that some need require with vacuum forming.For reaching the requirement of vacuum forming, this resin must possess high molten intensity, that is the high resin molecular weight, can possess good thickness homogeneity and dimensional stability when thermoforming or vacuum forming.But after generally improving the molecular weight of resin, will cause shortcomings such as mobile decline, processibility variation and productivity reduction.

For improving vacuum formability and flowability simultaneously, open day disclosure special permission communique such as spy that clear 59-149912, spy open flat 2-182711, the spy opens among the flat 8-269137 and discloses, improved in the mode of adding the difference agent, the general difference agent of being added belongs to multi-functional reaction monomers, for example divinyl compound (for example Vinylstyrene) or multivalence acrylate (acrylate) compound; But in manufacturing processed,, reduce and shortcomings such as processibility variation, cause easily and build bridge and cause resin to be attached to the pipeline surface forming carbide, and then cause productivity to reduce, and prepared resin form and aspect are not good though can avoid mobile if use this type of monomer.And when the production time of this resin increases (for example more than 2 weeks), the problems referred to above are named a person for a particular job more obvious.

Therefore, how improving resin flow and processing forming simultaneously and possess the good form and aspect of resin, is for be familiar with this technical field person, wish the problem that breaks through for a long time always.

Summary of the invention

Problem of the present invention promptly provides a kind of have simultaneously forming process and the good thermoplastic styrene resin compositions of form and aspect such as good flowability, vacuum formability.

The present invention provides a kind of thermoplastic styrene resin composition that contains thermoplastic styrene multipolymer (A), this thermoplastic styrene multipolymer (A) is by the nitrilation vinyl monomer derivative of the styrenic monomers derivative of (i-1) 15～100 weight parts, (i-2) 0～45 weight part, other copolymerizable vinyl monomer derivative of (i-3) 0～40 weight part, more than (i-1)～(i-3) add up to 100 weight parts, and the multi-functional maleimide of 0.0005～1.0 weight part be that the monomer derived thing is formed.

And the present invention provides a kind of modified rubber thermoplastic styrene resin composition in addition, it is the styrenic monomers derivative by (i-1) 15～100 weight parts, (i-2) the nitrilation vinyl monomer derivative of 0～45 weight part, (i-3) the copolymerizable vinyl monomer derivative of other of 0～40 weight part, more than (i-1)～(i-3) add up to 100 weight parts, and the multi-functional maleimide of 0.0005～1.0 weight part is that the thermoplastic styrene multipolymer (A) formed of monomer derived thing is as external phase, rubber particles (B) constitutes as disperse phase, and this rubber part amount is 1～40 weight %.

The thermoplastically styrene resin fat composition of modified rubber of the present invention, because of it is as external phase by thermoplastic styrene multipolymer (A), rubber particles (B) is former as what disperse phase constituted, mechanical properties excellences such as the thermostability of this constituent, impact strength, flowability, and vacuum forming adds man-hour, the homogeneity of the thick distribution of meat, and the application surface luster homogeneity of ejection formed piece is also quite good.

The object lesson of (i-1) used in the present invention styrenic monomers as: vinylbenzene, alpha-methyl styrene, right-t-butyl styrene, p-methylstyrene, neighbour-vinyl toluene ,-vinyl toluene, 2,4-dimethyl styrene, ethyl styrene, Alpha-Methyl-p-methylstyrene and bromstyrol etc., wherein, preferable with vinylbenzene or alpha-methyl styrene.Above-mentioned each compound can be used alone or as a mixture.Styrenic monomers of the present invention is 15～100 weight parts, is preferably 20～95 weight parts, is more preferred from 25～90 weight parts.

Being used in (i-2) of the present invention nitrilation vinyl monomer can be: vinyl cyanide, Alpha-Methyl vinyl cyanide etc., and wherein preferable with vinyl cyanide.Forming nitrilation vinyl monomer of the present invention is 0～45 weight part, is preferably 2～40 weight parts, is more preferred from 3～40 weight parts.

Being used in other copolymerizable vinyl monomer of the present invention can be: acrylic ester monomer, methacrylate ester monomer and simple function maleimide are monomer etc.

Wherein, the monomeric concrete example of acrylic ester as: methyl acrylate, ethyl propenoate, isopropyl acrylate, butyl acrylate polyethyleneglycol diacrylate (polyethylene glycol diacrylate) etc. wherein, are good with butyl acrylate.

And methacrylate ester monomeric object lesson is as methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, the methacrylic acid benzene methyl, N-Hexyl methacrylate, cyclohexyl methacrylate, methacrylic acid dodecane ester, methacrylic acid 2-hydroxyl ethyl ester, glytidyl methacrylate, dimethylaminoethyl methacrylate, ethylene dimethacrylate (ethylenedimethacrylate), dimethacrylate peopentyl esters (neopentyl dimethacrylate) etc. are wherein with methyl methacrylate, butyl methacrylate is good.

Be meant and only contain single maleimide functional group in the monomer and the simple function maleimide is a monomer, its object lesson is as maleimide, 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-methyl maleimide, N-2,3-3,5-dimethylphenyl maleimide, N-2,4-3,5-dimethylphenyl maleimide, N-2,3-diethyl phenyl maleimide, N-2,4-diethyl phenyl maleimide, N-2,3-dibutyl phenyl maleimide, N-2,4-dibutyl phenyl maleimide, N-2,6 3,5-dimethylphenyl maleimides, N-2,3-dichlorophenyl maleimide, N-2,4-dichlorophenyl maleimide, N-2,3-dibromo phenyl maleimide or N-2,4-dibromo phenyl maleimide etc., wherein preferable with N-phenylmaleimide.

In addition, ethene system single amount body, for example acrylic monomer (as: vinylformic acid that other common coincidence is possible, methacrylic acid), Maleic Acid, Anhydrous, anhydrous methyl-maleic acid, anhydrous methylfumaric acid, fumaric acid (fumaric acid), methylene-succinic acid unsaturated carboxylic acid based compounds such as (itaconic acid) with and esterification system single amount body (dimethyl fumarate for example, dibutyl itaconate), ethene, propylene, 1-butylene, the 1-amylene, 4-methyl-1-pentene, ethylene chloride, the ethylene chloride fork, tetrafluoroethylene, 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, triallyl isocyanate (triallyl isocyanate) etc.

Forming other copolymerizable vinyl monomer derivative of the present invention is 0～40 weight part, be preferably 2～40 weight parts, be more preferred from 3～38 weight parts, wherein the monomeric concrete example of other copolymerizable vinyl monomer derivative as described above, being preferably and being selected from a kind of acrylate monomer, methacrylate ester monomer or simple function maleimide at least is monomer.

Being used in multi-functional maleimide of the present invention is monomer, is meant the minimum compound that contains 2 maleimide functional groups, for example 2 or 3 or 4 maleimide functional groups' compound.Wherein, be that monomer is good with bismaleimides again, its structural formula can general expression (1) expression general expression (1)

[in the formula, X is the alkylidene group (alkylene) of carbon number 1～10, arylidene (arylene), carbonyl (carbonylgroup) ,-SO ₂-,-SO-,-O-, (R can be alkylidene group to-O-R-O-, arylidene)], concrete example is: N, N '-4,4 '-(3,3 '-dimethyl diphenylmethane) bismaleimides [N, N '-4,4 '-(3,3 '-dimethyl diphenylmethane) bismaleimide], N, N '-4,4 '-(3,3 '-the diethyl ditan) bismaleimides [N, N '-4,4 '-(3,3 '-diethyl diphenyl methane) bismaleimide], N, N '-4,4 '-ditan bismaleimides (N, N '-4,4 '-diphenyl methane bismaleimide), N, N '-4,4 '-2,2-diphenyl propane bismaleimides (N, N '-4,4 '-2,2-diphenyl propane bismaleimide), N, N '-4,4 '-diphenyl ether bismaleimides (N, N '-4,4 '-diphenyl ether bismaleimide), N, N '-3, the 3 '-all bismaleimidess of hexichol foundation stone (N, N '-3,3 '-diphenyl sulfone bismaleimide), N, N '-4, the 4 '-all bismaleimidess of hexichol foundation stone (N, N '-4,4 '-diphenyl sulfone bismaleimide), N, the all bismaleimidess of the inferior stone of N '-4,4 '-phenylbenzene (N, N '-4,4 '-diphenyl sulfoxide bismaleimide), N, N '-4,4 '-benzophenone bismaleimides (N, N '-4,4 '-benzophenone bismaleimide), N, N '-1,3-phenylene bismaleimides (N, N '-1,3-phenylene bismaleimide), wherein with N, N '-4,4 '-ditan bismaleimides, N, N '-1,3-phenylene bismaleimides is preferable.

