CN1337419A - Transparent rubber modified polystyrene resin composite - Google Patents
Transparent rubber modified polystyrene resin composite Download PDFInfo
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- CN1337419A CN1337419A CN 00122629 CN00122629A CN1337419A CN 1337419 A CN1337419 A CN 1337419A CN 00122629 CN00122629 CN 00122629 CN 00122629 A CN00122629 A CN 00122629A CN 1337419 A CN1337419 A CN 1337419A
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Abstract
The present invention relates to a transparent rubber modified styrene series resin composition which comprises rubber particle disperse phase formed from rubber-like copolymer and copolymer continuous phase consisting of styrene series monomer, (methyl) acrylic ester series monomer, acrylonitrile series monomer and other monomer which can be copolymerized. By controlling the content of polystyrene block of rubber-like copolymer, ratio of rubber particles containing internal included particles and content ratio of molecular weight being 3000-50000 in the continuous phase it can make the resin composite possess excellent resistance to chemicals and workability, at the same time it also can make its transparency and resistance to impact obtain equibalance.
Description
The present invention relates to a kind of transparent rubber modified polystyrene resin composite, particularly relate to a kind of by multipolymer external phase, form with the formed rubber particles disperse phase of rubbery copolymer, and have preferable chemical proofing, processibility, the good transparency and a shock-resistance rerum natura equilibrated resin combination.
The rubber modified polystyrene resin is a kind of material with good strength and processing forming, because this kind resin has above-mentioned advantage, so extensively be used in household supplies, tame electrical articles such as food product containers, packing material, on the shell of OA machine, but because ordinary rubber modified polystyrene resin is an opaque materials, therefore, can't be used in the moulding of transparent articles for use.For the intensity and the transparency that satisfies resin, and make the rerum natura of resin obtain balance, in existing skill, phenylethylene resin series and styrene-butadiene block copolymer can be mixed, but this kind method can't be filled a part intensity that improves resin, unsatisfactory in the use.
And Japanese kokai publication hei 4-180907 application for a patent for invention case, it provides a kind of in the presence of the segmented copolymer of styrene butadiene, the method of closing with vinylbenzene and methyl methacrylate copolymer, though this method can be improved the transparency and the intensity of resin, still can't satisfy the demand of processing forming.And Japanese kokai publication hei 8-239532 application for a patent for invention case is to provide a kind of by vinylbenzene-methyl methacrylate that styrene butadiene rubbers is close with the flexion rate formed copolymerization constituent.The average rubber particle size of this constituent is 0.1～2 μ m, and 1,2-vinyl ratio is 1～13.8 weight %, particle footpath dispersion index is 2～5, though this kind constituent can improve the transparency and the shock-resistance of resin, still can't improve the chemical proofing of resin.
This case contriver finds after research with keen determination, in the multipolymer external phase of being formed by styrenic monomers, (methyl) acrylic ester monomer and acrylic monomer, cooperate and contain the rubber particles disperse phase that rubbery copolymer forms, and cooperate specific formation of these external phases and disperse phase and condition, can make through rubber modified styrene-series resin compositions to have the preferable transparency and chemical proofing, also can obtain balance between each rerum natura of resin simultaneously.
The present invention is providing the good chemical proofing of a kind of tool, processibility, and the transparency and the good transparent rubber modified polystyrene resin composite of rerum natura balance such as shock-resistant.
Transparent rubber modified polystyrene resin composite of the present invention be by: rubber particles disperse phase (A) and multipolymer external phase (B) that rubbery copolymer forms are formed; Wherein, described rubbery copolymer is to contain styrenic monomers 10～50 weight %, segmented copolymer with diene monomer 90～50 weight %, the content of the polystyrene block in the above-mentioned rubbery copolymer accounts for 5～35 weight % of rubbery copolymer, and multipolymer external phase (B) is to be measured styrenic monomers 12～70 weight parts of 100 weight parts by total, (methyl) acrylic ester monomer 20～80 weight parts, acrylic monomer 1～20 weight part, form with other copolymerizable monomer 0～40 weight parts, and molecular weight is 3 in the multipolymer external phase (B), 000～50,000 account for 15～50 weight % of whole multipolymer external phases (B); Further say, the rubber particles number that contains the interior bag particle structure (occlusion) more than 4 or 4 in this rubber particles disperse phase (A) accounts for 2～20% of whole rubber particles numbers, and the rubber particles number of bag particle structure accounts for 20～80% of whole rubber particles numbers in not containing in the rubber particles disperse phase (A);
Composition according to above-mentioned resin can obtain have preferable chemical proofing and processibility required for the present invention, can obtain the resin combination of the good transparency and impact strength balance rerum natura simultaneously.
Rubbery copolymer used in the present invention is in the presence of organic solvent, use organolithium compound to be used as initiator, and and styrenic monomers, diene monomer, proper amount of solvent is carried out the segmented copolymer that anionic polymerisation forms, wooden Buddhist nun (Moony) viscosity (ML1+4) of above-mentioned multipolymer is 20～80, the viscosity of the styrene monomer solution of 25 ℃ 5 weight % is 3～60cps, and 1 in the diolefin series unit, the 2-vinyl structure accounts for more than the 8 weight %, the content of polystyrene block accounts for 5～35 weight % of rubbery copolymer, the structure of above-mentioned rubbery copolymer can be: all be homopolymer block (block) structure, partly disorderly arrange the structure of block, form part cumulative block (taper-block) structure, aligned structure and difference structure etc., its representative construction has:
1, linear block copolymers:
(1)(A-B)
n 
In the following formula, A is to be the polymer block of main composition with polystyrene, and B is to be the polymer block of main composition with diene, and the boundary of A block and B block not necessarily needs clear and definite differentiation, n=1 or 1 above integer.
2, difference shape segmented copolymer:
In the following formula, A, B are with the 1st explanation, and X is coupler residue (for example: silicon tetrachloride, tin tetrachloride etc.), or polyfunctional organolithium compound residue,
N and m are 1～10 integers.
3, the mixture of aforementioned the 1st and the 2nd 's arbitrary form.
In addition, forming a part cumulative block structure can be vinylbenzene incremental block structure, or divinyl incremental block structure, and the object lesson of above-mentioned incremental block structure has:
D-D/S-S (S-D/S)
n-S
D-S-D/S-S D/S-(S-D/S)
n
D-S-D/S-S-D X-[(S-D/S)
n]
m＋1
S-D-D/S-S X-[(D/S-S)
n]
m＋1
D/S-S-D-S X-[(S-D/S)
n-S]
m＋1
S-D/S-S X-[(D/S-S)
n-D/S]
m＋1
(S-D/S)
n D-D/S-S-S-D/S-D
Wherein, S is the polystyrene block, D is that polydiene is a block, D/S is the cumulative vinylbenzene of polystyrene or diolefin series component content-diolefin series copolymerization block, X is multi-functional initiator base or multi-functional coupler base, m, n are 1～10 integers, are preferable with D-D/S-S or D-S-D/S-S, D-D/S-S-S-D/S-D in the above-mentioned object lesson.For the present invention, more suitable with incremental block structure.
