CN1594417A - Heat-resistant rubber modified styrene resin compositions - Google Patents
Heat-resistant rubber modified styrene resin compositions Download PDFInfo
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- CN1594417A CN1594417A CN 03158915 CN03158915A CN1594417A CN 1594417 A CN1594417 A CN 1594417A CN 03158915 CN03158915 CN 03158915 CN 03158915 A CN03158915 A CN 03158915A CN 1594417 A CN1594417 A CN 1594417A
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Abstract
The invention provides heat-resistant rubber modified styrene resin compositions comprising phenethylene copolymer as continuous phase and rubber particles as discontinuous phase, wherein the phenylethene copolymer comprises (i-1) phenylethene monomer, (i-2) nitrile ethylene monomer, (i-3) other copolymerization ethylene monomer, 1-40 weight portions of mopnofunctional maleimide monomer, and 0.0005-1.0 weight portion of polyfunctional maleimide monomer.
Description
Technical field
The present invention is relevant with rubber modified styrene series resin composition, particularly provide a kind of when having good thermotolerance and stress cracking resistance, can keep the rerum natura equilibrated of good shock strength to have stable on heating rubber modified styrene-series resin compositions.
Background technology
Ordinary rubber modified styrene series 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.
But for the rubber modified styrene series resin, often require to have heat-stable characteristic in order to reach bigger use field, and general heat-stable rubber modified styrene series resin system mixed by alpha-methyl styrene system-acrylic copolymer or polystyrene-maleimide based copolymer or polystyrene-maleimide system-acrylic copolymer and rubber graft copolymer and gets, and for example Japanese kokai publication sho 58-129043, spy open that flat 2-47146, spy open flat 4-136059, the spy opens patents such as flat 7-26092.Though it has heat-stable character above-mentioned patent, when large-scale or complicated ejection formation, often need to penetrate forming under the pressure at height, therefore, on moulding product, produce the excessive and shortcoming that causes that the moulding product chap etc. of residual stress; The present invention has been and has solved this shortcoming, and research provides a kind of when having good thermotolerance and stress cracking resistance with keen determination, can keep the rerum natura equilibrated of good shock strength to have stable on heating rubber modified styrene-series resin compositions.
Summary of the invention
The object of the present invention is to provide a kind of stable on heating rubber modified styrene series resin composition that has, a kind of impact strength that keeps particularly is provided, and the good stable on heating rubber modified styrene series resin composition of tool of stress cracking resistance.
Therefore, the present invention has stable on heating rubber modified styrene-series resin compositions and is made of as disperse phase as external phase and rubber particles (B) styrene based copolymer (A), and styrene based copolymer (A) is by the nitrilation vinyl monomer of the styrenic monomers of (i-1) 50～90 weight parts, (i-2) 10～50 weight parts, other copolymerizable vinyl monomer of (i-3) 0～40 weight part, more than (i-1), (i-2), (i-3) add up to 100 weight parts, and the simple function maleimide of 1～40 weight part be monomer institute's copolymerization and getting; Wherein, the rubber amount with stable on heating rubber modified styrene series resin composition is 1～40 weight %; Styrene based copolymer (A) is MI (a g/10 branch) in 250 ℃ of temperature, the measured MFR of loading 1.0kg, and 250 ℃ of temperature, the measured MFR of loading 10kg are HMI (g/10 branch), its MIR (=HMI/MI) between 21.0～30.0; And the remaining simple function maleimide of resin combination is that monomer is below 600ppm.
Embodiment
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.Add up to 100 weight parts based on above-mentioned (i-1), (i-2), (i-3), the consumption of styrenic monomers of the present invention is 50～90 weight parts, is preferably 55～85 weight parts, is more preferred from 58～80 weight parts.
The object lesson of (i-2) used in the present invention nitrilation vinyl monomer is as vinyl cyanide, Alpha-Methyl vinyl cyanide etc., and is wherein preferable with vinyl cyanide.Add up to 100 weight parts based on above-mentioned (i-1), (i-2), (i-3), nitrilation vinyl monomer of the present invention is 10～50 weight parts, is preferably 15～45 weight parts, is more preferred from 20～42 weight parts.
(i-3) used in the present invention other copolymerizable vinyl monomer means to have vinyl, and can with the monomer of (i-1) of the present invention styrenic monomers, the copolymerization of (i-2) nitrilation vinyl monomer, object lesson is as acrylic ester monomer, methacrylate ester monomer etc.
Wherein, acrylic ester monomeric concrete example is as methyl acrylate, ethyl propenoate, isopropyl acrylate, butyl acrylate, polyethyleneglycol diacrylate etc., and is wherein, preferable 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, EDMA ethylene dimethacrylate (ethylene dimethacrylate), dimethacrylate peopentyl esters (neopentyldimethacrylate) etc. are wherein with methyl methacrylate, butyl methacrylate is preferable.
In addition, the vinyl monomer that other copolymerization is possible, for example acrylic monomer (as: vinylformic acid, 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 be monomer (dimethyl fumarate for example, dibutyl itaconate), ethene, propylene, 1-butylene, the 1-amylene, 4-methyl-1-pentene, ethylene chloride, 1.1-Ethylene Dichloride, 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.
Add up to 100 weight parts based on above-mentioned (i-1), (i-2), (i-3), other copolymerizable vinyl monomer consumption of the present invention is 0～40 weight part, is preferably 1～34 weight part, is more preferred from 3～30 weight parts.
Simple function maleimide of the present invention is that monomer is meant and only contains single maleimide functional group in the 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.
Simple function maleimide of the present invention is that monomer usage quantity when polymerization is preferably 1.5～35 weight parts for add up to 1.0～40 weight parts of 100 weight parts based on above-mentioned (i-1), (i-2), (i-3), is more preferred from 2.0～28 weight parts.If usage quantity is less than 1 weight part, the thermotolerance deficiency of resin then; If usage quantity is greater than 40 weight parts, then during polymerization because polymeric solution viscosity height is mobile poor, can't react smoothly, and resin form and aspect extreme difference, can't commercially produce.
Multi-functional maleimide used in the present invention is a monomer, is meant the minimum compound that contains 2 maleimide functional groups, for example 2 or 3 or 3 above 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 (carbonyl group) ,-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 diphenyl methane) bismaleimide], N, N '-4,4 '-(3,3 '-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-diphenylpropane bismaleimide), N, N '-4,4 '-diphenyl ether bismaleimides (N, N '-4,4 '-diphenyl ether bismaleimide), N, N '-3,3 '-sulfobenzide bismaleimides (N, N '-3,3 '-diphenyl sulfone bismaleimide), N, N '-4,4 '-sulfobenzide bismaleimides (N, N '-4,4 '-diphenyl sulfone bismaleimide), N, N '-4,4 '-diphenyl sulfoxide bismaleimides (N, N '-4,4 '-diphenyl sulfoxide bismaleimide), N, N '-4,4 '-benzophenone bismaleimides (N, N '-4,4 '-benzophenonebismaleimide), N, N '-1,3-phenylene bismaleimides (N, N '-1,3-phenylenebismaleimide), wherein with N, N '-4,4 '-ditan bismaleimides, N, N '-1,3-phenylene bismaleimides is preferable.Add up to 100 weight parts based on above-mentioned (i-1), (i-2), (i-3), multi-functional maleimide of the present invention is that monomeric consumption is 0.0005～1.0 weight part, is preferably 0.001～0.3 weight part, is more preferred from 0.003～0.15 weight part; If multi-functional maleimide is a monomeric consumption when being higher than 1.0 weight parts, then in the polymerization process of styrol copolymer (A), the viscosity of polymkeric substance will sharply rise, and reaction can't be carried out.
The manufacture method of styrene based copolymer of the present invention (A) can be finished by the general bulk of using or solution polymerization, emulsion polymerization reaction, outstanding turbid polyreaction; Wherein preferable with bulk or solution polymerization.The previous reaction device can comprise: column flow reactor (PFR), complete mixing reactor (CSTR) or contain the reactor etc. of silent oscillation mixing tank.Reactor quantity can be one, also can and use two or more, is preferably more than three or three.When using two or more reactor, first reactor is preferable with complete mixing reactor (CSTR), and final reactor is to use columnar flow formula reactor (PFR) preferable.When making styrene based copolymer of the present invention (A), its manufacture is sent into continuously for the material solution that will react usefulness and is reacted in the reactor, and the polymerization initiator can be added in the reaction.