Multi-functional maleimide of the present invention is that the monomer derived thing is 0.0005～1.0 weight part, is preferably 0.001～0.3 weight part, is more preferred from 0.003～0.1 weight part.

Thermoplastic styrene resin composition of the present invention is to contain thermoplastic styrene multipolymer (A), this multipolymer (A) is by the nitrilation vinyl monomer derivative of the styrenic monomers derivative of (i-1) 15～100 weight parts, (i-2) 0～45 weight part, other copolymerizable vinyl monomer derivative of (i-3) 0～40 weight part, more than (i-1)～(i-3) add up to 100 weight parts, and the multi-functional maleimide of 0.0005～1.0 weight part be that the monomer derived thing is formed.

Among the present invention, if with the total amount of aforementioned (i-1)～(i-3) as 100 weight parts, when the multi-functional maleimide in the thermoplastically styrol copolymer (A) is that the ratio of monomer derived thing is when being higher than 0.0005 weight part, then this thermoplastic styrene resin is when shaping, and its maximum elongation stress is preferable.When multi-functional maleimide is the ratio of monomer derived thing when being lower than 1.0 weight parts, then this thermoplastic styrene resin flow, form and aspect are preferable.

In the thermoplastic styrene resin composition of the present invention, remaining multi-functional maleimide is that amount of monomer is below the 100ppm, is preferably below the 60ppm, is more preferred from below the 30ppm, if there is not remaining the best fully.Its remaining monomeric mensuration mode is that this thermoplastic styrene resin composition is dissolved in the tetrahydrofuran (THF), with Hewlett-Packard's science and technology (Hewlett Packard) company, numbering 6890A is with the gas chromatograph (Gas Chromatography) of the flame analyzer mensuration that performs an analysis with this resin solution.Measuring numerical value unit is ppm, and it is the thermoplastic styrene resin composition based on 100wt%.

In the constituent, when remaining multi-functional maleimide is a monomer when being lower than 100ppm, then the form and aspect of this constituent are preferable.

In the thermoplastically styrol copolymer of the present invention (A), MZ (Z molecular-weight average)/MW (weight average molecular weight) is preferably 2.5～7 between 2～8, is more preferred from 3～6.Its mensuration mode is to utilize the gel dialysis chromatograph (GPC, Waters Company system) of the detecting of tool differential flexion rate and two functions of scattering of light detecting to measure as analyzer.When the MZ/MW of thermoplastic styrene multipolymer (A) between 2～8 the time, then the flowability of the thermoplastic styrene resin composition of thermoplastic styrene resin composition or modified rubber, maximum elongation viscosity and form and aspect are preferable.

The difference of thermoplastic styrene resin composition of the present invention than (gM) between 0.45～0.95, this difference than (gM) but through type (1) calculate and get

Formula (1)

$\mathrm{gM}=\frac{{\left(r^2\right)}_b}{{\left(r^2\right)}_1}$

Wherein, (r ²) _b: the rotation radius of difference molecule; (r ²) ₁: the mensuration mode of the rotation radius difference ratio of straight-chain molecule is to utilize gel dialysis chromatograph (GPC) the series connection Wyatt Technology Corporation system of Waters company earlier, the multiple angle laser light scattering system of type Minidawn (multi-angle laser light scattering MALLS) record when molar mass (molar mass) be 1 * 10 ⁶The rotation radius of difference molecule and straight-chain molecule during g/mole utilizes formula (1) to calculate and get again.Difference is than the difference structural regime index that is polymkeric substance, and is general, the polymkeric substance identical for molecular weight, and its value is littler, and then the difference structure is the more.Among the present invention, above-mentioned difference is than changing along with the ratio of multi-functional maleimide list amount body, and when the usage quantity of maleimide list amount body is adjusted in the specialized range of the present invention, then above-mentioned difference ratio will be easier to reach.

The difference of thermoplastic styrene resin composition of the present invention between 0.45～0.95, is preferably 0.5～0.9 than (gM), is more preferred from 0.6～0.8.When difference than gM between 0.45～0.95 the time, then the flowability of thermoplastic styrene resin composition, maximum elongation stress and form and aspect are preferable.

The manufacture method of thermoplastic styrene multipolymer of the present invention (A) can be finished by the general continous way bulk of using or solution polymerization, emulsion polymerization reaction, outstanding turbid polyreaction; Wherein preferable with continous way bulk or solution polymerization.The previous reaction device can comprise: column flow reactor (PFR), hybrid fully (CSTR) reactor or contain reactor of silent oscillation mixing tank etc. are good with complete mixing reactor wherein.And reactor quantity can be one, also can and use two or more.When the reactor that uses more than 2, final reactor is to use PFR preferable, and the quantity of reaction unit can be 1, more than 2 or 3 and use; When making thermoplastic styrene multipolymer of the present invention (A), its manufacture is the material solution of reaction usefulness to be sent in the reactor continuously react, and polymerization starter can be added in the reaction.

Thermoplastic styrene multipolymer of the present invention (A) in the mill, usually, addible polymerization starter, its usage quantity 0～1 weight part, be preferably 0.001～0.5 weight part, spendable polymerization starter can be: simple function initiator or multi-functional initiator, wherein, concrete simple function initiator for example is: dibenzoyl peroxide (benzoyl peroxide), dicumyl peroxide (dicumyl peroxide), tert-butyl peroxide (t-butyl peroxide), tert-butyl hydroperoxide (t-butyl hydroperoxide), Cumene Hydroperoxide 80 (cumene hydroperoxide), tert butyl peroxy benzoate ((t-butyl-peroxybenzoate), two-2-ethylhexyl peroxy dicarbonate (bis-2-ethylhexyl peroxy dicarbonate), tert-butyl hydroperoxide sec.-propyl carbonic ether (tert-butyl peroxy isopropyl carbonate, be called for short BPIC), cyclohexanone peroxide (cycolhexanone peroxide), 2,2 '-azo-two-isopropyl cyanide (2,2 '-azo-bis-isobutyronitrile), 1,1 '-azo bis cyclohexane-1-carbonyl nitrile (1, l '-azo-biscyclohexane-1-carbonitrile), 2,2 '-azo-two-2-methylbutyronitrile (2,2 '-azo-bis-2-methyl butyronitrile) etc.Wherein preferable with dibenzoyl peroxide, dicumyl peroxide.

The object lesson of the spendable multi-functional initiator of the present invention has: 1,1-pair-tert-butyl hydroperoxide hexanaphthene (1,1-bis-t-butyl peroxy cyclohexane, be called for short TX-22), 1,1-pair-tert-butyl hydroperoxide-3,3,5-trimethyl-cyclohexane (1,1-bis-t-butylperoxy-3,3,5-trimethyl cyclohexane, be called for short TX-29A), 2,5-dimethyl-2,5-pair-(2-ethyl peroxidation hexanoyl) hexane [2,5-dimethyl-2,5-bis-(2-ethylhexanoxy peroxy) hexane], 4-(tert-butyl hydroperoxide carbonyl)-3-hexyl-6-[7-(tert-butyl hydroperoxide carbonyl) heptyl] hexanaphthene 4-(t-butyl peroxycarbonyl)-3-hexyl-6-[7-(t-butyl peroxy carbonyl) heptyl] cyclohexane}, two-tertiary butyl diperoxy azelate (di-t-butyl-diperoxyazelate), 2,5-dimethyl-2, two (benzoyl the peroxidation)-hexanes [2 of 5-, 5-dimethyl-2,5-bis-(benzoyl peroxy) hexane], two-tert-butyl hydroperoxide-six hydrogen-terephthalate (di-t-butyl peroxy-hexahydro-terephthalate, be called for short BPHTH), 2,2-two (4,4-two-tert-butyl hydroperoxide) cyclohexyl propane [2,2-bis-(4,4-di-t-butyl peroxy) cyclohexyl propane], multi-functional single peroxycarbonates (multifunctional monoperoxycarbonate) (for example U.S. ATOFINA society system, trade(brand)name Luperox JWE) etc.; Wherein with 1,1-is two-tert-butyl hydroperoxide-3,3, and 5-trimethyl-cyclohexane, two-tert-butyl hydroperoxide-six hydrogen-terephthalate are preferable.