The content of the polystyrene block in the rubbery copolymer of the present invention is 5～35 weight %, be preferably 10～25 weight %, better is 14～22 weight %, when the content of polystyrene block is lower than 5 weight %, the transparency of resin is poor, and is opposite, and if this content is during greater than 35 weight %, the impact strength decreased that will cause resin can't be reached the transparency required for the present invention and shock strength rerum natura equilibrated purpose.In addition, 1 in the rubber of the present invention, the content of 2-vinyl structure are more than 8 weight %, and to be preferable more than the 14 weight %, when 1, when the content of 2-vinyl was higher than 14 weight %, the transparency of resin and the rerum natura balance between shock-resistance were preferable; Aforesaid styrenic monomers can be: vinylbenzene, alpha-methyl styrene, p-methylstyrene ,-vinyl toluene, neighbour-vinyl toluene, ethyl styrene, 2,4-dimethyl styrene, right-tributyl vinylbenzene, Alpha-Methyl-p-methylstyrene, bromo-vinylbenzene, two bromo-vinylbenzene, 2,4,6-tribromo-benzene ethene etc., above-mentioned styrenic monomers can use separately or several merge use.
Diene monomer of the present invention is to be selected from: 1,3-butadiene, 2-methyl isophthalic acid, 3-divinyl, 2-methyl isophthalic acid, 3-isoprene, 2,3-pair-methyl isophthalic acid, 3-divinyl, 1,3-isoprene, 1,3-hexadiene etc., above-claimed cpd can be used alone or two or more mixing is used, wherein, and again with 1,3-divinyl or 1,3-isoprene are preferable.
The employed organolithium compound catalyst of rubbery copolymer of the present invention is the compound that contains an above lithium atom in the molecule, and it can be selected from: one or more mix lithium ethide, just-amyl group lithium, sec.-propyl lithium, just-butyllithium, secondary butyllithium, hexyl lithium, cyclohexyl lithium, phenyl lithium, phenmethyl lithium, naphthyl lithium, the 3rd-butyllithium, trimethylene two lithiums, tetramethylene two lithiums, the two lithiums of divinyl and the two lithiums of isoprene etc. and use.
The rate of polymerization, 1 of rubbery copolymer of the present invention when polymerization, the 2-contents of ethylene, with reactivity ratio and the random rowization state of diene monomer with styrenic monomers, can change agent by polar compound or random row (random) and adjust, above-mentioned polar compound or random rowization agent are selected from: the potassium or the sodium salt of ethers, amine (amine), thioether amine, alkylbenzene, sulphur (sulfon) acids, trialkylphosphine oxide.
In the transparent rubber modified polystyrene resin composite of the present invention, its rubbery copolymer content is 1～40 weight %, and when this content was lower than 1 weight %, the shock strength of resin can reduce, surpass 40 weight %, the transparency of resin and formability can reduce.
In addition, multipolymer external phase of the present invention (B) is by (methyl) acrylic ester monomer of the styrenic monomers of 12～70 weight parts, 20～80 weight parts, the acrylic monomer of 1～20 weight part, form with other copolymerizable monomer of 0～40 weight part, demand based on chemical proofing, rigidity and the transparency, the monomeric content of this acrylic is preferable with 2～12 weight parts, better is 2～10 weight parts, wherein, the object lesson of styrenic monomers is the styrenic monomers of rubbery copolymer as described above, no longer heavily covers at this and enumerates explanation.
And aforementioned (methyl) acrylic ester monomer comprises: methyl acrylic ester and esters of acrylic acid, wherein, methyl acrylic ester can be for example: methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate etc., and esters of acrylic acid for example: methyl acrylate, ethyl propenoate, n-butyl acrylate, vinylformic acid 2-methyl amyl ester, vinylformic acid 2-ethyl pentyl group ester, Octyl acrylate etc., wherein, be preferable with methyl methacrylate and methyl acrylate again.Acrylic monomer of the present invention can be: vinyl cyanide, Alpha-Methyl vinyl cyanide etc., its content is at 1～20 weight part, if the monomeric content of acrylic is less than 1 weight part, the chemical proofing of resin and poor rigidity, when content was higher than 20 weight parts, the transparency of resin, form and aspect and processibility can variation.
Copolymerizable monomer 0～40 weight part of multipolymer external phase of the present invention (B), there is no particular restriction for the monomer whose kind, can adjust the content ratio of each copolymerization monomer according to need and adjust the flexion rate, it is transparent in necessary that last resin combination is reached, and the concrete example of above-mentioned copolymerizable monomer has: the unsaturated fatty acids of propylenedicarboxylic acid (Itaconic acid), maleic acid (maleic acid), fumaroyl (fumaric acid), butenoic acid (crotonicacid), dodecylic acid (1auric acid) etc.; N-methyl maleimide, N-ethyl maleimide, N-butyl maleimide, N-octyl group maleimide, N-sec.-propyl maleimide, N-phenylmaleimide, N-be right-maleimide of bromo-phenyl maleimide, N-neighbour-chloro-phenyl maleimide, N-cyclohexyl maleimide etc.; The unsaturated carboxylic acid anhydrides class of cis-1, propylenedicarboxylic acid acid anhydride, citraconic anhydride (citraconic anydride); The unsaturated compound class of amino-containeds such as allyl amine, (methyl) vinylformic acid amido ethyl ester, (methyl) vinylformic acid amido propyl ester; The acrylamide based compound of acrylamide, N methacrylamide etc.
In the resin combination of the present invention, the molecular weight of this multipolymer external phase (B) is 3,000～50,000 account for 15～50 weight % of whole multipolymer external phases (B), be preferably 20～45 weight %, better is 25～40 weight %, when molecular weight 3,000～50, when 000 content was lower than 15 weight %, the processibility of resin meeting variation was when the content that meets this scope is higher than 50 weight %, the shock strength meeting variation of resin, chemical proofing is variation also; That is to say that only meet above-mentioned scope, the shock-resistance of resin combination is good, also have preferable processing forming and chemical proofing simultaneously.
The polymer architecture of multipolymer external phase of the present invention (B) can be linearity or difference shape, and wherein the multipolymer external phase (B) of difference shape can obtain the rerum natura balance of better shock strength and processibility (flowability); Above-mentioned difference shape multipolymer external phase (B) can be reached by following method, for example: adopt during polymerization or add contain multi-functional unsaturated group monomer, multi-functional initiator, multi-functional chain transfer agent etc. a kind of or several and be used for reaching.