Styrene based copolymer of the present invention (A) in the mill, and is common, addible polymerization initiator.Based on above-mentioned (i-1), (i-2), (i-3) add up to 100 weight parts, the usage quantity of polymerization initiator is 0～1 weight part, be preferably 0.001～0.5 weight part, spendable polymerization initiator can be simple function polymerization initiator or multi-functional polymerization initiator, wherein, concrete simple function polymerization initiator is for example: dibenzoyl peroxide (benzoyl peroxide), dicumyl peroxide (dicumyl peroxide), tert-butyl peroxide (t-butyl peroxide), tert-butyl hydroperoxide (t-butylhydroperoxide), Cumene Hydroperoxide 80 (cumene hydroperoxide), tert butyl peroxy benzoate (t-butyl-peroxy benzoate), 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 (cyclohexanone peroxide), 2,2 '-azo-two-isobutyl (2,2 '-azo-bis-isobutyronitrile), 1,1 '-azo bis cyclohexane-1-carbonyl (1,1 '-azo-bis cyclohexane-1-carbonitrile), 2,2 '-azo-two-2-methyl fourth (2,2 '-azo-bis-2-methyl butyronitrile) etc.Wherein preferable with dibenzoyl peroxide, dicumyl peroxide.
The object lesson of multi-functional polymerization initiator 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-trimethylcyclohexane, 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-(tributyl peroxidation carbonyl) heptyl] hexanaphthene 4-(t-butylperoxy carbonyl)-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-butylperoxy) cyclohexyl propane, be called for short PX-12], multi-functional single peroxycarbonates (multifunctional monoperoxycarbonate, U.S. ATOFINA corporate system for example, trade(brand)name Luperox JWE) etc.; Wherein with 1,1-is two-tert-butyl hydroperoxide-3,3,5-trimethyl-cyclohexane, 2, two (4,4-two-tert-butyl hydroperoxide) the cyclohexyl propane of 2-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 80～240 ℃, and the pressure of reactor is to be controlled at 1～10kg/cm
2Between; And, can use chain-transfer agent among the present invention for the molecular weight of controlling polymers, and adding up to 100 weight parts based on above-mentioned (i-1), (i-2), (i-3), the usage quantity of chain-transfer agent 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-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, for example: pentaphenylethane (pentaphenylethane), α-Jia Jibenyixierjuwu (α-methyl styrene dimer), terpinolene (terpinolene), wherein with in the thio-alcohol just-lauryl mercaptan, the 3rd-lauryl mercaptan are preferable.
Multi-functional chain-transfer agent is for example: isoamyl tetrol four (3-mercaptopropionic acid ester) [pentaerythritoltetrakis (3-mercapto propionate)], isoamyl tetrol four (2-mercaptoacetate) [pentaerythritol tetrakis (2-mercapto acetate)], three-(2-Thiovanic acid) trishydroxymethyl propyl ester [trimethylolpropane tris (2-mercapto acetate)], three-(3-thiohydracrylic acid) trishydroxymethyl propyl ester [trimethylolpropane tris (3-mercapto propionate) is called for short TMPT], three-(6-mercaptohexanoic acid) trishydroxymethyl propyl ester [trimethylol-propanetris (6-mercapto hexanate)] etc.; Above-mentioned cited person, preferable with three-(3-thiohydracrylic acid) trishydroxymethyl propyl ester.
The method for making of above-mentioned styrene based copolymer (A), for being imported reaction unit continuously, material solution reacts, when the whole monomers in the material solution reach behind the fixed turnover ratio, again polymer solution is taken out continuously by reaction unit, importing the devolatilization device removes unreacted monomer and volatilization composition, afterwards, give granulation again.The final monomer turnover ratio of general polymerization reaction is more than the 50 weight %, is preferably more than the 60 weight %, is more preferred from more than the 70 weight %.General devolatilization device can use decompression degassing vessel device, or the extrusion de-gassing vessel.Reclaim unreacted monomer 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.
Styrene based copolymer of the present invention (A) optionally can add solvent in the mill.Add up to 100 weight parts based on above-mentioned (i-1), (i-2), (i-3), the usage quantity of solvent is 0～100 weight part, is preferably 0～60 weight part, is more preferred from 1～50 weight part; Spendable solvent can be: benzene, toluene, ethylbenzene, p-Xylol, o-Xylol, m-xylene, reach pentane, octane, hexanaphthene, and reach methylethylketone, acetone, methyl butyl ketone etc.
The weight average molecular weight of styrene based copolymer of the present invention (A) there is no specific limited, and is preferable 70,000～250 between 000 usually 60,000～350, between 000, is more preferably under 80,000～180, between 000.
Styrene based copolymer of the present invention (A) is MI (a g/10 branch) in 250 ℃ of temperature, the measured MFR of loading 1kg, 250 ℃ of temperature, the measured MFR of loading 10kg are HMI (g/10 branch), its MIR (=HMI/MI) usually between 21.0～30.0, preferable between 21.8～29.0, be more preferably under between 22.0～28.0.Wherein MFR means melt flow index, and this index system measures and gets with ASTM D-1238 method.The MIR mathematical control mode of styrene based copolymer (A) can and be used for reaching by a kind of of following method or several.Be that styrene based copolymer (A) is when copolymerization, multi-functional maleimide is monomeric addition and interpolation opportunity, the selection of multi-functional polymerization initiator and consumption, the selection of reactor, monomeric final transformation efficiency for example can be that the part consumption of monomer or multi-functional polymerization initiator mode such as add when moving to the later polymerization reactor of second or second is reached with the styrenic monomers of above-mentioned (i-1), multi-functional maleimide.
When reaching maintenance shock-resistance of the present invention, and has the good rubber modified styrene-series resin compositions of good stress cracking resistance, need to satisfy simultaneously: during (1) styrene based copolymer (A) polyreaction, multi-functional maleimide is that monomeric consumption is between 0.0005～1.0 weight part; (2) MIR of styrene based copolymer (A) is between 21.0～30.0.
Rubber modified styrene-series resin compositions of the present invention, be as external phase with styrene based copolymer (A), rubber particles (B) makes as disperse phase, and wherein, the amount of rubber part is generally 1～40 weight %, is preferably 3～35 weight %, is more preferred from 5～30 weight %.The amount of rubber part of the present invention is if between 1～40 weight % the time, and the rerum natura balance of the thermotolerance of then rubber modified styrene-series resin compositions and shock-resistance is preferable.
The manufacture method of rubber modified styrene-series resin compositions of the present invention, the rubber composition can be made an addition to and participate in reaction (following) in the polyreaction processing procedure of styrene based copolymer (A) 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 extrusion with styrene based copolymer of the present invention (A) and make (following with grafting mix method abbreviation).Aforesaid while grafting method, generally can adopt block polymerization, solution polymerization process, emulsion polymerization method or outstanding turbid polymerization to be finished, the manufacture method of aforesaid rubber graft copolymer generally can emulsion polymerization method, the block polymerization of emulsification finished, and is wherein preferable with emulsion polymerization method.
The manufacture method of rubber modified styrene-series resin compositions of the present invention, below enumerate two kinds of methods and be illustrated:
＜method one: the method for grafting simultaneously 〉
Method one can utilize bulk or solution polymerization to make rubber modified styrene-series resin compositions of the present invention.Method one employed reactor can comprise: column flow reactor (PFR), complete mixing reactor (CSTR) or contain the reactor etc. of silent oscillation mixing tank.Reactor quantity can be one, also can and use two or more, is preferably more than three or three.When using plural reactor, first reactor is preferable with complete mixing reactor (CSTR), and final reactor is to use columnar flow formula reactor (PFR) preferable.Manufacture is sent into continuously for the material solution (containing the rubber composition) that will be satisfied with rubber modified styrene-series resin compositions of the present invention earlier and is reacted in the reactor, temperature of reaction is to be controlled at 30～300 ℃, be preferably 60～250 ℃, be more preferred from 80～240 ℃, and the pressure of reactor normally is controlled at 1～10kg/cm
2Between; And be the molecular weight of controlling polymers, in the manufacturing of rubber modified styrene-series resin compositions of the present invention, can optionally use polymerization initiator or chain-transfer agent.
The method for making of above-mentioned rubber modified styrene-series resin compositions, be material solution to be imported reaction unit continuously react, when the whole monomers in the material solution reach behind the fixed turnover ratio, again polymer solution is taken out continuously by reaction unit, importing the devolatilization device removes unreacted monomer and volatilization composition, afterwards, give granulation again, and obtaining comprising styrene based copolymer (A) as external phase, rubber particles (B) is as the rubber modified styrene-series resin compositions of disperse phase.The final monomer turnover ratio of general polymerization reaction is more than the 50 weight %, is preferably more than the 60 weight %, is more preferred from more than the 70 weight %.General devolatilization device can use decompression degassing vessel device, or the extrusion de-gassing vessel.Reclaim unreacted monomer 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.