The temperature of reaction of above-mentioned reactor is to be controlled at 20～300 ℃, is preferably 60～250 ℃, is more preferred from 80～200 ℃, and the pressure of reactor is to be controlled at 1～10kg/cm ²Between, be trapped in time in the reactor generally at 0.5～15 hour as for material solution, be preferably 1～10 hour; And, can use chain-transfer agent among the present invention for the molecular weight of controlling polymers, its usage quantity is 0～2 weight part, is preferably 0.001～1 weight part; Employed chain-transfer agent can be simple function chain-transfer agent or multi-functional chain-transfer agent, and concrete simple function chain-transfer agent has:

1) mercaptan (mercaptan) class: methyl mercaptan, n-butyl mercaptan, cyclohexyl mercaptan, just-lauryl mercaptan, stearyl-mercaptan (stearyl mercaptan), uncle's lauryl mercaptan (t-dodecyl mercaptan is called for short TDM), just-propyl group mercaptan, n-octyl mercaptan, uncle-octyl mercaptan, uncle-nonyl mercaptan etc.

2) alkanamine (alkyl amines) class: single ethylamine, diethylamide, triethylamine, single isopropylamine, diisopropylamine, monobutyl amine, di-n-butyl amine, three-n-butylamine etc.

3) other are for example: pentaphenylethane (pentaphenylethane), α-Jia Jibenyixierjuwu (α-methyl styrene dimer), terpinolene (terpinolene), wherein with in the thio-alcohol just-lauryl mercaptan, uncle's lauryl mercaptan are preferable.

Multi-functional chain-transfer agent for example is: isoamyl tetrol four (3-mercaptopropionic acid ester) [pentaerythritoltetrakis (3-mercapto propionate)], isoamyl tetrol four (2-mercaptoacetate) [pentaerythritoltetrakis (2-mercapto acetate)], three-(2-Thiovanic acid) trishydroxymethyl propyl ester [trimethylolpropanetris (2-mercapto acetate)], three-(3-thiohydracrylic acid) trishydroxymethyl propyl ester [trimethylolpropanetris (3-mercapto propionate) is called for short TMPT], three-(6-mercaptohexanoic acid) trishydroxymethyl propyl ester [trimethylol-propane tris (6-mercapto hexanate)] etc.; Above-mentioned cited person, preferable with three-(3-thiohydracrylic acid) trishydroxymethyl propyl ester.

The method for making of above-mentioned thermoplastic styrene multipolymer (A), be material solution to be imported reaction unit continuously react, when the whole single amount bodies in the material solution reach behind the fixed turnover ratio, again doubling body solution is taken out continuously by reaction unit, importing the devolatilization device removes unreacted single amount body and volatilization composition, afterwards, give granulation again.General devolatilization device can use decompression degassing vessel device, or extrudes de-gassing vessel.Reclaim unreacted single amount body or volatilization composition with condenser more afterwards, after the moisture in the recovery liquid can being removed in case of necessity, use as material solution again.

When thermoplastic styrene multipolymer of the present invention (A) was made, employed material solution included: (i-1) 15～100 parts by weight of styrene are monomer, (i-2) 0～45 weight part nitrilation vinyl monomer, other copolymerizable vinyl monomer of (i-3) 0～40 weight part (above total 100 weight parts), and to add up to the multi-functional maleimide of 0.0005～1.0 weight part of 100 weight parts with respect to (i-1)～(i-3) be the solvent of monomer, 0～60 weight part.Above-mentioned (i-1) styrenic monomers is preferably 20～95 weight parts, is more preferred from 25～90 weight parts.(i-2) the nitrilation vinyl monomer is preferably 2～40 weight parts, is more preferred from 3～38 weight parts.(i-3) other copolymerizable vinyl monomer is preferably 2～40 weight parts, is more preferred from 3～38 weight parts.Multi-functional maleimide is that monomer is preferably 0.001～0.3 weight part, is more preferred from 0.003～0.1 weight part.

In the material solution used in the present invention, styrenic monomers, nitrilation vinyl monomer, other copolymerizable vinyl monomer and multi-functional maleimide are monomeric enumerating as hereinbefore, do not give unnecessary details at this.Wherein, the vinyl monomer that other is copolymerizable is preferably and is selected from least a acrylic ester monomer, and methacrylate ester monomer and simple function maleimide are monomer 0～40 weight part, are preferably 2～40 weight parts, are more preferred from 3～38 weight parts.

The employed solvent of material solution can be benzene, toluene, ethylbenzene, p-Xylol, o-Xylol, m-xylene, reaches pentane, octane, hexanaphthene, reaches methylethylketone, acetone, methyl butyl ketone etc.

Among the present invention, further can be with thermoplastic styrene multipolymer (A) as external phase, rubber particles (B) is as disperse phase, and makes the modified rubber thermoplastic styrene resin composition, wherein, amount 1～40 weight % of rubber part, be preferably 3～35 weight %.

The manufacture method of modified rubber thermoplastic styrene resin composition of the present invention is the rubber composition can be made an addition in the polyreaction processing procedure of thermoplastic styrene multipolymer (A), participates in reaction (following with while grafting method abbreviation).Perhaps rubber composition (as ordinary rubber or rubber graft copolymer, being good with rubber graft copolymer especially) is directly mixed to extrude with thermoplastic styrene multipolymer of the present invention (A) and make (following) with the mixing method abbreviation of grafting.Aforesaid while grafting method can adopt generally that block coincidence method, solution weight are legal, emulsification coincidence method or outstanding turbid coincidence method finished.The manufacture method of aforesaid rubber graft copolymer generally can the emulsification coincidence method, the block coincidence method of emulsification finished, and is wherein preferable with the emulsification coincidence method.

The thermoplastic styrene resin composition of modified rubber of the present invention, wherein, the weight average particle diameter of rubber particles (B) generally at 0.05～10 μ m, is preferably 0.1～5 μ m, is more preferred from 0.1～1 μ m.

The manufacture method of the thermoplastic styrene resin composition of modified rubber of the present invention, below enumerate two kinds of methods and be illustrated:

＜method one: the method for grafting simultaneously 〉

Method one can utilize continous way bulk or solution polymerization to make modified rubber thermoplastic styrene resin composition of the present invention.Method one employed reaction unit comprises: column flow reactor (PFR), hybrid fully (CSTR) reactor or contain reactor of silent oscillation mixing tank etc., be good wherein with complete mixing reactor, and reactor quantity can be one, also can and use two or more.When using a plurality of reaction unit, final reaction unit is to use PFR preferable.Manufacture is will be satisfied with the material solution of modified rubber thermoplastic styrene resin composition of the present invention (containing the rubber composition) earlier to send in the reactor continuously and react, temperature of reaction is to be controlled at 30～300 ℃, be preferably 60～250C, be more preferred from 80～200 ℃, and the pressure of reactor normally is controlled at 1～10kg/cm ²Between, the time that is trapped in the reactor as for material solution should be preferably 1～10 hour at 0.5～15 hour; And be the molecular weight of controlling polymers, in the manufacturing of modified rubber thermoplastic styrene resin composition of the present invention, can optionally use polymerization starter or chain-transfer agent.

The method for making of above-mentioned modified rubber thermoplastic styrene resin composition, be material solution to be imported reaction unit continuously react, when the whole single amount bodies in the material solution reach behind the fixed turnover ratio, again doubling body solution is taken out continuously by reaction unit, importing the devolatilization device removes unreacted single amount body and volatilization composition, afterwards, give granulation again, and get modified rubber thermoplastic styrene resin composition of the present invention.General devolatilization device can use decompression degassing vessel device, or extrudes de-gassing vessel.Reclaim unreacted single amount body or volatilization composition with condenser more afterwards, after the moisture in the recovery liquid can being removed in case of necessity, use as material solution again.

The employed material solution of the bulk of modified rubber thermoplastic styrene resin composition of the present invention or solution polymerization process includes: (i-1) 15～100 parts by weight of styrene are monomer, (i-2) 0～45 weight part nitrilation vinyl monomer, (i-3) other copolymerizable vinyl monomer of 0～40 weight part (above total 100 weight parts), the multi-functional maleimide of 0.0005～1.0 weight part that reaches with respect to (i-1)～(i-3) 100 weight parts is a monomer, the rubber of 0～60 weight part solvent and 0.5～25 weight part; Wherein, styrenic monomers, nitrilation vinyl monomer, other copolymerizable vinyl monomers, multi-functional maleimide are that monomer, solvent reach optionally and the polymerization starter of interpolation, the usage quantity of chain-transfer agent and specifying is same as the material solution of making thermoplastic styrene multipolymer (A), does not give unnecessary details at this.