In addition, the rubber particles number that contains interior bag particle (occlusion) structure more than 4 or 4 in the rubber particles disperse phase of the present invention (A) accounts for 2～20% of whole rubber particles, is preferably 3～15%, and better is 3～10%; And the rubber particles number of bag particle structure accounts for 20～80% of whole rubber particles numbers in not containing in the disperse phase (A), be preferably 30～75%, better is 40～70%, the ratio of the rubber particles number of bag particle structure in containing more than 4 or 4 in the rubber particles disperse phase (A), when the ratio of the rubber particles number of bag particle structure is in aforementioned setting range in not containing, can make the transparency of resin and shock-resistance obtain balance.
Bag particle (occlusion) structure in the present invention is so-called, be meant granular polystyrene-(methyl) acrylic ester-acrylic copolymer that is coated on rubber particles inside, and bag particle footpath must be in the begin definition of wrapping particle in according to the invention of 0.05 μ m or the above person of 0.05 μ m in it; In not containing in the disperse phase rubber particles of bag particle be meant rubber particles do not contain fully in bag particle or interior bag particle footpath less than 0.05 μ m.
Resin combination of the present invention is according to the collocation of various conditions, and for example: adjustment such as the adjustment of polymerization state composition, additive, devolatilization, extrusion, mist degree (Haze) can be reached the degree below 11.0.
The weight average molecular weight of multipolymer external phase (B) and without particular limitation generally is 50,000～300 in the resin combination of the present invention, 000, be preferably 60,000～200,000, better is 70,000～150,000, when weight average molecular weight is lower than at 50,000 o'clock, the impact strength of resin combination is poor, is higher than at 300,000 o'clock and work as weight average molecular weight, the flowability of resin combination can descend, and the poor in processability and the transparency are poor.In addition, there is no particular restriction for the weight average particle diameter of the rubber particles of resin combination of the present invention, generally at 0.1～2.0 μ m, be preferably 0.1～1.5 μ m, better is 0.2～1.0 μ m, when the weight average particle diameter of rubber particles during less than 0.1 μ m, and the impact strength decreased of resin combination, if weight average particle diameter is greater than 2.0 μ m, then the transparency of resin combination is poor.The picture that the weight average particle diameter of above-mentioned rubber particles is taken with the ultrathin sectioning of infiltration type electron microscope, in this photo minimum 300 more than the particle, and record weight average particle diameter with following formula.
Ni is the number of the rubber particles of particle diameter Di in the following formula.
There is no particular restriction for insoluble part of content in the resin combination of the present invention, generally be 2～40 weight %, be preferably 8～35 weight %, better is 12～30 weight %, when insoluble part content during, the shock strength deficiency of resin combination less than 2 weight %, and when insoluble part content during greater than 40 weight %, the mobile variation of resin combination, the processing forming and the transparency are also poor.In addition, there is no particular restriction for the swelling index in the resin combination of the present invention, generally 2～25, be preferably 3～20, better is 5～15, and when the swelling index of resin combination of the present invention was not in the scope 2～25, its rerum natura (shock strength) and the transparency can't balances.
The insoluble part content weight % and the swelling exponential of above-mentioned resin combination are measured mode, be that resin combination with 1g is dissolved in the mixed solvent of 1: 1 toluene and acetone, and after dissolving in 25 ℃, 24 hours, with whizzer (15000rpm, 20 minutes) separate, insoluble part weight after getting its subnatant then and obtaining expanding, again with insoluble part with dry 12 hours of 80 ℃ of vacuum universes, obtain insoluble part weight, calculate insoluble part content (weight %) then with following formula.
And swelling index of the present invention is to calculate with the following formula formula:
The manufacture method of rubber modified polystyrene resin composite of the present invention, be in the presence of rubbery copolymer and styrenic monomers, (methyl) acrylic monomer, acrylic monomer and add other copolymerizable monomer in case of necessity and criticize formula or continous way bulk or solution graft copolymerization polyreaction.With the continuous solution polymerization is example, at first above-mentioned rubbery copolymer and monomer are added appropriate solvent formation raw material mixing solutions, the aforementioned base materials mixing solutions can dissolve in tradition has the dissolving tank of high shear stress, high stirring velocity, this dissolving tank can use: have ribbon spiral formula paddle, propeller formula paddle or other can produce paddle of high shear stress etc., under time enough, above-mentioned rubbery copolymer can be dissolved into fully the state of rubber solutions, carry out with the operation that makes things convenient for pumping to be transported to reactor; With aforementioned base materials solution or monomer solution respectively successive feed in first reactor and/or second reactor and/or its follow-up reactor, and cooperate need first and/or second and/or its follow-up reactor add under chain transfer agent, the initiator and carry out graft polymerization reaction.
Above-mentioned reactor can be a continuously stirring formula reactor (CSTR), or embolism flow reactor (Plug flowreactor), or same a kind of or different types of combination of static(al) hybrid (static reactor) reactor; Its temperature of reaction is controlled at 70～230 ℃, and final monomer conversion can reach 30～95%, but is preferable with 50～90%.
The polymerization methods of the rubber modified polystyrene resin that the present invention is transparent, be preferably first reactor and adopt continuously stirring formula reactor (CSTR), and then connecing second and/or follow-up reactor, above-mentioned follow-up reactor can be continuously stirring formula reactor, embolism flow reactor or static(al) mixing reactor etc.
The monomer conversion of general first reactor is preferably 2～25 weight % about 1～30 weight %, and better is 3～22 weight %.And the monomer conversion of aforementioned first reactor is selected, be to adjust according to difference such as employed rubbery copolymer content kind, viscosity, just manage to make the phase reversion phenomenon of rubber not produce at first reactor, and in follow-up reactor (as the second or the 3rd reactor), just produce phase reversion, so, could obtain good rerum natura.
The transparent rubber modified phenylethylene resin series of the present invention is when polymerization, spendable solvent species has: aromatic hydrocarbons, ketone, ester class, wherein, best aromatic hydrocarbons is for example: toluene, ethylbenzene and dimethylbenzene, and ketone best be butanone, the ester class is good with vinyl acetic monomer; In addition, the present invention also just can use-ethane, hexanaphthene, just-aliphatic hydrocarbons such as heptane are the some of solvent.