In the preceding method one, the employed material solution of the bulk of rubber modified styrene-series resin compositions or solution polymerization process includes: (i-1) 50～90 parts by weight of styrene are monomer, (i-2) 10～50 weight part nitrilation vinyl monomers, (i-3) other copolymerizable vinyl monomer of 0～40 weight part (above total 100 weight parts), and with respect to (i-1), (i-2), (i-3) the simple function maleimide of 1～40 weight part of 100 weight parts is a monomer, 0.0005 the multi-functional maleimide of～1.0 weight parts is a monomer, the rubber of 0～100 weight part solvent and 0.5～25 weight part; Wherein, styrenic monomers, nitrilation vinyl monomer, other copolymerizable vinyl monomer, simple function maleimide are that monomer, multi-functional maleimide are that monomer, solvent reach optionally and the polymerization initiator of interpolation, specifying of the kind of chain-transfer agent and usage quantity is same as the material solution of making styrene based copolymer (A), do not give unnecessary details at this.
In the aforesaid method one, also available emulsion polymerization reacts and makes rubber modified styrene-series resin compositions.The method for making of the method for making of emulsion polymerization reaction and following rubber like graft copolymer (B ') is identical, but described in the consumption employing method one of monomer and rubber.
In the bulk or solution polymerization of rubber modified styrene-series resin compositions of the present invention, rubber and styrenic monomers, the nitrilation vinyl monomer, monomeric mixing solutionss such as simple function maleimide system are in the polymeric initial stage, rubber phase is that the state with external phase exists, but graft polymerization reaction along with rubber, styrenic monomers, the nitrilation vinyl monomer, the simple function maleimide is that monomeric transformation efficiencys such as monomer increase gradually, and be accompanied by the stirring of reactor, the rubber composition is gradually by styrenic monomers, the nitrilation vinyl monomer, monomers such as simple function maleimide system and polymkeric substance thereof surround, and change dispersed particle state (disperse phase) into, on the other hand, styrenic monomers, the nitrilation vinyl monomer, monomers such as simple function maleimide system and polymer transition thereof are 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 0.1～2 μ m.
Ethylene-propylene rubber), polyacrylic ester is rubber, polysiloxane series rubber etc. in the method one, the concrete example of rubber composition has: diene series rubber, polyolerin elastomer (example:.Aforementioned diene series rubber is: at the polymer below 0 ℃, the concrete example of diene series rubber is the diene monomer composition through glass tansition temperature after the polymerization: divinyl rubber, synthetic polyisoprene, neoprene, EPDM rubber, vinylbenzene-diene series rubber, vinyl cyanide-diene series rubber etc.; Wherein, divinyl rubber has high-cis (Hi-Cis) content and low cis (Low-Cis); 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 (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 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 copolymerization zoarium, 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 grafting method of mixing 〉
Method two can be mixed by styrene based copolymer (A) and rubber graft copolymer (B '), and extrusion makes rubber modified styrene-series resin compositions of the present invention.
In the method two, usually system is with styrene based copolymer (A) and rubber graft copolymer (B '), with the Han Xieer mixing machine of general use do mix after, again with after the mixing machine melting mixing such as extrusion mixing machine, kneader or Banbury (Banbury) internal mixer etc., extrusion granulation again.
The method for making of rubber graft copolymer (B ') generally can use bulk or solution polymerization, emulsion polymerization reaction or outstanding turbid polyreaction to be finished.Wherein, rubber graft copolymer (B ') with the manufacture method of bulk or solution polymerization, is that material solution is carried out graft polymerization reaction.Material solution is: (i-1) other copolymerizable vinyl monomer of the nitrilation vinyl monomer of the styrenic monomers of 50～90 weight parts, (i-2) 10～50 weight parts, (i-3) 0～40 weight part, more than (i-1), (i-2) and (i-3) add up to the solvent of 100 weight parts, 0～100 weight part and 0.5～25 parts by weight of rubber, and optionally and the polymerization initiator that adds, chain-transfer agent; 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.Wherein, styrenic monomers, nitrilation vinyl monomer, other copolymerizable vinyl monomer, solvent reach optionally and the polymerization initiator of interpolation, specifying of the kind of chain-transfer agent and usage quantity is same as the material solution of making styrene based copolymer (A), 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 styrenic monomers, monomeric mixing solutionss such as nitrilation vinyl monomer are in the polymeric initial stage, rubber phase is that the state with external phase exists, but graft polymerization reaction along with rubber, styrenic monomers, monomeric transformation efficiencys such as nitrilation vinyl monomer increase gradually, and be accompanied by the stirring of reactor, the rubber composition is gradually by styrenic monomers, monomers such as nitrilation vinyl monomer and polymkeric substance thereof surround, and change dispersed particle state (disperse phase) into, on the other hand, styrenic monomers, monomers such as nitrilation vinyl monomer and polymer transition thereof are 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 0.1～2 μ m.
In addition, rubber graft copolymer (B ') also can be finished by emulsion polymerization, 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 15～95 weight %, nitrilation vinyl monomer 5～50 weight %, other copolymerizable monomer 0～35 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.
In the resin combination of the present invention residual simple function maleimide be monomer content below 600ppm, preferable below 300ppm, best below 200ppm; If in the resin combination residual simple function maleimide be monomer content more than 600ppm, then the form and aspect of resin are not good, heat-resistant quality is poor, thermotolerance is poor slightly.
In the above-mentioned resin combination residual simple function maleimide be monomer content what can and be used for by a kind of of following method or several adjusting:
(1). the final transformation efficiency of polymeric temperature of reaction, residence time, monomer of styrene based copolymer (A), preferable is that monomer conversion is more than 70%; Perhaps
(2). the pattern of polymerization reactor and the combination of quantity, preferable is that minimum 3 reactors in series or last reactor adopt the PFR formula; Perhaps
(3). during polymerization, multi-functional maleimide is monomeric interpolation opportunity, and for example: respectively at adding multi-functional maleimide in first, second reactor is monomer, and preferable reactor in the end added in the past.Perhaps
(4). the temperature of devolatilization and the adjustment of the residence time of devolatilization.
In the rubber modified styrene-series resin compositions of the present invention, can add various additives in case of necessity, as antioxidant, lubricant, UV light absorber, ultra-violet stabilizer, charged preventor, tinting material etc., the interpolation time can or mix the extrusion stage in the polymerization stage of styrene based copolymer (A) or the styrene-series resin compositions that each is rubber modified.Based on the rubber modified styrene-series resin compositions of 100 weight parts, the consumption of additive is generally below 6 weight parts.Other additive such as incombustible agent, impact modification agent etc. also can optionally add, and based on the rubber modified styrene-series resin compositions of 100 weight parts, the consumption of the additive of incombustible agent, impact modification agent etc. is generally below 30 weight parts.
In the rubber modified styrene-series resin compositions of the present invention, but benzene mixed vinyl copolymer (A) resin in addition in case of necessity.That is, in the rubber modified styrene-series resin compositions, can contain external phase is styrene based copolymer (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, propylene-divinyl-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.Based on the rubber modified styrene-series resin compositions of 100 weight parts, the consumption of this polymkeric substance is generally below 80 weight parts.
[evaluation method]
1.MIR：
Styrene based copolymer (A) is MI (a g/10 branch) in 250 ℃ of temperature, the measured MFR of loading 1kg, and 250 ℃ of temperature, the measured MFR of loading 10kg are HMI (g/10 branch), the ratio of its MIR=(HMI/MI).Wherein, MFR measures according to ASTM D-1238 method.
2. rubber amount:
Fourier transform infrared line spectrometer (FourierTransform Infrared Spectrometer) test with Nicolet corporate system, model Nexus 470.Unit: weight %.
3. shock-resistance:
Measure according to ASTM D-256 method: test film is of a size of 1/4 inch, attached breach; Unit: kg-cm/cm.
4. stress cracking resistance:
The test film of 100mm * 12.7mm * 3mm is positioned over impregnated in 50% the spirituous solution time that be full of cracks takes place in determination test sheet dipping back on the tool that radius-of-curvature is 165mm again.Time, long more then stress cracking resistance was good more.
More than zero: 48 hour
△: 24～48 hours
*: in 24 hours
5. thermotolerance (S.P): softening point temperature (Vicat softening temperature) is according to the test of ASTM D-1525 regulation, and unit is with a ℃ expression.