In the aforesaid method one, also available emulsion polymerization reacts and makes the modified rubber thermoplastic styrene resin composition.The method for making of emulsion polymerization reaction is identical with the method for making of following rubber like graft copolymer (B '), but the consumption of single amount body is slightly different.

In the bulk or solution polymerization of modified rubber thermoplastic styrene resin composition of the present invention, rubber and polystyrene list amount body, the mixing solutions of single amount bodies such as nitrilation ethene system single amount body is in the polymeric initial stage, rubber phase is that the state with external phase exists, but graft polymerization reaction along with rubber, polystyrene list amount body, the transformation efficiency of list amount bodies such as nitrilation ethene system single amount body increases gradually, and be accompanied by the stirring of reactor, the rubber composition is gradually by polystyrene list amount body, body measured by lists such as nitrilation ethene system single amount body and polymkeric substance surrounds, and change dispersed particle state (disperse phase) into, on the other hand, polystyrene list amount body, body measured by lists such as nitrilation ethene system single amount body and polymer transition is an external phase.Last rubber particles forms mutually.Weight average particle diameter 0.05～10 μ m of rubber particles is preferably 0.1～5 μ m, is more preferred from 0.1～1 μ m.

The concrete example of the rubber composition in the method one has: diene series rubber, polyolerin elastomer (routine ethylene-propylene rubber), polyacrylic ester are rubber, polysiloxane series rubber etc.Aforementioned diene series rubber be for: diene monomer composition through glass tansition temperature after the polymerization at the polymer below 0 ℃, the concrete example of diene series rubber: divinyl rubber, synthetic polyisoprene, neoprene, EPDM rubber, vinylbenzene-diene series rubber, vinyl cyanide-diene series rubber 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 (94～99%)/(0～5%), and all the other compositions then are trans (Trans) structure; Its 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 compositing range of cis/vinyl is in (20～40%)/(6～20%), and all the other are transconfiguration, and its Mooney (Mooney) viscosity is at 20～120, and molecular weight ranges is with 100,000～800, and 000 is good; The concrete example of vinylbenzene-diene series rubber such as styrene butadiene rubbers, styrene isoprene rubber etc., that it can be block copolymer, random copolymers or constituent is cumulative/multipolymer of (taper) decrescence.Wherein cinnamic part by weight scope is with preferable below the 50 weight % in the styrene/butadiene rubbers, and molecular weight ranges is preferably 50,000～600, and 000 is preferable; Above-mentioned rubber is good with divinyl rubber and styrene/butadiene rubbers.

＜method two: the mixing method of grafting 〉

Method two can be mixing by thermoplastic styrene multipolymer (A) and rubber graft copolymer (B '), extrudes and make modified rubber thermoplastic styrene resin composition of the present invention.

Method two, usually system is with thermoplastic styrene multipolymer (A) and rubber graft copolymer (B '), with the Han Xieer mixing machine of general use do mix after, again with such as after the mixing machine melting mixing of extruding mixing machine, kneader or Banbury (Banbury) Banbury mixer etc., extruding pelletization again.

The method for making of rubber graft copolymer (B '), general spendable bulk or solution polymerization, emulsion polymerization reaction or outstanding turbid polyreaction are finished.Wherein rubber graft copolymer (B ') is that material solution is carried out graft polymerization reaction with the manufacture method of bulk or solution polymerization.Material solution is: (i-1) other copolymerizable vinyl monomer of the nitrilation vinyl monomer of the styrenic monomers of 15～100 weight parts, (i-2) 0～45 weight part, (i-3) 0～40 weight part, the more than solvent and 0.5～25 parts by weight of rubber of total 100 weight parts, 0～60 weight part; It is monomer that material solution does not comprise multi-functional maleimide usually, is monomer if use multi-functional maleimide, and its used in amounts is below usage quantity lower limit of the present invention.And the explanation of the composition concrete example of rubber composition is with the explanation of method one.

In the bulk or solution polymerization of rubber graft copolymer of the present invention (B '), rubber and polystyrene list amount body, the mixing solutions of single amount bodies such as nitrilation ethene system single amount body is in the polymeric initial stage, rubber phase is that the state with external phase exists, but graft polymerization reaction along with rubber, polystyrene list amount body, the transformation efficiency of list amount bodies such as nitrilation ethene system single amount body increases gradually, and be accompanied by the stirring that reaction is, the rubber composition is gradually by polystyrene list amount body, body measured by lists such as nitrilation ethene system single amount body and polymkeric substance surrounds, and change dispersed particle state (disperse phase) into, on the other hand, polystyrene list amount body, body measured by lists such as nitrilation ethene system single amount body and polymer transition is an external phase.Last rubber particles forms mutually.Weight average particle diameter 0.05～10 μ m of rubber particles is preferably 0.1～5 μ m, is more preferred from 0.1～1 μ m.

Rubber graft copolymer (B ') also can be finished by emulsion polymerization in addition, its manufacture method is with rubber latex 40～90 weight parts (solid) and monomer or monomer mixture 60～10 weight parts such as styrenic monomers 100～15 weight %, nitrilation vinyl monomer 0～45 weight %, other copolymerizable monomer 0～40 weight %, and the emulsifying agent, initiator and the chain-transfer agent that optionally add carry out graft polymerization reaction, and obtain the rubber graft copolymer emulsion; Again with aforementioned graft copolymer emulsion via condense, dehydration, drying and other steps, to obtain rubber graft copolymer required for the present invention (B ').

Rubber composition concrete example explanation in the aforementioned rubber latex is good with diene series rubber again wherein with the explanation of the rubber composition in the method one.The manufacture method of diene series rubber emulsion, can diene monomer (for example divinyl) or diene monomer 100～50 weight % and other copolymerizable monomer 0～50 weight %, for example: copolymerizable monomer such as vinylbenzene, vinyl cyanide and (methyl) acrylate aggregate into the diene series rubber emulsion of weight average particle diameter 0.05～0.6 μ m with emulsion polymerization method; After also aforementioned monomer can being made the small particle size diene series rubber emulsion of weight average particle diameter 0.05～0.20 μ m with emulsion polymerization method, again with the loose method of freezing loose method, mechanical loose method or additive, with the big particle diameter diene series rubber emulsion of the loose one-tenth of aforementioned small particle size diene series rubber emulsion weight average particle diameter 0.22～0.6 μ m, 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 be salt-base substances such as sodium-chlor, Repone K, calcium chloride, and (methyl) vinylformic acid-(methyl) acrylate copolymer (as methacrylic acid-butyl acrylate copolymer, EUDRAGIT L100-55) etc. contains carboxylic acid group's polymer coagulant.

Among the present invention, the rubber amount of modified rubber thermoplastic styrene resin composition is 1～40 weight %, be preferably 34～35 weight %, be more preferred from 6～30 weight %, when the rubber amount between 1～40 weight %, then mechanical properties such as the impact strength of modified rubber thermoplastic styrene resin composition, flowability are preferable.

In the modified rubber thermoplastic styrene resin composition of the present invention, remaining multi-functional maleimide is that monomer is below the 100ppm, is preferably below the 60ppm, is more preferred from below the 30ppm, if do not have remaining then best fully.When remaining multi-functional maleimide is that monomer is lower than 100ppm, then the thermostability of this modified rubber thermoplastic styrene resin composition is preferable, the stain number is less.

The difference of modified rubber thermoplastic styrene resin composition of the present invention between 0.45～0.95, is preferably 0.5～0.9 than (gM), is more preferred from 0.6～0.8.When difference than (gM) between 0.45～0.95 the time, the flowability and the form and aspect of modified rubber thermoplastic styrene resin composition are preferable.Difference is described before being same as than the mensuration mode of (gM), but when measuring, needs earlier the rubber particles of disperse phase is removed from the modified rubber thermoplastic styrene resin composition.The difference of for example measuring the modified rubber thermoplastic styrene resin composition that makes with while grafting method is during than (gM), needs earlier selected solubilized thermoplastic styrene multipolymer (A) but solvent that can not the dissolving rubber particle, as methylethylketone; Use this solvent to go ahead of the rest behind the dissolving rubber modification thermoplastic styrene resin composition, remove by filter the rubber particles part, again with solvent evaporation and do not contain the composition of rubber particles, measure it again.And when MZ that measures modified rubber thermoplastic styrene resin composition of the present invention or MW, also need use as the above-mentioned thermoplastic styrene resin composition of removing rubber particles during mensuration.