The transparent rubber modified phenylethylene resin series of the present invention in the mill, its addition of spendable initiator is monomeric 0～2 weight part with respect to 100 weight parts, be preferably 0.001～0.7 weight part, concrete example has: dibenzoyl peroxide (benzoyl peroxide), peroxidation diisopropyl benzene (dicumylperoxide), surpass oxidation dibenzoyl (di benzoyl superoxide), peroxidation tributyl (t-butyl peroxide), hydrogen peroxide tributyl (t-butyl hydroxy peroxide), hydrogen peroxide isopropyl benzene (cumene hydroperoxide), peroxidation tributyl benzoic ether (t-butyl peroxybenzoate), two-2-peroxidation second hexyl, two carbonic ethers (di-2-ethylhexyl peroxy dicarbonate) peroxidation tributyl sec.-propyl carbonic ether (tert-butyl peroxy isopropyl carbonate, be called for short BPIC), cyclohexanone peroxide (cycolhexanoe peroxide), 2,2 '-azo-two-isopropyl cyanide (2,2 '-azo-bis-isobutyronitrile), 1,1 '-azo-two-1-hexanaphthene carbonyl nitrile (1,1 '-azo-bis-1-cyclohexane carbonitrile), 2,2 '-azo-two-2-methylbutyronitrile (2,2 '-azo-bis-2-methylbutyronitrile), azo-two-isopropyl cyanide (azo-bis-isobutyronitrile), 1,1-diperoxyization tributyl hexanaphthene (1,1-di-t-butyl peroxy cyclohexane, be called for short TX-22), 1,1-two-peroxidation tributyl-3,3,5-trimethyl-cyclohexane (1,1-di-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-(peroxide tributyl carbonyl)-3-hexyl-6-[7-(peroxidation tributyl carbonyl) heptyl] hexanaphthene 4-(t-butyl peroxycarbonyl)-3-hexyl-6-[7-(t-butyl peroxy carbonyl) heptyl] cyclohexane}, two-Di tributyl diperoxy nonane diacid (di-t-butyl-diperoxyazelate), 2,5-dimethyl-2, two (the benzoyl peroxide)-hexanes [2 of 5-, 5-dimethyl-2,5-bis-(benzoyl peroxy) hexane], two-peroxidation tributyl-six hydrogen-terephthalate (di-t-butyl peroxy-hexahydro-terephthalate, be called for short BPHTP), 2,2-two (4,4-two-peroxidation tributyl) cyclohexyl propane [2,2-bis-(4,4-di-t-butyl peroxy) cyclohexanyl propane] etc.
The transparent rubber modified phenylethylene resin series of the present invention in the mill, the addition that can use chain transfer agent is 0～2 weight part with respect to 100 weight parts monomers, is preferably 0.01～0.7 weight part, concrete example has:
1) mercaptan (mercaptan) class: methyl mercaptan, n-butyl mercaptan, cyclohexyl mercaptan, just-lauryl mercaptan, stearyl-mercaptan (stearyl mercaptan), the 3rd-lauryl mercaptan (t-dodeylmercaptan is called for short TDM), just-propyl group mercaptan, n-octyl mercaptan, the 3rd-octyl mercaptan, the 3rd-nonyl mercaptan etc.
2) alkanamine (alkyl amines) class: single ethylamine, diethylamide, triethylamine, single isopropylamine, two single propyl group amine, monobutyl amine, di-n-butyl amine, three-n-butylamine etc.
3) four (3-thiohydracrylic acid) tetramethylolmethane [pentaerythritol tetrakis (3-mercaptopropionate)], four (2-Thiovanic acid) isoamyl tetrol [pentaerythritol tetrakis (2-mercaptoethanate)], four (4-sulfydryl butyric acid) isoamyl tetrol [pentaerythritol tetrakis (4-mercaptobutanate)], four (5-sulfydryl valeric acid) isoamyl tetrol [pentaerythritol tetrakis (5-mercaptopentanate)], four (6-mercaptohexanoic acid) isoamyl tetrol [pentaerythritol tetrakis (6-mercaptohexanate)], three-(2-Thiovanic acid) TriMethylolPropane(TMP)s [trimethylolpropane tris (2-mercapto ethanate)], three-(3-thiohydracrylic acid) TriMethylolPropane(TMP)s [trimethylolpropanetris (3-mercapto propionate) is called for short TMPT], three-(4-sulfydryl butyric acid) TriMethylolPropane(TMP)s [trimethylolpropane tris (4-mercapto butanate)], three-(5-sulfydryl valeric acid) TriMethylolPropane(TMP)s [trimethylolpropane tris (5-mercapto pentanate)], three-(6-mercaptohexanoic acid) TriMethylolPropane(TMP)s [trimethylol-propane tris (6-mercapto hexanate)] etc.
Other are for example: pentaphenylethane (pentaphenylethane), α-Jia Jibenyixierjuwu (α-methyl styrene dimer), terpinylene (terpinolene).
The monomeric addition of aforementioned multi-functional unsaturated group is preferably 0.005～0.6 weight part with respect to monomeric 0～1 weight part of 100 weight parts, its concrete example as:
1) Vinylstyrene (di vinyl benzene), 1,2,4-trivinylbenzene (1,2,4-tri vinylbenzene), 1,3,5-trivinylbenzene divinyl classes such as (1,3,5-tri vinyl benzene).
2) ethylene glycol bisthioglycolate methyl acrylate (ethylene glycol dimethacrylate), two ethylene glycol bisthioglycolate methyl acrylates (di ethylene glycol dimethacrylate), three-ethylene glycol bisthioglycolate methyl acrylate (triethylene glycol dimethacrylate), polyoxyethylene glycol diacrylate methyl esters (polyethyleneglycol dimethacrylate), 1, ammediol diacrylate methyl esters (1,3-propylene glycoldimethacrylate), 1,4-butyleneglycol diacrylate methyl esters (1,4-butylene glycoldimethacrylate), 1,6-hexanediyl methyl esters (1,6-hexanene glycoldimethacrylate), neopentyl alcohol diacrylate methyl esters (neo pentyl glycol dimethacrylate, be called for short PGDMA), dipropylene glycol diacrylate methyl esters (dipropylene glycol dimethacrylate), polypropylene glycol diacrylate methyl esters (polypropylene glycol dimethacrylate), 2,2-pair-(4-methacrylic acyloxy diethoxy phenyl) propane diacrylate methyl esters classes such as [2,2-bis-(4-methacryloxy diethoxy phenyl) propane].
3) three methyl acrylate classes of trimethylolpropane tris methyl acrylate (trimethylol propane trimethacrylate), trihydroxyethyl ethane three methyl acrylates (triethylol ethane trimethacrylate) etc.
4) glycol diacrylate (ethylene glycol diacrylate), diethylene glycol diacrylate (diethylene glycol diacrylate), triethylene glycol diacrylate (tri ethylene glycoldiacrylate), polyethyleneglycol diacrylate (polyethylene glycol diacrylate), 1,3-glycol 1,2-propanediol diacrylate (1,3-di-propylene glycol diacrylate), 1,4-two-butylene glycol diacrylate (1,4-di-butylene glycol diacrylate), 1,6-hexanediyl ester (1,6-hexylene glycol diacrylate), neopentyl alcohol diacrylate (neopentyl glycoldiacrylate, be called for short PGDA), propylene glycol diacrylate (di propylene glycoldiacrylate), polypropyleneglycol diacrylate (polypropylene glycol diacrylate), 2, two (the 4-propylene acyloxy phenyl) propane [2 of 2-, 2-bis (4-acryloxy propoxy phenyl) propane], 2, the diacrylate class of two (4-propylene acyloxy diethoxy phenyl) propane [2,2-bis (4-acryloxy di ethoxyphenyl) propane] of 2-etc.
5) the triacrylate class of Viscoat 295 (trimethylol propane triacrylate), trihydroxyethyl ethane triacrylate (triethylol ethane triacrylate) etc.