[embodiment and comparative example]
Aforementioned and other technology contents, characteristics and effect of the present invention in the explanation of following cooperation embodiment and comparative example, can clearly be understood.
[synthesis example of styrene based copolymer (A)]
Synthesis example a
Synthesizing of styrene based copolymer (A-1)
At three in-line reactors, be respectively first, two reactors are complete mixing reactor (CSTR), the 3rd reactor is column flow reactor (PFR), with styrene monomer 64.5 weight parts, acrylonitrile monemer 35.5 weight parts, N-phenylmaleimide 10 weight parts, N, N '-4,4 '-ditan bismaleimide amine monomers, 0.025 weight part, polymerization initiator dibenzoyl peroxide 0.025 weight part, the mixing solutions of chain-transfer agent lauryl mercaptan 0.1 weight part and ethylbenzene 25 weight parts, with 36kg/ hour flow, be supplied to first reactor continuously and carry out polyreaction; The polymers soln of the first reactor gained is imported second reactor, and with styrene monomer 100 weight parts, N, N '-4, the mixing solutions of 4 '-ditan bismaleimide amine monomers, 0.22 weight part, with 2kg/ hour flow, be supplied to second reactor continuously and carry out polyreaction; Polymers soln with the second reactor reaction gained imports the 3rd reactor again, and with styrene monomer 100 weight parts, N, N '-4, the mixing solutions of 4 '-ditan bismaleimide amine monomers, 0.04 weight part, with 2kg/ hour flow, be supplied to the 3rd reactor continuously and carry out polyreaction; Wherein, the volume of first, second, third reactor is respectively 40,40,75 liters, and the temperature of reactive tank is respectively 95,105,135 ℃, and stir speed (S.S.) is respectively 120,90,35rpm; The monomer conversion 74 weight % of final reactor outlet.
After polymerization ends, normally will import the devolatilization device by the copolymer solution of the 3rd reactor reaction gained, the devolatilization device removes unreacted monomer and other fugitive constituent as decompression devolatilization device or extrusion devolatilization device etc. with this device; And through the polymerization melts of devolatilization, its extrusion granulated can obtain styrene based copolymer of the present invention (A-1); The manufacturing prescription and the Physical Property Analysis thereof of this styrene based copolymer (A-1) are listed in table one.
Synthesis example b
Synthesizing of styrene based copolymer (A-2)
At three in-line reactors, be respectively first, two reactors are complete mixing reactor (CSTR), the 3rd reactor is column flow reactor (PFR), with styrene monomer 65.5 weight parts, acrylonitrile monemer 34.5 weight parts, N-phenylmaleimide 10 weight parts, N, N '-4,4 '-ditan bismaleimide amine monomers, 0.022 weight part, polymerization initiator 1,1-pair-tert-butyl hydroperoxide-3,3,5-trimethyl-cyclohexane 0.01 weight part, chain-transfer agent lauryl mercaptan 0.1 weight part, and the mixing solutions of ethylbenzene 25 weight parts, with 37kg/ hour flow, be supplied to first reactor continuously and carry out polyreaction; The polymers soln of the first reactor reaction gained is imported second reactor, and with styrene monomer 100 weight parts, N, N '-4, the mixing solutions of 4 '-ditan bismaleimide amine monomers, 0.15 weight part, with 3kg/ hour flow, be supplied to second reactor continuously and carry out polyreaction; Again the polymers soln of the second reactor reaction gained is imported the 3rd reactor and carry out polyreaction; Wherein, the volume of first, second, third reactor is respectively 40,40,75 liters, and the temperature of reactive tank is respectively 100,110,135 ℃, and stir speed (S.S.) is respectively 120,90,35rpm; The monomer conversion 75 weight % of final reactor outlet.
After polymerization ends, will import the devolatilization device by the copolymer solution of the 3rd reactor reaction gained with synthesis example a, remove unreacted monomer and other fugitive constituent; And through the polymerization melts of devolatilization, its extrusion granulated can obtain styrene based copolymer of the present invention (A-2); The manufacturing prescription and the Physical Property Analysis thereof of this styrene based copolymer (A-2) are listed in table one.
Synthesis example c
Synthesizing of styrene based copolymer (A-3)
At four in-line reactors, be respectively first, two reactors are complete mixing reactor (CSTR), the 3rd, the 4th reactor is column flow reactor (PFR), with styrene monomer 64.5 weight parts, acrylonitrile monemer 35.5 weight parts, N-phenylmaleimide 15 weight parts, N, N '-4,4 '-ditan bismaleimide amine monomers, 0.007 weight part, polymerization initiator 2,2-two (4,4-two-tert-butyl hydroperoxide) cyclohexyl propane 0.007 weight part, chain-transfer agent lauryl mercaptan 0.1 weight part, and the mixing solutions of ethylbenzene 25 weight parts, with 36kg/ hour flow, be supplied to first reactor continuously and carry out polyreaction; The polymers soln of the first reactor reaction gained is imported second reactor, and with styrene monomer 100 weight parts, N, N '-4,4 '-ditan bismaleimide amine monomers, 0.066 weight part, polymerization initiator 1,1-pair-tributyl peroxidation-3,3, the mixing solutions of 5-trimethyl-cyclohexane 0.054 weight part, with 2kg/ hour flow, be supplied to second reactor continuously and carry out polyreaction; Polymers soln with the second reactor reaction gained imports the 3rd reactor again, and with styrene monomer 100 weight parts and polymerization initiator 1,1-pair-tributyl peroxidation-3,3, the mixing solutions of 5-trimethyl-cyclohexane 0.013 weight part, with 2kg/ hour flow, be supplied to the 3rd reactor continuously and carry out polyreaction; Again the polymers soln of the 3rd reactor reaction gained is imported the 4th reactor and carry out polyreaction; Wherein, the volume of first, second, third, fourth reactor is respectively 40,40,75,75 liters, and the temperature of reactive tank is respectively 100,110,130,135 ℃, and stir speed (S.S.) is respectively 120,90,38,35rpm; The monomer conversion 74 weight % of final reactor outlet.
After polymerization ends, will import the devolatilization device by the copolymer solution of the 4th reactor reaction gained with synthesis example a, remove unreacted monomer and other fugitive constituent; And through the polymerization melts of devolatilization, its extrusion granulated can obtain styrene based copolymer of the present invention (A-3); The manufacturing prescription and the Physical Property Analysis thereof of this styrene based copolymer (A-3) are listed in table one.
Synthesis example d
Synthesizing of styrene based copolymer (A-4)
At three in-line reactors, be respectively first, two reactors are complete mixing reactor (CSTR), the 3rd reactor is column flow reactor (PFR), with styrene monomer 64.5 weight parts, acrylonitrile monemer 35.5 weight parts, N-phenylmaleimide 10 weight parts, N, N '-4,4 '-ditan bismaleimide amine monomers, 0.028 weight part, polymerization initiator 2,2-two (4, the peroxidation of 4-two-Di tributyl) cyclohexyl propane 0.009 weight part, the mixing solutions of chain-transfer agent lauryl mercaptan 0.1 weight part and ethylbenzene 25 weight parts, with 36kg/ hour flow, be supplied to first reactor continuously and carry out polyreaction; The polymers soln of the first reactor reaction gained is imported second reactor, and with styrene monomer 100 weight parts, polymerization initiator 1,1-pair-tributyl peroxidation-3,3, the mixing solutions of 5-trimethyl-cyclohexane 0.033 weight part, with 2kg/ hour flow, be supplied to second reactor continuously and carry out polyreaction; Polymers soln with the second reactor reaction gained imports the 3rd reactor again, and with the solution of styrene monomer 100 weight parts, with 2kg/ hour flow, is supplied to the 3rd reactor continuously and carries out polyreaction; Wherein, the volume of first, second, third reactor is respectively 40,40,75 liters, and the temperature of reactive tank is respectively 100,110,135 ℃, and stir speed (S.S.) is respectively 120,90,35rpm; The monomer conversion 75 weight % of final reactor outlet.
After polymerization ends, will import the devolatilization device by the copolymer solution of the 3rd reactor reaction gained with synthesis example a, remove unreacted monomer and other fugitive constituent; And through the polymerization melts of devolatilization, its extrusion granulated can obtain styrene based copolymer of the present invention (A-4); The manufacturing prescription and the Physical Property Analysis thereof of this styrene based copolymer (A-4) are listed in table one.