In the modified rubber thermoplastically styrene resin fat composition of the present invention, in the composition of the thermoplastically styrol copolymer (A) of formation external phase, multi-functional maleimide is that the content of monomer derived thing is 0.0005～1.0 weight part, be preferably 0.001～0.3 weight part, be more preferred from 0.003～0.1 weight part; When multi-functional maleimide is that the content of monomer derived thing is when being higher than 0.0005 weight part, modified rubber thermoplastic styrene resin composition then, especially when being used as thermoplastically formed material purposes, it is when vacuum forming, the thick homogeneity of meat is good, and during injection molding, the surface luster homogeneity of application is good; When multi-functional maleimide is that the content of monomer derived thing is when being lower than 1.0 weight parts, modified rubber thermoplastic styrene resin composition then, especially when being used as thermoplastically formed material purposes, its thermostability is good, stain is few and during injection molding, the surface luster homogeneity of application is good; And mobile moderate because of polymkeric substance can carry out when the successive polyreaction smoothly.

In thermoplastic styrene resin composition of the present invention or the modified rubber thermoplastic styrene resin composition, can add various additives such as antioxidant, lubricant, UV light absorber, ultra-violet stabilizer, charged preventor, tinting material etc. in case of necessity, the interpolation time can or mixingly be extruded the stage in coincidence stage of thermoplastic styrene multipolymer (A) or each resin combination.Below 6 weight parts of its usage quantity with respect to the resin combination of 100 weight parts.Other additives such as incombustible agent, impact modifying agent etc. also can optionally add, and its addition is generally below 30 weight parts with respect to the resin combination of 100 weight parts.

In thermoplastic styrene resin composition of the present invention or the modified rubber thermoplastic styrene resin composition, but mixture heat plasticity-styrene based copolymer (A) resin in addition in case of necessity.That is: in the modified rubber thermoplastic styrene resin composition, can contain external phase is thermoplastic styrene multipolymer (A) various polymkeric substance in addition.This polymkeric substance can be acrylonitrile-butadiene-styrene resin, acrylonitrile styrene resin (AS), acrylonitrile-butadiene-αJia Jibenyixi resin, acrylonitrile-styrene-methyl-methacrylate resin, acrylonitrile-styrene-N phenyl maleimide resin, vinylbenzene-Maleic Acid, Anhydrous resin, vinylbenzene-N-phenylmaleimide resin, polymethylmethacrylate, polycarbonate resin, vinylbenzene-methacrylic resin, methacrylic acid-butadiene styrene resin, acrylonitrile-butadiene-N phenyl maleimide-styrene resin, polyamide resin, vibrin, polyphenylene oxide resin, vinyl cyanide-acrylic elastomer-styrene resin, vinyl cyanide-(ethylene-propylene diene series rubber)-styrene resin, vinyl cyanide-silica gel-styrene resin and other resin, this resin can separately or merge use.Its usage quantity is generally below 80 weight parts with respect to the resin combination of 100 weight parts.

Description of drawings

Shown in Figure 1 is the orthographic plan of maximum elongation viscosimeter of the present invention.

The figure number explanation:

Well heater 10 capillary rheometers 20

First roller, 30 second rollers 40

Export 50 molten resins 90

Embodiment

The preparation of embodiment 1[thermoplastic styrene multipolymer (A-1)]

With styrene monomer 68 weight parts, acrylonitrile monemer 32 weight parts, N, N '-4,4 '-raw material of ditan bismaleimide amine monomers 0.02 weight part, ethylbenzene 20 weight parts, polymerization starter benzoyl peroxide 0.02 weight part and chain-transfer agent uncle lauryl mercaptan 0.2 weight part mixed, this material solution is supplied to two tandems continuously mixes flow reactor fully, the volume of its reactor is respectively 40 liters and 70 liters, the interior temperature of 2 reactors keeps 100 ℃ and 120 ℃ respectively, and the pressure of reactor all keeps 4kg/cm ², the 2 hours total holdup time in the reactor, the monomer turnover ratio of two reactors keeps 30 weight % and 50 weight % respectively.

After polymerization ended, normally the copolymer solution with gained imported the devolatilization device, and the devolatilization device is as decompression devolatilization device or extrude devolatilization device etc., removes unreacted monomer and other fugitive constituents with this device; And, its extrusion granulator can be obtained thermoplastic styrene multipolymer of the present invention (A-1) through the polymerization melts of devolatilization; The manufacturing prescription and the Physical Property Analysis thereof of this thermoplastic styrene multipolymer (A-1) are listed in table 1.

The preparation of embodiment 2[thermoplastic styrene multipolymer (A-2)]

With the operating method of embodiment 1, difference is with N, and N '-4,4 '-monomeric consumption of ditan bismaleimides is adjusted into 0.01 weight part; The manufacturing prescription and the Physical Property Analysis thereof of this thermoplastic styrene multipolymer (A-2) are listed in table 1.

The preparation of embodiment 3[thermoplastic styrene multipolymer (A-3)]

Operating method with embodiment 1, difference is that each monomer blended consumption is done an adjustment, be respectively styrene monomer 58 weight parts, acrylonitrile monemer 22 weight parts, N, N '-4,4 '-ditan bismaleimide amine monomers 0.01 weight part, add N-phenylmaleimide monomer (N-phenyl maleimide is called for short N-PMI) 20 weight parts in addition, polymerization starter uses benzoyl peroxide 0.015 weight part and TX-29A0.005 weight part and uses; The manufacturing prescription and the Physical Property Analysis thereof of this thermoplastic styrene multipolymer (A-3) are listed in table 1.

The preparation of embodiment 4[thermoplastic styrene multipolymer (A-4)]

With styrene monomer 100 weight parts, N, N '-4,4 '-raw material of ditan bismaleimide amine monomers 0.02 weight part, ethylbenzene 8 weight parts, polymerization starter dibenzoyl peroxide 0.02 weight part and chain-transfer agent uncle lauryl mercaptan 0.02 weight part mixed, this material solution is supplied to three tandem column flow reactors (PFR) continuously, the volume of its reactor is all 100 liters, the interior temperature of reactor keeps 110 ℃, 130 ℃ and 160 ℃ respectively, and the pressure of reactor all keeps 3kg/cm ², the total holdup time in the reactor is 7 hours, the monomer turnover ratio of three reactors keeps 30 weight %, 60 weight % and 85 weight % respectively.

After polymerization ended, normally the copolymer solution with gained imported the devolatilization device, and the devolatilization device is as decompression devolatilization device or extrude devolatilization device etc., removes unreacted monomer and other fugitive constituents with this device; And, its extrusion granulator can be obtained thermoplastic styrene multipolymer of the present invention (A-4) through the polymerization melts of devolatilization, this thermoplastic styrene multipolymer (A-4) changes thermoplastic styrene resin composition into; The manufacturing prescription and the Physical Property Analysis thereof of this thermoplastic styrene multipolymer (A-4) are listed in table 1.

The preparation of comparative example 1[thermoplastic styrene multipolymer (A-5)]

With the operating method of embodiment 1, difference is not use N, N '-4,4 '-ditan bismaleimide amine monomers.The manufacturing prescription and the Physical Property Analysis thereof of this thermoplastic styrene multipolymer (A-5) are listed in table 1.

Comparative example 2

With the operating method of embodiment 1, difference is with N, and N '-4,4 '-monomeric consumption of ditan bismaleimides is adjusted into 1.5 weight parts; In the reaction process, because of the rapid rising of viscosity of reaction system, follow the form and aspect variation of resultant of reaction, stain to increase, polyreaction can't be proceeded as a result.