6) the tetraacrylate class of tetramethylol methane tetraacrylate (tetramethylol methane tetraacrylate) etc.
After the aforementioned polyreaction, from reactor, take out, low-volatiles such as unreacted monomer, solvent are removed, after polymer recovery, just can make the transparent rubber modified styrene-series resin compositions of the present invention through the devolatilization device.
Above-mentioned devolatilization device can be: single shaft or twin shaft have the extruder of devolatilization mouth, and can add the devolatilization auxiliary agent according to need in extruder, as: water, hexanaphthene, carbonic acid gas etc.And extruder also can be provided with according to need and pinches confounding section (kneading zone), pushes section etc., and screw speed is 120～350rpm.In addition, also can use devolatilization groove with vaccum-pumping equipment, above-mentioned devolatilization groove can one or several series connection use, its temperature is controlled at 180～350 ℃, be preferably 200～320 ℃, better is 220～300 ℃, and the vacuum degree control of devolatilization groove is below 300Torr, preferable below 200Torr, be more preferably under below the 100Torr; Other devolatilization equipment such as thin-film evaporator (thin film) also can adopt.
Via the processing of aforementioned devolatilization device, fugitive constituents such as residual monomer in the resin, solvent, two amount bodies, three amount bodies are reduced to below the 1 weight %, be preferably below the 0.8 weight %, better is below the 0.5 weight %.
Significantly do not decrease and the scope of the effect of resin combination of the present invention in, adjustable other compositions, these other compositions are for example: the additive of colorant, weighting agent, incombustible agent, difficult combustion auxiliary agent (ANTIMONY TRIOXIDE SB 203 99.8 PCT etc.), light stabilizer, thermal stabilizer, plasticizer, lubrication prescription, parting agent, tackifier, charged preventor, antioxidant, conductive agent etc.; Above-mentioned additive can be for example: mineral oil, for example: the ester of butyl stearate is that plasticizer, polyester are that organopolysiloxane, higher fatty acid and its metal-salt, the bulky amine of plasticizer, for example polydimethylsiloxane is antioxidant, glass fibre etc., and it can use or mix use separately.Above-mentioned composition can add after polymerization stage or reaction are finished according to need and mixes.
Aforementioned ester be the usage quantity (based on resin combination) of plasticizer or mineral oil generally at 0～5 weight %, preferable at 0.05～2 weight %, and the usage quantity of organopolysiloxane is preferable at 0.002～0.2 weight % generally at 0～0.5 weight %.
In addition, significantly do not decrease and the transparent situation of resin combination of the present invention under, can further allocate other resin, and addible other resins are as polystyrene-(methyl) acrylic ester-acrylic copolymer, polystyrene-(methyl) acrylate based copolymer, polystyrene-(methyl) acrylic ester-acrylic-maleimide based copolymer, polystyrene-(methyl) acrylic ester-maleimide based copolymer, (methyl) acrylic ester-maleimide based copolymer, or through the aforementioned multipolymer of diene series rubber upgrading (or grafting upgrading).
The aforementioned resin usage quantity is 0～200 weight part with respect to transparent rubber modified polystyrene resin composite 100 weight parts, and it can adjust or improve thermotolerance, rigidity and the flow processability of resin combination.
The purposes of transparent rubber styrene-series resin compositions of the present invention is also without particular limitation, its various moulding product, extrusion molding, blow and prolong the made finished product of moulding, thermoforming, vacuum forming and slush molding applicable to ejection formation, compressed moulding, for example give as security plate, film forming product etc., and can reach demands such as high workability, high heat resistance according to the prescription allotment.
The interpolation of aforementioned other compositions or resin mixes to mix by the general mixing muller of Bradley Bender plastometer, Ban Baili muller, kneading-mixing machine, roller press, one or two extruders etc. and makes.Usually after mixing by means of mixing such as these extruders; again the extrudate that signature is made cooled off, granulation; above-mentioned mixing generally is to carry out under 160～280 ℃, and is good with 180～250 ℃ temperature, the mixing of respectively allocating composition again mix and out-of-order on special restriction.
[physical property measurement]
One, processibility (flowability is called for short MI): according to the mobility-thickness product of ASTM D-1238 standard test resin under 200 ℃ * 5kg.
Two, chemical proofing (oil-proofness): the test piece that resin ejection formed 23cm is long, and test piece is fixed on forms crooked arciformly on the arc tester, the test piece surface is coated with spreads sweet oil and place again under the room temperature, after 6 hours, observe its outward appearance.
Zero: expression test piece outward appearance does not change.
△: expression test piece outward appearance has the be full of cracks vestige slightly.
*: the be full of cracks of expression test piece outward appearance is serious.
Three, shock-resistance (IZOD): measure Emhorn shock strength (23 ℃ of thick test films of 1/4 inch) with breach according to ASTM D-256.
Four, the transparency (mist degree, Haze): the test piece that resin ejection formed 3mm is thick, and according to the ASTM D-1003 standard test transparency, when the high more expression transparency of Haze value poor more.
Five, the molecular weight 3 of external phase (B), 000～50,000 content (weight %) are measured: resin combination is dissolved in the tetrahydrofuran (THF) (being called for short THF), remove insoluble part through centrifugation, the part with solvable part is its molecular weight distribution of standard test with gel dialysis process (being called for short GPC) employing polystyrene again; In the scope by GPC mensuration, with molecular weight 3,000～12, the total integral area of 000,000 resin signals is used as 100%, and the area of molecular weight 3,000～50,000 accounts for the per-cent of total integral area.Above-mentioned GPC measures according to following condition:
Tubing string: KD-806M, analyzer: RI-410, UV-486, mobile phase: THF (flow velocity 1.0c.c./min).
Six, the content of polystyrene block (wt%) is measured: get rubbery copolymer and be dissolved in the benzene dissolving of heating, add 1 again, 2-two chloro-tributyl hydroperoxide (1,2-di-choro-t-butyl hydroperoxide) solution and perosmic anhydride continued Hybrid Heating 15 minutes, cooling back also adds methyl alcohol and sulfuric acid stirs, dry with filter paper filtering, the universe then, weigh.
Seven, 1 of rubber, 2-contents of ethylene (%) is measured:
Measure with IR.
Eight, the interior bag particle structure content (%) in the rubber particles is measured: take resin in the photo that obtains 25000 times with the penetrating type electron microscope, get in the scope of photo 12cm * 16cm, measure rubber particles respectively and add up to (N), and the rubber particles number that is surrounded by interior bag particle more than 4 or 4 (interior bag particle diameter needs 〉=0.05 μ) in the rubber particles is (N
1), the rubber particles number of bag particle is not (N in not containing
2), that is to say that wherein rubber particles is counted N
2In comprise: bag particle in not containing fully in the rubber particles, perhaps in bag particle footpath at 0.05 μ m or the interior bag particle below the 0.05 μ m.