Synthesis example e
Synthesizing of styrene based copolymer (A-5)
At three in-line reactors, be respectively first, two reactors are complete mixing reactor (CSTR), the 3rd reactor is column flow reactor (PFR), with styrene monomer 64.5 weight parts, acrylonitrile monemer 35.5 weight parts, N-phenylmaleimide 25 weight parts, N, N '-4,4 '-ditan bismaleimide amine monomers, 0.02 weight part, polymerization initiator dibenzoyl peroxide 0.02 weight part, the mixing solutions of chain-transfer agent lauryl mercaptan 0.1 weight part and ethylbenzene 25 weight parts, with 30kg/ hour flow, be supplied to first reactor continuously and carry out polyreaction; The polymers soln of the first reactor reaction gained is imported second reactor, and with styrene monomer 100 weight parts, N, N '-4,4 '-ditan bismaleimide amine monomers, 0.2 weight part, polymerization initiator 1,1-pair-tributyl peroxidation-3,3, the mixing solutions of 5-trimethyl-cyclohexane 0.08 weight part, with 2kg/ hour flow, be supplied to second reactor continuously and carry out polyreaction; Polymers soln with the second reactor reaction gained imports the 3rd reactor again, and with the solution of styrene monomer 100 weight parts, with 2kg/ hour flow, is supplied to the 3rd reactor continuously and carries out polyreaction; Wherein, the volume of first, second, third reactor is respectively 40,40,75 liters, and the temperature of reactive tank is respectively 95,110,135 ℃, and stir speed (S.S.) is respectively 120,90,35rpm; The monomer conversion 76 weight % of final reactor outlet.
After polymerization ends, will import the devolatilization device by the copolymer solution of the 3rd reactor reaction gained with synthesis example a, remove unreacted monomer and other fugitive constituent; And through the polymerization melts of devolatilization, its extrusion granulated can obtain styrene based copolymer of the present invention (A-5); The manufacturing prescription and the Physical Property Analysis thereof of this styrene based copolymer (A-5) are listed in table one.
Synthesis example f
Synthesizing of styrene based copolymer (A-6)
Operating method with synthesis example b, difference is that employed monomer consumption is done an adjustment in the charging mixing solutions with first reactor, be respectively styrene monomer 60 weight parts, acrylonitrile monemer 34 weight parts, methyl methacrylate 6 weight parts, the monomer conversion 74 weight % of final reactor outlet; The manufacturing prescription and the Physical Property Analysis thereof of this styrene based copolymer (A-6) are listed in table one.
Synthesis example g
Synthesizing of styrene based copolymer (A-7)
Operating method with synthesis example b, difference is that employed monomer consumption is done an adjustment in the charging mixing solutions with first reactor, be respectively styrene monomer 61 weight parts, acrylonitrile monemer 39 weight parts, the monomer conversion 74 weight % of final reactor outlet; The manufacturing prescription and the Physical Property Analysis thereof of this styrene based copolymer (A-7) are listed in table one.
Synthesis example h
Synthesizing of styrene based copolymer (A-8)
Operating method with synthesis example b, difference is with employed N in the charging mixing solutions of first, second reactor, N '-4,4 '-ditan bismaleimide amine monomers consumption is done one and is adjusted, the consumption of first, second reactor is adjusted into 0.066 weight part, 0.45 weight part respectively, the monomer conversion 75 weight % of final reactor outlet; The manufacturing prescription and the Physical Property Analysis thereof of this styrene based copolymer (A-8) are listed in table one.
Synthesis example i
Synthesizing of styrene based copolymer (A-9)
At two in-line reactors is complete mixing reactor (CSTR), with styrene monomer 73 weight parts, acrylonitrile monemer 27 weight parts, N-phenylmaleimide 6 weight parts, N, N '-4,4 '-ditan bismaleimide amine monomers, 0.044 weight part, polymerization initiator 1,1-pair-tributyl peroxidation-3,3, the mixing solutions of 5-trimethyl-cyclohexane 0.01 weight part, chain-transfer agent lauryl mercaptan 0.1 weight part and ethylbenzene 24 weight parts, with 37kg/ hour flow, be supplied to first reactor continuously and carry out polyreaction; The polymers soln of the first reactor reaction gained is imported second reactor; Polymers soln with the second reactor reaction gained imports the 3rd reactor again, wherein, the volume of first, second, third reactor is respectively 40,40,75 liters, and the temperature of reactive tank is respectively 100,110,130 ℃, and stir speed (S.S.) is respectively 120,90,35rpm; The monomer conversion 60 weight % of final reactor outlet.
After polymerization ends, will import the devolatilization device by the copolymer solution of the second reactor reaction gained with synthesis example a, remove unreacted monomer and other fugitive constituent; And through the polymerization melts of devolatilization, its extrusion granulated can obtain styrene based copolymer of the present invention (A-9); The manufacturing prescription and the Physical Property Analysis thereof of this styrene based copolymer (A-9) are listed in table one.
Compare synthesis example j
Synthesizing of styrene based copolymer (A-10)
At two in-line reactors, first and second reactor is all complete mixing reactor (CSTR), mixing solutions with styrene monomer 68 weight parts, acrylonitrile monemer 32 weight parts, N-phenylmaleimide 8 weight parts, polymerization initiator dibenzoyl peroxide 0.025 weight part, chain-transfer agent lauryl mercaptan 0.1 weight part and ethylbenzene 25 weight parts, with 40kg/ hour flow, be supplied to first reactor continuously and carry out polyreaction; Again the polymers soln of the first reactor reaction gained is imported second reactor and carry out polyreaction; Wherein, the volume of first, second reactor is respectively 40,40 liters, and the temperature of reactive tank is respectively 100,125 ℃, and stir speed (S.S.) is respectively 120,90rpm; The monomer conversion 55 weight % of final reactor outlet.
After polymerization ends, will import the devolatilization device by the copolymer solution of the second reactor reaction gained with synthesis example a, remove unreacted monomer and other fugitive constituent; And through the polymerization melts of devolatilization, its extrusion granulated can obtain styrene based copolymer of the present invention (A-10); The manufacturing prescription and the Physical Property Analysis thereof of this styrene based copolymer (A-10) are listed in table one.
Compare synthesis example k
Synthesizing of styrene based copolymer (A-11)
With the operating method of synthesis example j relatively, difference is in the charging mixing solutions with first reactor, to add N, N '-4,4 '-ditan bismaleimide amine monomers, 0.01 weight part, the monomer conversion 56 weight % of final reactor outlet; The manufacturing prescription and the Physical Property Analysis thereof of this styrene based copolymer (A-11) are listed in table one.
Compare synthesis example l
Synthesizing of styrene based copolymer (A-12)
With the operating method of synthesis example b, difference is that N-phenylmaleimide changes 0 weight part in the charging mixing solutions with first reactor, the monomer conversion 72 weight % of final reactor outlet; The manufacturing prescription and the Physical Property Analysis thereof of this styrene based copolymer (A-12) are listed in table one.
Compare synthesis example m
Synthesizing of styrene based copolymer (A-13)
A complete mixing reactor (CSTR), with styrene monomer 68 weight parts, acrylonitrile monemer 32 weight parts, N-phenylmaleimide 6.8 weight parts, N, N '-4,4 '-ditan bismaleimide amine monomers, 0.05 weight part, polymerization initiator dibenzoyl peroxide 0.02 weight part, the mixing solutions of chain-transfer agent lauryl mercaptan 0.1 weight part and ethylbenzene 25 weight parts, flow with 50kg/ hour, be supplied to first reactor continuously and carry out polyreaction, the volume of reactor is 40 liters, the temperature of reactive tank is 120 ℃, and stir speed (S.S.) is 120rpm; The monomer conversion 50 weight % of final reactor outlet; The manufacturing prescription and the Physical Property Analysis thereof of this styrene based copolymer (A-13) are listed in table one.
Compare synthesis example n
Synthesizing of styrene based copolymer (A-14)
Operating method with synthesis example b, difference is that N-phenylmaleimide changes 45 weight parts in the charging mixing solutions with first reactor, can't react smoothly because polymeric solution viscosity is too high, and the form and aspect of resin and mobile poor can't be commercially produced.
Compare synthesis example o
Synthesizing of styrene based copolymer (A-15)
With the operating method of synthesis example b relatively, difference is in the charging mixing solutions with first reactor, to add N-phenylmaleimide 10 weight parts, N, N '-4,4 '-ditan bismaleimide amine monomers, 1.5 weight parts; In the reaction process, the viscosity that is because of reaction sharply rises, follow form and aspect variation, the many high-molecular weight bridge formation foreign matters of generation and the stain of resultant of reaction, cause polyreaction to proceed, and the resultant of reaction that takes out is 33.0 through the MIR of mobility-thickness product determinator analysis.