The preparation of embodiment 5[modified rubber thermoplastic styrene resin composition (C-1)]

With styrene monomer 74 weight parts, acrylonitrile monemer 26 weight parts, divinyl rubber 12 weight parts, N, N '-4,4 '-ditan bismaleimide amine monomers 0.02 weight part, ethylbenzene 20 weight parts, the raw material of polymerization starter dibenzoyl peroxide 0.05 weight part and chain-transfer agent uncle lauryl mercaptan 0.3 weight part is mixed, be supplied to four tandems continuously and mix flow reactor fully, the volume of its reactor is all 45 liters, the interior temperature of reactor keeps 95 ℃ respectively, 100 ℃, 110 ℃ and 120 ℃, the pressure of reactor keeps 4.5kg/cm respectively ², 4kg/cm ², 4kg/cm ²And 4kg/cm ², the total holdup time in the reactor is 4 hours, the monomer turnover ratio of four reactors keeps 22 weight %, 31 weight %, 45 weight % and 52 weight % respectively.

After polymerization ended, normally the copolymer solution with gained imported the devolatilization device, and the devolatilization device is as decompression devolatilization device or extrude devolatilization device etc., removes unreacted monomer and other fugitive constituents with this device; And through the polymerization melts of devolatilization, the thermoplastic styrene multipolymer (A) that its extrusion granulator can be obtained being made up of styrenic monomers derivative, nitrilation vinyl monomer derivative is as external phase, rubber particles (B) is as the modified rubber thermoplastic styrene resin composition (C-1) that disperse phase constituted, the weight average particle diameter 0.81 μ m of its rubber particles (B); The manufacturing prescription and the Physical Property Analysis thereof of this modified rubber thermoplastic styrene resin composition (C-1) are listed in table 2.

The preparation of comparative example 3[modified rubber thermoplastic styrene resin composition (C-2)]

With the operating method of embodiment 5, difference is not use N, N '-4,4 '-ditan bismaleimide amine monomers; Rubber particles (B) the weight average particle diameter 0.8 μ m of this modified rubber thermoplastic styrene resin composition (C-2); The manufacturing prescription and the Physical Property Analysis thereof of this modified rubber thermoplastic styrene resin composition (C-2) are listed in table 2.

The preparation of comparative example 4[modified rubber thermoplastic styrene resin composition (C-3)]

With the operating method of embodiment 5, difference is cancellation N, N '-4, the 4 '-monomeric interpolation of ditan bismaleimides, and add the PGDA0.02 weight part separately; The manufacturing prescription and the Physical Property Analysis thereof of this thermoplastic styrene resin composition (C-3) are listed in table 2.

The preparation of reference example 1[rubber graft copolymer (D-1)]

The raw material of styrene monomer 72 weight parts, acrylonitrile monemer 28 weight parts, ethylbenzene 20 weight parts, divinyl rubber 6.5 weight parts, polymerization starter dibenzoyl peroxide 0.05 weight part and chain-transfer agent uncle lauryl mercaptan 0.3 weight part is mixed, be supplied to four complete mixing reactors of tandem continuously, the volume of its reactor is all 45 liters, the interior temperature of reactor keeps 90 ℃, 100 ℃, 110 ℃ and 120 ℃ respectively, and the pressure of reactor all keeps 4kg/cm ², the monomer turnover ratio of four reactors keeps 23 weight %, 35 weight %, 42 weight % and 51 weight % respectively.

After polymerization ended, normally the copolymer solution with gained imported the devolatilization device, and the devolatilization device is as decompression devolatilization device or extrude devolatilization device etc., removed unreacted monomer and other evaporate into part with this device; And, its extrusion granulator can be obtained rubber graft copolymer of the present invention (D-1) (the weight average particle diameter 0.79 μ m of rubber content 10 weight %, rubber particles (B)) through the polymerization melts of devolatilization.

The preparation of reference example 2[rubber graft copolymer (D-2)]

[table 3]

Composition	Weight part
		1,3-butadiene	150.00
Potassium persulfate solution (1%)	15.00
		Potassium oleate	2.00
Distilled water	190.00
		Ethylene glycol dimethacrylate	0.13

According to the reaction 14 hours under 65 ℃ of temperature of reaction of above table 3 prescription, the synthetic rubber latex that obtain transformation efficiency and be 94%, solids content is about 36%, weight average particle diameter is about 0.1 μ m.

In addition, the polymer coagulant that contains the carboxylic acid group with composition manufacturing listed in the following table 4:

[table 4]

Composition	Weight part
		Butyl acrylate	90.00
Methacrylic acid	10.00
		Potassium persulfate solution (1%)	0.50
Sodium dodecyl sulfate solution (10%)	0.50
		The n-lauryl mercaptan	1.0
Distilled water	200.00

Under 75 ℃ of temperature of reaction, reacted 5 hours according to above prescription, obtain that transformation efficiency is about 95%, the polymer coagulant emulsion that contains the carboxylic acid group of pH value 6.0.

Afterwards, utilize the synthetic rubber latex of next loose 100 weight parts of the polymer coagulant that contains the carboxylic acid group of 3 weight parts (dry weight), the pH value of resulting rubber latex is 8.5, and its rubber weight average particle diameter is about 0.31 μ m.

At last, with the prescription of aforementioned enlarged rubber emulsion, the rubber latex of aforementioned hypertrophyization is carried out graft polymerization reaction with styrene-acrylonitrile copolymer again, to make rubber graft copolymer (D-2) according to following table 5.

[table 5]

Composition	Weight part
		Enlarged rubber emulsion (dry weight)	100.0
Vinylbenzene	75.0
		Vinyl cyanide	25.0
Uncle's lauryl mercaptan	2.0
		Cumene Hydroperoxide 80	3.0
Copperas solution (0.2%)	3.0
		Formaldehyde sodium sulfoxylate solution (10%)	0.9
Ethylene dinitrilotetra-acetic acid solution (0.25%)	3.0

Condense with calcium chloride according to the last table prepared rubber graft copolymer emulsion of filling a prescription, again through dehydration, be dried to below 2%, can make rubber graft copolymer required for the present invention (D-2) (rubber content 50 weight %, rubber weight average particle diameter 0.31 μ m).

The preparation of embodiment 6[modified rubber thermoplastic styrene resin composition (C-4)]

With rubber graft copolymer (D-1) 20 weight parts, rubber graft copolymer (D-2) 30 weight parts, thermoplastic styrene multipolymer (A-1) 50 weight parts and ethylidine bis-stearamides (ethylenebisstearamide, be called for short EBS) 0.3 weight part, after do mixing with the Han Xieer mixing machine, again with 200～220 ℃ of raw material tank temperature, the biaxial extruder with venting port that die head temperature is 220 ℃ dissolves mixing, can make the modified rubber thermoplastic styrene resin composition (C-4) of tool particle (pellet) shape, its rubber particles (B) median size 0.36 μ m; The manufacturing prescription and the Physical Property Analysis thereof of this modified rubber thermoplastic styrene resin composition (C-4) are listed in table 6.

The preparation of embodiment 7[modified rubber thermoplastic styrene resin composition (C-5)]

With the operating method of embodiment 6, difference is that thermoplastic styrene multipolymer (A-1) is replaced with thermoplastic styrene multipolymer (A-3), and the raw material tank temperature is 220～240 ℃, 240 ℃ of die head temperatures; The manufacturing prescription and the Physical Property Analysis thereof of this modified rubber thermoplastic styrene resin composition (C-5) are listed in table 6.

The preparation of embodiment 8[modified rubber thermoplastic styrene resin composition (C-6)]

With rubber graft copolymer (D-2) 36 weight parts, thermoplastic styrene multipolymer (A-1) 64 weight parts and ethylidine bis-stearamides 0.3 weight part, after do mixing with the Han Xieer mixing machine, again with 200～220 ℃ of raw material tank temperature, the biaxial extruder with venting port that die head temperature is 220 ℃ dissolves mixing, can make the modified rubber thermoplastic styrene resin composition (C-6) of tool particle (pellet) shape, the weight average particle diameter 0.31 μ m of rubber particles (B); The manufacturing prescription and the Physical Property Analysis thereof of this modified rubber thermoplastic styrene resin composition (C-6) are listed in table 6.

The preparation of embodiment 9[modified rubber thermoplastic styrene resin composition (C-7)]

With the operating method of embodiment 8, difference is that thermoplastic styrene multipolymer (A-1) is replaced with thermoplastic styrene multipolymer (A-3), and the raw material tank temperature is 220～240 ℃, 240 ℃ of die head temperatures; The manufacturing prescription and the Physical Property Analysis thereof of this modified rubber thermoplastic styrene resin composition (C-7) are listed in table 6.