N
1/ N * 100%=4 content % individual or rubber particles of interior bag particle more than 4
N
2The content % of the rubber particles of bag particle in/N * 100%=does not contain
[embodiment]
Embodiment 1
With rubbery copolymer 8.4 weight parts (phenylethylene/butadiene content=25/75 weight %, 1,2-contents of ethylene=15.4%, the cumulative segmented copolymer of wood Buddhist nun viscosity 45, contain 1 tool styrene block in this segmented copolymer, 1 polybutadiene block, with 1 phenylethylene/butadiene block that the vinyl toluene composition is cumulative, wherein the content of polystyrene block is 18 weight %), vinylbenzene 21.6 weight parts, methyl methacrylate 34.5 weight parts, vinyl cyanide 5.5 weight parts, ethylbenzene 30 weight parts, lauryl mercaptan 0.1 weight part, form feedstock solution with dibenzoyl peroxide 0.1 weight part, with aforementioned feedstock solution with the continuous pump to 4 of a 35kg/hr placed in-line complete hybrid reactor (capacity of every still is 40 liters) continuous polymerization unit, wherein, the temperature of reaction of first still is controlled at 110 ℃, the temperature of reaction of second still is controlled at 115 ℃, the temperature of reaction of the 3rd still is controlled at 125 ℃, the temperature of reaction of the 4th still is controlled at 130 ℃, react the back transformation efficiency and be about 57%, through the extrusion of devolatilization equipment, just can obtain transparent rubber modified polystyrene resin of the present invention.
Contain vinylbenzene tectonic element 32 weight parts, methyl methacrylate 60 weight parts, vinyl cyanide 8 weight parts in the external phase of above-mentioned composition, its molecular weight 3,000～50,000 account for 29 weight %, the rubber particles number of bag particle structure accounts for 6% of whole rubber in containing more than 4, and the rubber particles number of bag particle structure does not account for 64% in not containing, and the measured rerum natura of this resin is as shown in table 1.
Embodiment 2
With rubbery copolymer 8.4 weight parts (phenylethylene/butadiene content=25/75 weight %, 1,2-contents of ethylene=18.0%, the cumulative segmented copolymer of wood Buddhist nun viscosity 47), vinylbenzene 22.8 weight parts, methyl methacrylate 37.0 weight parts, vinyl cyanide 1.8 weight parts, ethylbenzene 30 weight parts, lauryl mercaptan 0.1 weight part, form feedstock solution with dibenzoyl peroxide 0.1 weight part, with aforementioned feedstock solution with the continuous pump to 4 of a 35kg/hr placed in-line complete hybrid reactor (capacity of every still is 40 liters) continuous polymerization unit, wherein, the temperature of reaction of first still is controlled at 110 ℃, the temperature of reaction of second still is controlled at 115 ℃, the temperature of reaction of the 3rd still is controlled at 125 ℃, the temperature of reaction of the 4th still is controlled at 130 ℃, react the back transformation efficiency and be about 60%, through the extrusion of devolatilization equipment, just can obtain transparent rubber modified polystyrene resin of the present invention.
Contain vinylbenzene tectonic element 34 weight parts, methyl methacrylate 63 weight parts, vinyl cyanide 3 weight parts in the external phase of above-mentioned composition, its molecular weight 3,000～50,000 account for 34 weight %, and the block content of the polystyrene of rubbery copolymer is 19 weight %, bag particle structure person accounted for 8% of whole rubber particles numbers in rubber particles contained more than 4, and the rubber particles number of bag particle structure does not account for 60% in not containing, and the measured rerum natura of this resin is as shown in table 1.
Embodiment 3
With rubbery copolymer 8.4 weight parts (phenylethylene/butadiene content=25/75 weight %, 1,2-contents of ethylene=15.4%, the cumulative segmented copolymer of wood Buddhist nun viscosity 45), vinylbenzene 22.8 weight parts, methyl methacrylate 37.0 weight parts, vinyl cyanide 1.8 weight parts, ethylbenzene 30 weight parts, lauryl mercaptan 0.1 weight part, form feedstock solution with dibenzoyl peroxide 0.1 weight part, with aforementioned feedstock solution with the continuous pump to 4 of a 35kg/hr placed in-line complete hybrid reactor (capacity of every still is 40 liters) continuous polymerization unit, wherein, the temperature of reaction of first still is controlled at 110 ℃, the temperature of reaction of second still is controlled at 115 ℃, the temperature of reaction of the 3rd still is controlled at 125 ℃, the temperature of reaction of the 4th still is controlled at 130 ℃, react the back transformation efficiency and be about 60%, through the extrusion of devolatilization equipment, just can obtain transparent rubber modified polystyrene resin of the present invention.
Contain vinylbenzene tectonic element 34 weight parts, methyl methacrylate 63 weight parts, vinyl cyanide 3 weight parts in the external phase of above-mentioned composition, its molecular weight 3,000～50,000 account for 33 weight %, and the block content of the polystyrene of rubbery copolymer is 18 weight %, bag particle structure person accounted for 5% of whole rubber particles numbers in rubber particles contained more than 4, and the rubber-like population of bag particle structure does not account for 65% in not containing, and the measured rerum natura of this resin is as shown in table 1.
Embodiment 4
With rubbery copolymer 8.4 weight parts (phenylethylene/butadiene content=25/75 weight %, 1,2-contents of ethylene=12.5%, the cumulative segmented copolymer of wood Buddhist nun viscosity 49), vinylbenzene 22.8 weight parts, methyl methacrylate 37.0 weight parts, vinyl cyanide 1.8 weight parts, ethylbenzene 30 weight parts, lauryl mercaptan 0.1 weight part, form feedstock solution with dibenzoyl peroxide 0.1 weight part, with aforementioned feedstock solution with the continuous pump to 4 of a 35kg/hr placed in-line complete hybrid reactor (capacity of every still is 40 liters) continuous polymerization unit, wherein, the temperature of reaction of first still is controlled at 110 ℃, the temperature of reaction of second still is controlled at 115 ℃, the temperature of reaction of the 3rd still is controlled at 125 ℃, the temperature of reaction of the 4th still is controlled at 130 ℃, react the back transformation efficiency and be about 60%, through the extrusion of devolatilization equipment, just can obtain transparent rubber modified polystyrene resin of the present invention.
Contain vinylbenzene tectonic element 34 weight parts, methyl methacrylate 63 weight parts, vinyl cyanide 3 weight parts in the external phase of above-mentioned composition, its molecular weight 3,000～50,000 account for 36 weight %, and the block content of the polystyrene of rubbery copolymer is 15 weight %, bag particle structure person accounted for 4% of whole rubber particles numbers in rubber particles contained more than 4, and the rubber particles number of bag particle structure does not account for 58% in not containing, and the measured rerum natura of this resin is as shown in table 1.