[synthesis example of rubber graft copolymer (B '-1)]
At four in-line reactors, the first～four reactor is all complete mixing reactor (CSTR), mixing solutions with styrene monomer 68 weight parts, acrylonitrile monemer 32 weight parts, divinyl rubber 7.0 weight parts, polymerization initiator dibenzoyl peroxide 0.03 weight part, chain-transfer agent lauryl mercaptan 0.1 weight part and ethylbenzene 35 weight parts, with 40kg/ hour flow, be supplied to first reactor continuously and carry out polyreaction; Wherein, the volume of first, second, third, fourth reactor is all 40 liters, and the temperature of reactive tank is respectively 100,105,115,130 ℃, and stir speed (S.S.) is respectively 300,200,150,90rpm; The monomer conversion 65 weight % of final reactor outlet.
After polymerization ends, will import the devolatilization device by the copolymer solution of the 4th reactor reaction gained with synthesis example a, remove unreacted monomer and other fugitive constituent; And through the polymerization melts of devolatilization, its extrusion granulated can obtain rubber graft copolymer of the present invention (B '-1), rubber constituent amount 10 weight %.
[synthesis example of rubber graft copolymer (B '-2)]
| 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 |
Under 65 ℃ of temperature of reaction, reacted 14 hours 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 according to above tabular prescription.
| 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 tabular 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 the styrene-propene multipolymer again, to make rubber graft copolymer (B '-2) according to following tabular.
| Composition | Weight part |
| Enlarged rubber emulsion (dry weight) | 100.0 |
| Styrene monomer | 75.0 |
| Acrylonitrile monemer | 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, through dewatering, being dried to below 2%, can make rubber graft copolymer required for the present invention (B '-2) (rubber content 50 weight %, rubber weight average particle diameter 0.31 μ m) again.
[embodiment of rubber modified styrene-series resin compositions and comparative example]
The method of grafting simultaneously
Embodiment 1
At four in-line reactors, be respectively first, two reactors are complete mixing reactor (CSTR), the 3rd, the 4th reactor is column flow reactor (PFR), with styrene monomer 65.5 weight parts, acrylonitrile monemer 34.5 weight parts, divinyl rubber 10.0 weight parts, N, N '-4,4 '-ditan bismaleimide amine monomers, 0.022 weight part, polymerization initiator 1,1-pair-tributyl peroxidation-3,3,5-trimethyl-cyclohexane 0.04 weight part, chain-transfer agent lauryl mercaptan 0.2 weight part, the mixing solutions of plasticizer butyl stearate 1.5 weight parts and ethylbenzene 50 weight parts, with 37kg/ hour flow, be supplied to first reactor continuously and carry out polyreaction; The polymers soln of the first reactor reaction gained is imported second reactor, and with styrene monomer 100 weight parts, N, N '-4, the mixing solutions of 4 '-ditan bismaleimide amine monomers, 0.15 weight part, with 3kg/ hour flow, be supplied to second reactor continuously and carry out polyreaction; Again the polymers soln of the second reactor reaction gained is imported the 3rd reactor and carry out polyreaction; And polymers soln of its reaction gained imports the 4th reactor again and carries out polyreaction; Wherein, the volume of first, second, third, fourth reactor is respectively 40,40,75,75 liters, and the temperature of reactive tank is respectively 100,105,115,130 ℃, and stir speed (S.S.) is respectively 300,200,150,90rpm; The monomer conversion 75 weight % of final reactor outlet.
After polymerization ends, will import the devolatilization device by the copolymer solution of the 4th reactor reaction gained with synthesis example a, remove unreacted monomer and other fugitive constituent; And through the polymerization melts of devolatilization, its extrusion granulated can obtain rubber modified styrene-series resin compositions of the present invention, rubber constituent amount 10 weight %; The styrene-series resin compositions that this is rubber modified is dissolved in the acetone soln, obtains styrene based copolymer (A) external phase, and the value of MIR is 23.1, and the manufacturing prescription and the Physical Property Analysis thereof of the styrene-series resin compositions that this is rubber modified are listed in table two.
Comparative example 1
At four in-line reactors, be respectively first, two reactors are complete mixing reactor (CSTR), the 3rd, the 4th reactor is column flow reactor (PFR), with styrene monomer 68 weight parts, acrylonitrile monemer 32 weight parts, divinyl rubber 9.0 weight parts, N, N '-4,4 '-ditan bismaleimide amine monomers, 0.0002 weight part, polymerization initiator 1,1-pair-tributyl peroxidation-3,3,5-trimethyl-cyclohexane 0.04 weight part, chain-transfer agent lauryl mercaptan 0.2 weight part, the mixing solutions of plasticizer butyl stearate 1.5 weight parts and ethylbenzene 45 weight parts, with 40kg/ hour flow, be supplied to first reactor continuously and carry out polyreaction; Wherein, the volume of first, second, third, fourth reactor is respectively 40,40,75,75 liters, and the temperature of reactive tank is respectively 100,105,115,130 ℃, and stir speed (S.S.) is respectively 300,200,150,90rpm; The monomer conversion 74 weight % of final reactor outlet.
After polymerization ends, will import the devolatilization device by the copolymer solution of the 4th reactor reaction gained with synthesis example a, remove unreacted monomer and other fugitive constituent; And through the polymerization melts of devolatilization, its extrusion granulated can obtain rubber modified styrene-series resin compositions of the present invention, rubber constituent amount 10 weight %; The styrene-series resin compositions that this is rubber modified is dissolved in the acetone soln, obtains styrene based copolymer (A) external phase, and the value of MIR is 20.7; The manufacturing prescription and the Physical Property Analysis thereof of the styrene-series resin compositions that this is rubber modified are listed in table two.
The grafting method of mixing
Embodiment 2
With rubber graft copolymer (B '-1) 20 weight parts, rubber graft copolymer (B '-2) 30 weight parts, styrene based copolymer (A-1) 50 weight parts and ethylenebisstearamide (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 twin shaft extruder fusion with venting port that die head temperature is 220 ℃ is mixed, can make the rubber modified styrene-series resin compositions of particle (pellet) shape, rubber constituent amount 17 weight %; The manufacturing prescription and the Physical Property Analysis thereof of this resin combination are listed in table three.
Embodiment 3
Rubber modified styrene-series resin compositions 20 weight parts and ethylenebisstearamide (ethylene bisstearamide with rubber graft copolymer (B '-2) 30 weight parts, styrene based copolymer (A-2) 50 weight parts, embodiment 1, 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 twin shaft extruder fusion with venting port that die head temperature is 220 ℃ is mixed, can make the rubber modified styrene-series resin compositions of tool particle (pellet) shape, rubber constituent amount 17 weight %; The manufacturing prescription and the Physical Property Analysis thereof of this resin combination are listed in table three.
Embodiment 4
With rubber graft copolymer (B '-2) 34 weight parts, styrene based copolymer (A-1) 66 weight parts and ethylenebisstearamide (ethylene bisstearamide, 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 twin shaft extruder fusion with venting port that die head temperature is 220 ℃ is mixed, can make the rubber modified styrene-series resin compositions of tool particle (pellet) shape, rubber constituent amount 17 weight %; The manufacturing prescription and the Physical Property Analysis thereof of this resin combination are listed in table three.
Embodiment 5～12
With the operating method of embodiment 4, difference is that the kind of styrene based copolymer (A) and consumption are done an adjustment; The manufacturing prescription and the Physical Property Analysis thereof of the styrene-series resin compositions that this is rubber modified are listed in table three.
Comparative example 2
With the operating method of embodiment 2, difference is the kind of styrene based copolymer (A) to be done one change; The manufacturing prescription and the Physical Property Analysis thereof of the styrene-series resin compositions that this is rubber modified are listed in table three.
Comparative example 3～6
With the operating method of embodiment 4, difference is the kind of styrene based copolymer (A) to be done one change; The manufacturing prescription and the Physical Property Analysis thereof of the styrene-series resin compositions that this is rubber modified are listed in table three, and the initial stage form and aspect YI of comparative example 6 is 26, and the initial stage form and aspect YI of embodiment 1 is 21, and the form and aspect of old friend's comparative example 6 are poor than embodiment.