The preparation of comparative example 5[modified rubber thermoplastic styrene resin composition (C-8)]

With the operating method of embodiment 6, difference is that thermoplastic styrene multipolymer (A-1) is replaced with thermoplastic styrene multipolymer (A-6); The manufacturing prescription and the Physical Property Analysis thereof of this thermoplastic styrene resin composition (C-8) are listed in table 6.

The preparation of comparative example 6[modified rubber thermoplastic styrene resin composition (C-9)]

With the operating method of embodiment 8, difference is that thermoplastic styrene multipolymer (A-1) is replaced with thermoplastic styrene multipolymer (A-6): the manufacturing prescription and the Physical Property Analysis thereof of this modified rubber thermoplastic styrene resin composition (C-9) are listed in table 6.

Physical property measurement benchmark among the present invention in each embodiment and the comparative example, as shown below:

1, the composition of thermoplastic styrene resin composition

Fourier transform infrared line spectrometer (FourierTransform Infrared Spectrometer) test with Nicolet corporate system, model Nexus 470.Wherein the unit of the rubber amount of thermoplastic styrene resin composition (below, contain the thermoplastic styrene resin composition of modified rubber) is weight %.The content of BMI monomer derived thing is calculated and is got by the volatile component of the raw material feeding in the polyreaction, each monomer conversion and each recovery.

2, remaining BMI monomer

Thermoplastic styrene resin composition is dissolved in the tetrahydrofuran (THF), and this solution re-uses Hewlett-Packard's science and technology (Hewlett Packard) company numbering 6890A with the gas chromatograph (GC) of the flame analyzer mensuration that performs an analysis.Do not detected (N.D): represent that remaining BMI monomer is below 2ppm.

3, MZ and MW

Utilize the gel dialysis chromatograph (GPC) of two functions of tool differential tortuosity ratio and scattering of light detecting, the Waters corporate system, the mensuration that performs an analysis, analysis condition is

Tubing string: KD-806M

Analyzer: Water RI-2410

Mobile phase: THF (flow velocity 1.0/min)

4, difference is than (gM):

Utilize the gel dialysis chromatograph series connection Wyatt Technology corporate system of Waters company, the multi-angle laser system at random of type Minidawn (multi-angle laser light scattering, MALLS) record when molar mass (molar mass) be 1 * 10 ⁶The rotation radius of difference molecule and straight-chain molecule during g/mole is utilized formula (1) to calculate again and is got mensuration.And the difference ratio is defined as:

Formula (1)

$\mathrm{gM}=\frac{{\left(r^2\right)}_b}{{\left(r^2\right)}_1}$

Wherein, (r ²) _b: the rotation radius of difference molecule; (r ²) ₁: the rotation radius of straight-chain molecule

5, MI (melt flow index)

According to the test of ASTM D-1238 method, 220 ℃ of probe temperatures, loading 10kg.Unit is/10 minutes (g/10min) of gram.

6, maximum elongation viscosity:

The variation of the melt strength of difference resin is to represent with elongation viscosity among the present invention, bigger its melt strength of expression of numerical value is better, and its determinator, see also shown in Figure 1, it is the determinator of maximum elongation viscosity, this device is with a well heater (nitrogen heating) 10 heating, this hot nitrogen is discharged by outlet 50, a pair of first roller 30 of discharge port outside adjunction of one capillary rheometer 20 (capillary rheometer) is to draw the molten resin 90 that takes out material, for guiding this molten resin 90 to this outlet 50, between this first roller 30 and this outlet 50, establish a pair of second roller 40, make this second roller 40 via this first roller 30 draw get after, unlikely by-pass flow is to other spaces, and this molten resin 90 is directed to this outlet 50 by this second roller 40, wherein, this first roller 30 is provided with load cell and draws the power (Pa) of getting to respond to it, and this draws the power of getting and promptly is defined as elongation viscosity.And condition determination is to stretch with 0.1～0.51/sec shear rate speed under 150 ℃ the nitrogen.

7, form and aspect

With Nippon Denshoku corporate system, resin is directly measured in the test of the color difference meter of type NDJ-300A.Employed quartzy cell (cell) is of a size of 5.5cm * 4.0cm * 2.4cm.

8, thermostability (Δ YI)

With above-mentioned thermoplastic styrene resin composition, ejaculator (penetrating 230 ℃ of temperature) ejection formation in shake male 4.2oz (117.6g) capacity, the moulding product are the disk of 5 centimeters of diameters, thickness 1/8inch, after this disk was placed baking oven 2 hours, temperature is set at 200 ℃, therebetween, the yellowness index (YI) before and after test plate is heated respectively with the color difference meter of Datacolor International corporate system, model Spectraflash 500 changes.

The Δ YI=back YI-preceding YI that is heated that is heated

9, the thick homogeneity of meat

Above-mentioned thermoplastic styrene resin composition is made single shaft forcing machine (diameter 90mm) in Ship-building Company of Hitachi, extrude the thick flat board of 500mm * 500mm * 2mm with 235 ℃, again with vacuum forming machine in 160 ℃ of compacted under refrigerator cold-storage storehouse inwalls, on these moulding product, get 10 after the moulding and select that to measure meat thick, ask the poor of its maximum value and minimum value.

Zero: the thick homogeneity of meat is good, and difference is below the 0.5mm.

*: the thick homogeneity of meat is bad, and difference is more than the 0.5mm.

10, application surface luster

With above-mentioned thermoplastic styrene resin composition, in the male corporate system ejaculator of shake with 230 ℃ ejaculation temperature under, penetrates the flat board of long 15cm, wide 7cm, thick 0.3cm, and spray coats with lacquer with acryl, observe its color and luster variation.

Zero: application surface luster homogeneous.

*: application surface luster heterogeneity has the lacquer of suction phenomenon.

11, stain

After getting 10 grams above-mentioned thermoplastic styrene resin composition being pressed into the thin rounded flakes of diameter 200mm, thickness 0.3mm with thermocompressor, observe the stain number.

12, weight average particle diameter

Above-mentioned thermoplastic styrene resin composition is made ultrathin section(ing), take a picture with the transmission electron microscope of 10000 multiplying powers in dyed back, with about 200～1000 of the rubber dispersed particle of gained in the photograph, each measures its particle diameter, tries to achieve weight average particle diameter with following formula again.

Weight average particle diameter=∑ niDi ⁴/ ∑ niDi ³

The ni=rubber particles directly is the rubber particles number of Di

Consult shown in the table one, the prepared thermoplastic styrene resin composition of the present invention, its shaping processability excellence, and modified rubber thermoplastic styrene resin composition of the present invention is shown in table two, table six, mechanical properties such as its thermostability, impact strength, flowability are also good, and rerum naturas such as thick homogeneity of meat and application surface luster homogeneity connect quite good.Thermoplastic styrene resin composition of the present invention and modified rubber thermoplastic styrene resin composition are particularly useful for the forming process of refrigerator plate except that applicable to general electronics, the electric articles for use.Therefore, the present invention is a novelty, progress really, and has the thermoplastic styrene resin composition and the modified rubber thermoplastic styrene resin composition of utility value on the industry.

Only the above only for several preferable possible embodiments of the present invention, has the knack of this skill people bodyguard such as, and it all ought to be included in the technical solution of the present invention scope according to modification or change that the present invention's spirit category is done.