Comparative example 1
With rubbery copolymer 8.4 weight parts (phenylethylene/butadiene content=30/70 weight %, 1,2-contents of ethylene=11.0%, the cumulative segmented copolymer of wood Buddhist nun viscosity 45), vinylbenzene 24.6 weight parts, methyl methacrylate 37.0 weight parts, ethylbenzene 30 weight parts, lauryl mercaptan 0.07 weight part, form feedstock solution with dibenzoyl peroxide 0.12 weight part, with aforementioned feedstock solution with the continuous pump to 4 of a 35kg/hr placed in-line complete hybrid reactor (capacity of every still is 40 liters) continuous polymerization unit, but temperature of reaction changes into: the temperature of reaction of first still is controlled at 95 ℃, the temperature of reaction of second still is controlled at 110 ℃, the temperature of reaction of the 3rd still is controlled at 120 ℃, the temperature of reaction of the 4th still is controlled at 125 ℃, react the back transformation efficiency and be about 55%, through the extrusion of devolatilization equipment, just can obtain transparent rubber modified polystyrene resin of the present invention.
Contain vinylbenzene tectonic element 37 weight parts, methyl methacrylate 63 weight parts, its molecular weight 3 in the external phase of above-mentioned composition, 000～50,000 account for 12 weight %, and the block content of the polystyrene of rubbery copolymer is 21 weight %, bag particle structure person accounted for 1.8% of whole rubber particles numbers in rubber particles contained more than 4, and the rubber particles number of bag particle structure does not account for 75% in not containing, and the measured rerum natura of this resin is as shown in table 1.
Comparative example 2
With rubbery copolymer 8.4 weight parts (phenylethylene/butadiene content=15/85 weight %, 1,2-contents of ethylene=15.4%, the cumulative segmented copolymer of wood Buddhist nun viscosity 45), vinylbenzene 30.0 weight parts, methyl methacrylate 28.0 weight parts, vinyl cyanide 3.6 weight parts, ethylbenzene 30 weight parts, lauryl mercaptan 0.1 weight part, form feedstock solution with dibenzoyl peroxide 0.1 weight part, with aforementioned feedstock solution with the continuous pump to 4 of a 35kg/hr placed in-line complete hybrid reactor (capacity of every still is 40 liters) continuous polymerization unit, wherein, the temperature of reaction of first still is controlled at 110 ℃, the temperature of reaction of second still is controlled at 115 ℃, the temperature of reaction of the 3rd still is controlled at 125 ℃, the temperature of reaction of the 4th still is controlled at 130 ℃, react the back transformation efficiency and be about 58%, through the extrusion of devolatilization equipment, just can obtain transparent rubber modified polystyrene resin of the present invention.
Contain vinylbenzene tectonic element 47 weight parts, methyl methacrylate 47 weight parts, vinyl cyanide 6 weight parts in the external phase of above-mentioned composition, its molecular weight 3,000～50,000 account for 33 weight %, and the block content of the polystyrene of rubbery copolymer is 2 weight %, bag particle structure person accounted for 9% of whole rubber particles numbers in rubber particles contained more than 4, and the rubber particles number of bag particle structure does not account for 15% in not containing, and the measured rerum natura of this resin is as shown in table 1.
Comparative example 3
With rubbery copolymer 8.4 weight parts (phenylethylene/butadiene content=5/95 weight %, 1,2-contents of ethylene=18.0%, the cumulative segmented copolymer of wood Buddhist nun viscosity 45), vinylbenzene 27.1 weight parts, methyl methacrylate 32.7 weight parts, vinyl cyanide 1.8 weight parts, ethylbenzene 30 weight parts, lauryl mercaptan 0.1 weight part, form feedstock solution with dibenzoyl peroxide 0.1 weight part, with aforementioned feedstock solution with the continuous pump to 4 of a 35kg/hr placed in-line complete hybrid reactor (capacity of every still is 40 liters) continuous polymerization unit, wherein, the temperature of reaction of first still is controlled at 110 ℃, the temperature of reaction of second still is controlled at 115 ℃, the temperature of reaction of the 3rd still is controlled at 125 ℃, 130 ℃ of the temperature of reaction controls of the 4th still, react the back transformation efficiency and be about 61%, through the extrusion of devolatilization equipment, just can obtain transparent rubber modified polystyrene resin of the present invention.
Contain vinylbenzene tectonic element 44 weight parts, methyl methacrylate 53 weight parts, vinyl cyanide 3 weight parts in the external phase of above-mentioned composition, its molecular weight 3,000～50,000 account for 33 weight %, and the block content of the polystyrene of rubbery copolymer is 0%, bag particle structure person accounted for 30% of whole rubber particles numbers in rubber particles contained more than 4, and the rubber particles number of bag particle structure does not account for 2% in not containing, and the measured rerum natura of this resin is as shown in table 1.
Comparative example 4
With rubbery copolymer 8.4 weight parts (phenylethylene/butadiene content=25/75 weight %, 1,2-contents of ethylene=15.4%, the cumulative segmented copolymer of wood Buddhist nun viscosity 45), vinylbenzene 16.8 weight parts, methyl methacrylate 43.0 weight parts, vinyl cyanide 1.8 weight parts, ethylbenzene 30 weight parts, lauryl mercaptan 0.25 weight part, form feedstock solution with dibenzoyl peroxide 0.14 weight part, with aforementioned feedstock solution with the continuous pump to 4 of a 35kg/hr placed in-line complete hybrid reactor (capacity of every still is 40 liters) continuous polymerization unit, but temperature of reaction changes into: the temperature of reaction of first still is controlled at 120 ℃, the temperature of reaction of second still is controlled at 125 ℃, the temperature of reaction of the 3rd still is controlled at 130 ℃, the temperature of reaction of the 4th still is controlled at 135 ℃, react the back transformation efficiency and be about 62%, through the extrusion of devolatilization equipment, just can obtain transparent rubber modified polystyrene resin of the present invention.
Contain vinylbenzene tectonic element 33 weight parts, methyl methacrylate 64 weight parts, vinyl cyanide 3 weight parts in the external phase of above-mentioned composition, its molecular weight 3,000～50,000 account for 52 weight %, and the block content of the polystyrene of rubbery copolymer is 18 weight %, bag particle structure person accounted for 5% of whole rubber particles numbers in rubber particles contained more than 4, and the rubber particles number of bag particle structure does not account for 65% in not containing, and the measured rerum natura of this resin is as shown in table 1.
Embodiment 5
With rubbery copolymer 9.0 weight parts (phenylethylene/butadiene content=25/75 weight %, 1,2-contents of ethylene=15.4%, the cumulative segmented copolymer of wood Buddhist nun viscosity 45, wherein the content of polystyrene block is 18 weight %), vinylbenzene 24.2 weight parts, methyl methacrylate 33.2 weight parts, vinyl cyanide 1.8 weight parts, N-phenylmaleimide 1.2 weight parts, polydimethylsiloxane 0.0045 weight part, ethylbenzene 30.6 weight parts, lauryl mercaptan 0.1 weight part, form feedstock solution with two-peroxidation tributyl-six hydrogen-terephthalate 0.1 weight part, with aforementioned feedstock solution with the continuous pump to 4 of a 35kg/hr placed in-line complete hybrid reactor (capacity of every still is 40 liters) continuous polymerization unit, in addition, N-phenylmaleimide is continuously pumped into second still with the speed of 0.32kg/hr, wherein the temperature of reaction of first still is controlled at 100 ℃, the temperature of reaction of second still is controlled at 105 ℃, the temperature of reaction of the 3rd still is controlled at 115 ℃, the temperature of reaction of the 4th still is controlled at 130 ℃, react the back transformation efficiency and be about 60%, through the extrusion of devolatilization equipment, just can obtain transparent rubber modified polystyrene resin of the present invention.