[subordinate list explanation]
Table one is reaction conditions, the analysis of manufacturing prescription transitivity of the synthesis example and the comparison synthesis example of styrene based copolymer of the present invention (A)
Table two is reaction conditions, the analysis of manufacturing prescription transitivity of the rubber modified styrene-series resin compositions of the legal system of grafting simultaneously
Table three is the mix manufacturing prescription transitivity analysis of the legal system embodiment of the invention and comparative example of grafting
The synthesis example of [table one] styrene based copolymer (A)
| Synthesis example | ????a | ????b | ????c | ????d | ????e | ????f | ????g | ????h | ????i | ????j | ????k | ????l | ????m | ||||
| Styrene based copolymer (A) | ???A-1 | ????A-2 | ????A-3 | ????A-4 | ????A-5 | ????A-6 | ????A-7 | ????A-8 | ????A-9 | ????A-10 | ????A-11 | ????A-12 | ????A-13 | ||||
| Reaction conditions | First reactor (R1) | Temperature (℃) | ???95 | ????100 | ????100 | ????100 | ????95 | ????100 | ????100 | ????100 | ????100 | ????100 | ????100 | ????100 | ????120 | ||
| Stirring velocity (rpm) | ???120 | ????120 | ????120 | ????120 | ????120 | ????120 | ????120 | ????120 | ????120 | ????120 | ????120 | ????120 | ????120 | ||||
| Feed rate (kg/hr) | ???36 | ????37 | ????36 | ????36 | ????30 | ????37 | ????37 | ????37 | ????37 | ????40 | ????40 | ????37 | ????50 | ||||
| Feed composition | ????SM | (weight part) | ???64.5 | ????65.5 | ????64.5 | ????64.5 | ????64.5 | ????60 | ????61 | ????65.5 | ????73 | ????68 | ????68 | ????65.5 | ????68 | ||
| ????AN | (weight part) | ???35.5 | ????34.5 | ????35.5 | ????35.5 | ????35.5 | ????34 | ????39 | ????34.5 | ????27 | ????32 | ????32 | ????34.5 | ????32 | |||
| ????MMA | (weight part) | ???- | ????- | ????- | ????- | ????- | ????6 | ????- | ????- | ????- | ????- | ????- | ????- | ||||
| ????BMI | (weight part) | ???0.025 | ????0.022 | ????0.007 | ????0.028 | ????0.02 | ????0.022 | ????0.022 | ????0.066 | ????0.044 | ????0 | ????0.01 | ????0.022 | ????0.05 | |||
| ????PMI | (weight part) | ???10 | ????10 | ????15 | ????10 | ????25 | ????10 | ????10 | ????10 | ????6 | ????8 | ????8 | ????0 | ????6.8 | |||
| ????DVB | (weight part) | ???- | ????- | ????- | ????- | ????- | ????- | ????- | ????- | ????- | ????- | ????- | ????- | ||||
| The polymerization initiator | Kind | ???BPO | ????TX-29A | ????PX-12 | ????PX-12 | ????BPO | ????RX-29A | ????TX-29A | ????TX-29A | ????TX-29A | ????BPO | ????BPO | ????TX-29A | ????BPO | |||
| (weight part) | ???0.025 | ????0.01 | ????0.007 | ????0.009 | ????0.02 | ????0.01 | ????0.01 | ????0.01 | ????0.01 | ????0.025 | ????0.025 | ????0.01 | ????0.02 | ||||
| Chain-transfer agent | Kind | ???TDM | ????TDM | ????TDM | ????TDM | ????TDM | ????TDM | ????TDM | ????TDM | ????TDM | ????TDM | ????TDM | ????TDM | ????TDM | |||
| (weight part) | ???0.1 | ????0.1 | ????0.1 | ????0.1 | ????0.1 | ????0.1 | ?????0.1 | ????0.1 | ????0.1 | ????0.1 | ????0.1 | ????0.1 | ????0.1 | ||||
| ????EB | (weight part) | ???25 | ????25 | ????25 | ????25 | ????25 | ????25 | ????25 | ????25 | ????24 | ????25 | ????25 | ????25 | ????25 | |||
| Second reactor (R2) | Temperature (℃) | ???105 | ????110 | ????110 | ????110 | ????110 | ????110 | ????110 | ????110 | ????110 | ????125 | ????125 | ????110 | ||||
| Stirring velocity (rpm) | ???90 | ????90 | ????90 | ????90 | ????90 | ????90 | ????90 | ????90 | ????90 | ????90 | ????90 | ????90 | |||||
| Feed rate kg/hr) | ???2 | ????3 | ????2 | ????2 | ????2 | ????3 | ????3 | ????3 | ????3 | ????- | ????- | ????3 | |||||
| Feed composition | ????SM | (part heavily) | ???100 | ????100 | ????100 | ????100 | ????100 | ????100 | ????100 | ????100 | ????100 | ????- | ????- | ????100 | |||
| ????BMI | (weight part) | ???0.22 | ????0.15 | ????0.066 | ????- | ????0.2 | ????0.15 | ????0.15 | ????0.45 | ????- | ????- | ????- | ????0.15 | ||||
| The polymerization initiator | Kind | ???- | ????- | ????TX-29A | ????TX-29A | ????TX-29A | ????- | ????- | ????- | ????- | ????- | ????- | ????- | ||||
| (weight part) | ???- | ????- | ????0.054 | ????0.033 | ????0.08 | ????- | ????- | ????- | ????- | ????- | ????- | ????- | |||||
| The 3rd reactor (R3 | Temperature (℃) | ???135 | ????135 | ????130 | ????135 | ????135 | ????135 | ????135 | ????135 | ????130 | ????- | ????- | ????135 | ||||
| Stirring velocity (rpm) | ???35 | ????35 | ????38 | ????35 | ????35 | ????35 | ????35 | ????35 | ????35 | ????- | ????- | ????35 | |||||
| Feed rate kg/hr) | ???2 | ????- | ????2 | ????2 | ????2 | ????- | ????- | ????- | ????- | ????- | ????- | ????- | |||||
| Feed composition | ????SM | (weight part) | ???100 | ????- | ????100 | ????100 | ????100 | ????- | ????- | ????- | ????- | ????- | ????- | ????- | |||
| ????BMI | (weight part) | ???0.04 | ????- | ????- | ????- | ????- | ????- | ????- | ????- | ????- | ????- | ????- | ????- | ||||
| The polymerization initiator | Kind | ???- | ????- | ????TX-29A | ????- | ????- | ????- | ????- | ????- | ????- | ????- | ????- | ????- | ||||
| (weight part) | ???- | ????- | ????0.013 | ????- | ????- | ????- | ????- | ????- | ????- | ????- | ????- | ????- | |||||
| The 4th reactor (R4) | Temperature (℃) | ???- | ????- | ????135 | ????- | ????- | ????- | ????- | ????- | ????- | ????- | ????- | ????- | ||||
| Stirring velocity (rpm) | ???- | ????- | ????35 | ????- | ????- | ????- | ????- | ????- | ????- | ????- | ????- | ????- | |||||
| Feed rate (kg/hr) | ???- | ????- | ????- | ????- | ????- | ????- | ????- | ????- | ????- | ????- | ????- | ????- | |||||
| MIR | ???23.8 | ????23.2 | ????22.6 | ????23 | ????23.1 | ????23.3 | ????23.5 | ????27.3 | ????24.2 | ????20.3 | ????20.8 | ????24.1 | ????23.4 | ||||
| Final?con.(％) | ???74 | ????75 | ????74 | ????75 | ????76 | ????74 | ????74 | ????75 | ????60 | ????55 | ????56 | ????72 | ????50 | ||||
R1，R2：CSTR：R3，R4：plug?flow???????????????????????????????????????R1，R2：CSTR：R3，R4：plug?flow
The SM styrene monomer
The AN propylene monomer
The MMA methyl methacrylate
BMI N, N '-4,4 '-ditan bismaleimide amine monomers
The DVB Vinylstyrene
The BPO dibenzoyl peroxide
PX-12 2, two (4, the peroxidation of 4-two-Di tributyl) the cyclohexyl propane of 2-
TX-29A 1, and 1-pair-tributyl peroxidation-3,3, the 5-trimethyl-cyclohexane
The TDM lauryl mercaptan
EB ethylbenzene
The modulation of the styrene resin fat composition that [table two] is rubber modified
| Rubber modified styrene resin | Embodiment | Comparative example | ||||
| ????1 | ????1 | |||||
| Reaction conditions | First reactor (R1) | Temperature (℃) | ????100 | ????100 | ||
| Stirring velocity (rpm) | ????300 | ????300 | ||||
| Feed rate (kg/hr) | ????37 | ????40 | ||||
| Feed composition | ????SM | (weight part) | ????65.5 | ????68 | ||
| ????AN | (weight part) | ????34.5 | ????32 | |||
| ????BD | (weight part) | ????10 | ????9 | |||
| ????PMI | (weight part) | ????5 | ????5 | |||