[table 1]

Multipolymer (A) No			Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4	Comparative example 1
								(A-1)	(A-2)	(A-3)	(A-4)	(A-5)
			Reaction conditions	Supply with monomeric composition (weight part)	The ST monomer	68	68						58	100	68
The AN monomer	32	32						22	0	32
					The N-PMI monomer	0	0				20	0	0
The BMI monomer	0.02	0.01						0.01	0.02	0
					Polymerization starter (weight part)	BPO(0.02)	BPO(0.02)				BPO(0.015) TX-29A(0.005)	BPO(0.02)	BP0(0.02)
Chain-transfer agent (weight part)	TDM(0.2)	TDM(0.2)						TDM(0.2)	TDM(0.02)	TDM(0.2)
					Temperature of reaction (℃)		100/120				100/120	100/120	110/130/160	100/120
Reaction pressure (kg/cm 2)		4.0/4.0		4.0/4.0				4.0/4.0	3.0/3.0/3.0	4.0/4.0
					Residence time (hr) in the reactor		2				2	2	7	2
Analytical results	Resin is formed (weight part)	ST monomer derived thing		72				72	60	100					72
			AN monomer derived thing		28	28	20				0	28
		N-PMI monomer derived thing		0				0	20	0			0
			BMI monomer derived thing		0.02	0.01	0.01				0.02	0
		Remaining BMI monomer (ppm)		N.D.				N.D.	N.D.	N.D.			N.D.
	MZ (ten thousand)				130.5	78.3	58.0				112	39.9
			MW (ten thousand)					31.8	26.1	22.1			35	23.3
	MZ/MW				4.1	3	2.62				3.2	1.71
			Branching ratio (gM)					0.61	0.75	0.73			0.68	0.98
	Physical properties	MI			40	42	29				80	45
Maximum elongation viscosity (Pa * 10 6)				12.3				9.1	8.3	8.1			1.2
		Form and aspect			51	49	67				40	48

ST: vinylbenzene (styrene)

AN: vinyl cyanide (acrylonitrile)

N-PMI: N-phenylmaleimide (N-phenyl maleimide)

BMI: N, N '-4,4 '-ditan bismaleimides (N, N '-4,4 '-diphenyl methane bismaleimide)

BPO: dibenzoyl peroxide (benzoyl peroxide)

TDM: uncle's lauryl mercaptan (t-dodecyl mercaptan)

TX-29A: 1,1-pair-tert-butyl hydroperoxide-3,3,5-trimethyl-cyclohexane (1,1-bis-butyl peroxy-3,3,5-trimethyl cyclohexane)

Temperature of reaction: be followed successively by the temperature of the complete hybrid in the 1st complete hybrid reaction unit/2nd or the temperature of the complete hybrid reaction in the 1st complete hybrid reaction/2nd/complete hybrid reaction unit

Reaction pressure: be followed successively by the pressure of the complete hybrid in the 1st complete hybrid reaction unit/2nd or the pressure of the complete hybrid reaction in the 1st complete hybrid reaction/2nd/the 3rd complete hybrid reaction unit

[table 2]

The modified rubber thermoplastic styrene resin composition			Embodiment 5	Comparative example 3	Comparative example 4
						(C-1)	(C-2)	(C-3)
			Reaction conditions	Supply with monomeric composition (weight part)	The ST monomer				74	74	74
The AN monomer	26	26				26
					BD rubber		12	12	12
The BMI monomer	0.02	0				0
					The PGDA monomer		0	0	0.02
Polymerization starter (weight part)	BPO(0.05)	BPO(0.05)				BPO(0.05)
					Chain-transfer agent (weight part)		TDM(0.3)	TDM(0.3)	TDM(0.3)
Temperature of reaction (℃)		95/100/110/120				95/100/110/120				95/100/110/120
				Reaction pressure (kg/cm 2)			4.5/4/4/4	4.5/4/4/4	4.5/4/4/4
Residence time (hr) in the reactor		4				4				4
				Analytical results	Resin is formed (weight part)		ST monomer derived thing	75	75		75
AN monomer derived thing	25	25	25
						BMI monomer derived thing	0.02	0	0
Rubber amount (weight %)		16	16							16
					Remaining BMI monomer (ppm)		N.D.	N.D.	0
Physical properties	MI		32							35	26
				Thermostability		45	46	58
	The thick homogeneity of meat		○						×	×
				Application surface luster		○	×	×

PGDA: dimethyltrimethylene glycol diacrylate ((neopentyl glycol diacrylate)

Mark in the table 2 is identical with table 1, reaction conditions as shown below

Temperature of reaction: the temperature that is followed successively by the complete hybrid reaction unit in the 1st complete hybrid reaction unit/2nd/the 3rd complete hybrid reaction unit/the 4th complete hybrid reaction unit

Reaction pressure: the pressure that is followed successively by the complete hybrid reaction unit in the 1st complete hybrid reaction unit/2nd/the 3rd complete hybrid reaction unit/the 4th complete hybrid reaction unit

[table 6]

The modified rubber thermoplastic styrene resin composition		Embodiment 6	Embodiment 7	Embodiment 8	Embodiment 9	Comparative example 5	Comparative example 6
								(C-4)	(C-5)	(C-6)	(C-7)	(C-8)	(C-9)
		Form (weight part)	Rubber graft copolymer (D-1)	20	20	0	0							20	0
Rubber graft copolymer (D-2)	30							30	36	36	30	36
			Thermoplastic styrene multipolymer (A-1)	50	0	64	0						0	0
Thermoplastic styrene multipolymer (A-3)	0							50	0	64	0	0
			Thermoplastic styrene multipolymer (A-5)	0	0	0	0						50	64
EBS	0.3							0.3	0.3	0.3	0.3	0.3
			Analytical results	Rubber amount (weight %)	17	17	18						18	17	18
Remaining BMI monomer (ppm)	N.D	N.D						N.D	N.D	N.D	N.D
				Extrusion condition	Forcing machine raw material tank temperature (℃)	200-220	220-240					200-220	220-240	200-220	200-220
Forcing machine die head temperature (℃)	220	240	220					240	220	220
					Physical properties	MI	10.9				6	12.3	5.2	11.1	12.7
Thermostability	47	44	45	42				42	48
						Stain is counted	1			3	2	3	2	0
The thick homogeneity of meat	○	○	○	○				×	×
						Application surface luster	○			○	○	○	×	×

EBS: ethylidine bis-stearamides (ethylene bisstearamide)

Claims (10)

1, a kind of thermoplastic styrene resin composition, it is characterized in that, it contains thermoplastic styrene multipolymer (A), this thermoplastic styrene multipolymer (A) is other the copolymerizable vinyl monomer by nitrilation vinyl monomer (i-3) 0～40 weight part of the styrenic monomers of (i-1) 15～100 weight parts, (i-2) 0～45 weight part, more than (i-1)～(i-3) add up to 100 weight parts, and the multi-functional maleimide of 0.0005～1.0 weight part be that the raw material that monomer is formed makes.

2, thermoplastic styrene resin composition according to claim 1, it is characterized in that, described other copolymerizable vinyl monomer is that to be selected from least a acrylic ester monomer, methacrylate ester monomer and simple function maleimide be monomer.

3, thermoplastic styrene resin composition according to claim 1 is characterized in that, the content of described other copolymerizable vinyl monomer is 2～40 weight parts.

4, thermoplastic styrene resin composition according to claim 1 is characterized in that, its contained remaining multi-functional maleimide is that monomer content is below 100ppm.

5, thermoplastic styrene resin composition according to claim 1 is characterized in that, wherein the Z molecular-weight average/weight average molecular weight (Mz/Mw) of thermoplastic styrene multipolymer (A) is 2～8.

6, thermoplastic styrene resin composition according to claim 1 is characterized in that its difference than (gM)=0.45～0.95, this difference than (gM) but through type (1) calculate and get:

$\mathrm{gM}=\frac{{\left(r^2\right)}_b}{{\left(r^2\right)}_l}$ Formula (1)

Wherein, (r ²) _b: the rotation radius of difference molecule, (r ²) _l: the rotation radius of straight-chain molecule.

7, a kind of modified rubber thermoplastic styrene resin composition, it is characterized in that its styrenic monomers by (i-1) 15～100 weight parts, (i-2) the nitrilation vinyl monomer of 0～45 weight part, (i-3) other copolymerizable vinyl monomer of 0～40 weight part, more than (i-1)～(i-3) add up to 100 weight parts, and the multi-functional maleimide of 0.0005～1.0 weight part is that the thermoplastic styrene multipolymer (A) that makes of raw material that monomer is formed is as external phase, rubber particles (B) constitutes as disperse phase, and the rubber amount of this modified rubber thermoplastic styrene resin composition is 1～40 weight %.

8, modified rubber thermoplastic styrene resin composition according to claim 7 is characterized in that, the weight average particle diameter of this rubber particles (B) is 0.05 μ m～10 μ m.

9, modified rubber thermoplastic styrene resin composition according to claim 7 is characterized in that remaining multi-functional maleimide is that monomer content is below 100ppm.

10, modified rubber thermoplastic styrene resin composition according to claim 7 is characterized in that its difference than (gM)=0.45～0.95, this difference than (gM) but through type (1) calculate and get:

$\mathrm{gM}=\frac{{\left(r^2\right)}_b}{{\left(r^2\right)}_l}$ Formula (1)

Wherein, (r ²) _b: the rotation radius of difference molecule, (r ²) _l: the rotation radius of straight-chain molecule.