Contain vinylbenzene tectonic element 28 weight parts, methyl methacrylate 66 weight parts, vinyl cyanide 3 weight parts, N-phenylmaleimide 3 weight parts in the external phase of above-mentioned composition, survey its transparency (Haze) 6.1%, mobile (g/10min) 1.9, impact strength (kg/cm-cm) 18, chemical proofing good (zero).
Experimental result by comparative example 1 is learnt, multipolymer in resin combination is formed and is not contained acrylic monomer composition, molecular weight 3,000～50,000 content are less than 15 weight %, when the rubber particles number of bag particle structure was on the low side a little in adding more than 4 or 4, processibility of resin (flowability) and chemical proofing were not good, and the shock-resistance of resin is also not good simultaneously; And learn that by the test-results of comparative example 2 polystyrene block content is less than 5 weight % in the rubbery copolymer of resin combination, and the rubber particles of bag particle structure is counted ratio when on the low side in not containing, resin transparent relatively poor; And the polystyrene block content of working as rubbery copolymer is lower than 5 weight %, and the ratio of the rubber particles number of bag particle structure is higher in having more than 4 or 4, and when the ratio of rubber particles number of bag particle structure is on the low side in not containing, the transparency of resin is poor, and this experimental result by comparative example 3 is provable; In addition, learnt by comparative example 4 that molecular weight 3,000～50 in multipolymer external phase, when 000 ratios that account for whole multipolymer external phases (B) were higher than 50 weight %, impact strength and chemical proofing were relatively poor.
And consult various embodiments of the present invention, the present invention is by the content of controlling polystyrene block in the rubbery copolymer, molecular weight 3 in the multipolymer external phase (B), 000～50,000 ratio, the acrylic composition of multipolymer external phase (B), the rubber particles of bag particle structure is counted ratio in containing more than 4 or 4, the ratio of the rubber particles number of bag particle structure in not containing, really can make resin combination have preferable chemical proofing, processibility, simultaneously also can obtain the good transparency and shock-resistance, therefore, the present invention really is a novelty, progressive, and the resin combination with utility value on the industry.
Table 1
Claims (6)
1. transparent rubber modified polystyrene resin composite, it is characterized in that: described resin combination is by the formed rubber particles disperse phase of rubbery copolymer (A), and multipolymer external phase (B) is formed, wherein, this rubbery copolymer is for containing: styrenic monomers 10～50 weight %, with the segmented copolymer of diene monomer 90～50 weight %, the content of the polystyrene block in the above-mentioned rubbery copolymer accounts for 5～35 weight % of rubbery copolymer; And this multipolymer external phase (B) be by: total is measured styrenic monomers 12～70 weight parts, (methyl) acrylic ester monomer 20～80 weight parts, acrylic monomer 1～20 weight part of 100 weight parts, form with other copolymerizable monomer 0～40 weight parts, and molecular weight is 3 in the multipolymer external phase (B), 000～50,000 account for 15～50 weight % of whole multipolymer external phases (B).
2. transparent rubber modified polystyrene resin composite as claimed in claim 1 is characterized in that: the rubber particles number of bag particle structure accounts for 2～20% of whole rubber particles numbers in containing more than 4 or 4 in the rubber particles disperse phase (A).
3. transparent rubber modified polystyrene resin composite as claimed in claim 1 is characterized in that: the rubber particles number of bag particle structure does not account for 20～80% of whole rubber particles numbers in not containing in the rubber particles disperse phase (A).
4. transparent rubber modified polystyrene resin composite as claimed in claim 1 is characterized in that: rubbery copolymer is for forming a part cumulative segmented copolymer.
5. transparent rubber modified polystyrene resin composite as claimed in claim 1 is characterized in that: the content of the polystyrene block in this rubbery copolymer is 10～25 weight %.
6. transparent rubber modified polystyrene resin composite as claimed in claim 1 is characterized in that: the content of the polystyrene block in this rubbery copolymer is 14～22 weight %.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101565532B (en) * | 2008-04-22 | 2011-01-05 | 奇美实业股份有限公司 | Resin composition of rubber modified (methyl) acrylic ester |
| CN101506300B (en) * | 2006-09-12 | 2011-05-04 | 第一毛织株式会社 | Transparent ABS resin composition having excellent impact strength and flowability |
| CN101205274B (en) * | 2006-12-18 | 2011-06-01 | 奇美实业股份有限公司 | Rubber modified styrene series resin composition |
| US8093332B2 (en) | 2003-09-29 | 2012-01-10 | Fina Technology, Inc. | High impact polystyrene and process for preparing same |
| CN102344537A (en) * | 2010-07-30 | 2012-02-08 | 奇美实业股份有限公司 | Block copolymer and polymer composition prepared with block copolymer |
| CN101809087B (en) * | 2007-09-26 | 2015-04-22 | 波利玛利欧洲股份公司 | Transparent compositions based on high-impact vinyl aromatic copolymers |
| CN104892859A (en) * | 2015-05-27 | 2015-09-09 | 长春工业大学 | Transparent rubber modified styrene resin and preparation method thereof |
-
2000
- 2000-08-04 CN CNB001226290A patent/CN1149258C/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8093332B2 (en) | 2003-09-29 | 2012-01-10 | Fina Technology, Inc. | High impact polystyrene and process for preparing same |
| CN101506300B (en) * | 2006-09-12 | 2011-05-04 | 第一毛织株式会社 | Transparent ABS resin composition having excellent impact strength and flowability |
| CN101205274B (en) * | 2006-12-18 | 2011-06-01 | 奇美实业股份有限公司 | Rubber modified styrene series resin composition |
| CN101809087B (en) * | 2007-09-26 | 2015-04-22 | 波利玛利欧洲股份公司 | Transparent compositions based on high-impact vinyl aromatic copolymers |
| CN101565532B (en) * | 2008-04-22 | 2011-01-05 | 奇美实业股份有限公司 | Resin composition of rubber modified (methyl) acrylic ester |
| CN102344537A (en) * | 2010-07-30 | 2012-02-08 | 奇美实业股份有限公司 | Block copolymer and polymer composition prepared with block copolymer |
| CN104892859A (en) * | 2015-05-27 | 2015-09-09 | 长春工业大学 | Transparent rubber modified styrene resin and preparation method thereof |
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| CN1149258C (en) | 2004-05-12 |
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