| ????BMI | (weight part) | ????0.022 | ????0.0002 | |||
| The polymerization initiator | Kind | ????TX-29A | ????TX-29A | |||
| (weight part) | ????0.04 | ????0.04 | ||||
| Chain-transfer agent | Kind | ????TDM | ????TDM | |||
| (weight part) | ????0.2 | ????0.2 | ||||
| ????EB | (weight part) | ????50 | ????45 | |||
| Second reactor (R2) | Temperature (℃) | ????105 | ????105 | |||
| Stirring velocity (rpm) | ????200 | ????200 | ||||
| Feed rate (kg/hr) | ????3 | ????- | ||||
| Feed composition | ????SM | (weight part) | ????100 | ????- | ||
| ????BMI | (weight part) | ????0.15 | ????- | |||
| The 3rd reactor (R3) | Temperature (℃) | ????115 | ????115 | |||
| Stirring velocity (rpm) | ????150 | ????150 | ||||
| The 4th reactor (R4) | Temperature (℃) | ????130 | ????130 | |||
| Stirring velocity (rpm) | ????90 | ????90 | ||||
| Analytical results | Rubber amount (weight %) | ????10 | ????10 | |||
| Rubber size (μ m) | ????0.43 | ????0.43 | ||||
| MIR (styrene based copolymer (A) external phase) | ????23.1 | ????20.7 | ||||
| Residual PMI content (ppm) | ????26 | ????30 | ||||
| Physical properties | Thermotolerance (S.P.) | ????118.8 | ????119.8 | |||
| Stress cracking resistance | ????○ | ????× | ||||
| Impact strength (kg-cm/cm) | ????8.5 | ????8.4 | ||||
R1，R2：CSTR：R3，R4：plug?flow
The SM styrene monomer
The AN propylene monomer
The BD divinyl rubber
BMI N, N '-4,4 '-ditan bismaleimide amine monomers
TX-29A 1, and 1-pair-tributyl peroxidation-3,3, the 5-trimethyl-cyclohexane
The TDM lauryl mercaptan
The BS butyl stearate
EB ethylbenzene
The modulation of the styrene resin fat composition that [table three] is rubber modified
| Rubber modified styrene resin | Embodiment | Comparative example | ||||||||||||||||
| ????2 | ????3 | ????4 | ????5 | ????6 | ????7 | ????8 | ????9 | ????10 | ????11 | ????12 | ????2 | ????3 | ????4 | ????5 | ????6 | |||
| Form (weight part) | Rubber graft copolymer | ????B’-1 | ????20 | ????20 | ||||||||||||||
| ????B’-2 | ????30 | ????30 | ????34 | ????34 | ????34 | ????34 | ????34 | ????28 | ????42 | ????34 | ????34 | ????30 | ????34 | ????34 | ????34 | ????34 | ||
| Styrene based copolymer (A) | ????A-1 | ????50 | ????66 | |||||||||||||||
| ????A-2 | ????50 | ????66 | ||||||||||||||||
| ????A-3 | ????66 | |||||||||||||||||
| ????A-4 | ????66 | |||||||||||||||||
| ????A-5 | ????66 | |||||||||||||||||
| ????A-6 | ????72 | |||||||||||||||||
| ????A-7 | ????58 | |||||||||||||||||
| ????A-8 | ????66 | |||||||||||||||||
| ????A-9 | ????66 | |||||||||||||||||
| ????A-10 | ????50 | ????66 | ||||||||||||||||
| ????A-11 | ????66 | |||||||||||||||||
| ????A-12 | ????66 | |||||||||||||||||
| ????A-13 | ????66 | |||||||||||||||||
| The rubber modified styrene resin of embodiment 1 | ????20 | |||||||||||||||||
| Analytical results | Rubber amount (weight %) | ????17 | ????17 | ????17 | ????17 | ????17 | ????17 | ????17 | ????14 | ????21 | ????17 | ????17 | ????17 | ????17 | ????17 | ????17 | ????17 | |
| Rubber size (μ m) | ????0.5 | ????0.38 | ????0.3 | ????0.3 | ????0.3 | ????0.3 | ????0.3 | ????0.3 | ????0.3 | ????0.3 | ????0.3 | ????0.5 | ????0.3 | ????0.3 | ????0.3 | ????0.3 | ||
| Residual PMI content (ppm) | ????21 | ????41 | ????30 | ????50 | ????0 | ????22 | ????81 | ????65 | ????43 | ????51 | ????24 | ????88 | ????125 | ????121 | ????0 | ????1080 | ||
| Physical properties | Thermotolerance (S.P.) | ????116.1 | ??120.695 | ????117.2 | ????117 | ????131 | ????117.4 | ????141.3 | ????118.1 | ????115.6 | ????117.6 | ????115.1 | ????115.5 | ????116.1 | ????116.1 | ????105.4 | ????113.2 | |
| Stress cracking resistance | ????○ | ????○ | ????○ | ????○ | ????○ | ????○ | ????○ | ????○ | ????○ | ????○ | ????○ | ????× | ????× | ????× | ????○ | ????○ | ||
| Impact strength (kg-cm/cm) | ????18.8 | ????16.4 | ????18.2 | ????17.8 | ????13.5 | ????18 | ????11.2 | ????12.2 | ????21.4 | ????17.6 | ????19.7 | ????19 | ????18.6 | ????18.4 | ????23.2 | ????18 | ||
.P.：Vicat?softening?temperatur
Claims (1)
1. one kind has stable on heating rubber modified styrene series resin composition, it is characterized in that it is made of as disperse phase as external phase and rubber particles (B) styrene based copolymer (A), and styrene based copolymer (A) is the styrenic monomers by (i-1) 15～95 weight parts, (i-2) the nitrilation vinyl monomer of 5～85 weight parts, (i-3) other copolymerizable vinyl monomer of 0～40 weight part, more than (i-1), (i-2), (i-3) add up to 100 weight parts, and the simple function maleimide of 1～40 weight part is a monomer, 0.0005 the multi-functional maleimide of～1.0 weight parts is monomer institute's copolymerization and getting;
Wherein, the rubber amount with stable on heating rubber modified styrene series resin composition is 1～40 weight %;
Styrene based copolymer (A) is the MIg/10 branch in 250 ℃ of temperature, the measured melt flow index mfr of loading 1.0kg), 250 ℃ of temperature, the measured melt flow index mfr of loading 10kg are the HMIg/10 branch, and its melt flow index ratio MIR=HMI/MI is between 21.0～30.0;
And the remaining simple function maleimide of resin combination is that monomer is below the 600ppm.
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| CN 03158915 CN1264913C (en) | 2003-09-12 | 2003-09-12 | Heat-resistant rubber modified styrene resin compositions |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101815615A (en) * | 2007-10-02 | 2010-08-25 | 陶氏环球技术公司 | Multilayer coextruded shrink labels of oriented polystyrene film containing small rubber particles and low rubber particle gel content and block copolymers |
| CN101932652B (en) * | 2006-07-27 | 2012-10-03 | 陶氏环球技术有限责任公司 | Shrink labels of oriented polystyrene film containing small rubber particles and low rubber particle gel content and block copolymers |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI465506B (en) * | 2012-12-28 | 2014-12-21 | Chi Mei Corp | Heat-resistance styrene-based resin composition, method for preparing the same and modling products made therefrom |
| TWI481655B (en) * | 2012-12-28 | 2015-04-21 | Chi Mei Corp | Rubber modified methacrylate-based resin composition |
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2003
- 2003-09-12 CN CN 03158915 patent/CN1264913C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101932652B (en) * | 2006-07-27 | 2012-10-03 | 陶氏环球技术有限责任公司 | Shrink labels of oriented polystyrene film containing small rubber particles and low rubber particle gel content and block copolymers |
| CN101815615A (en) * | 2007-10-02 | 2010-08-25 | 陶氏环球技术公司 | Multilayer coextruded shrink labels of oriented polystyrene film containing small rubber particles and low rubber particle gel content and block copolymers |
| CN101815615B (en) * | 2007-10-02 | 2013-07-10 | 陶氏环球技术公司 | Multilayer coextruded shrink labels of oriented polystyrene film containing small rubber particles and low rubber particle gel content and block copolymers |
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