CN100335557C - Transparent rubber modified polyphenylethylene series resin - Google Patents
Transparent rubber modified polyphenylethylene series resin Download PDFInfo
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- CN100335557C CN100335557C CNB031249531A CN03124953A CN100335557C CN 100335557 C CN100335557 C CN 100335557C CN B031249531 A CNB031249531 A CN B031249531A CN 03124953 A CN03124953 A CN 03124953A CN 100335557 C CN100335557 C CN 100335557C
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Abstract
The present invention provides transparent rubber modified polystyrene series resin which is composed of a copolymer continuous phase and a rubber particle dispersed phase formed by a rubbery copolymer, and a forming article of the resin ejected by a mirror surface mould is determined by a surface roughness meter. The maximal height difference value delta Hmax of the forming article is smaller than 3200*, the average height difference value delta Have of the forming article is smaller than 2000*, and rubber particles with the long diameter of larger than 0.3 mu m are observed by an electronic microscope in the depth of 1.8 to 2.2 mu m under the surface of the forming article. Under the anneal condition of 120 DEG C*40 min, the average ratio of the long diameter a of the rubber particles to the short diameter b of the rubber particles before anneal is A1, the average ratio of the long diameter a of the rubber particles to the short diameter b of the rubber particles after the anneal is A2, and the ratio of A1 to A2 is from 1.08 to 2.35. The resin can have good practical transparence and good physical performances by the conditional control.
Description
Technical field
The present invention is about a kind of transparent rubber modified polystyrene resin, is meant a kind ofly by multipolymer external phase especially, and the formed rubber particles disperse phase of rubbery copolymer forms, and has the resin of the transparent transitivity of good practicality.
Technical background
Rubber modified polystyrene resin is a kind of have good mechanical strength and good material of processing forming, because this resin has above-mentioned advantage, so extensively be used in household supplies, tame electrical articles such as food product containers, packing material, and on the shell of OA machine, but because the 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 known skill, polystyrene resin and styrene-butadiene block copolymer can be mixed, but this kind method can't be filled a part physical strength that improves resin, unsatisfactory in the use.Generally speaking, the resin that so-called transparency is good is that synthetic resin is measured with 90 degree input angles (with moulding product angle), its transparency is good, but when we when the skew back face is observed the moulding product, but usually find the transparency variation, i.e. transparency variation in the practicality.Because this practical transparency is not good, cause the overall quality impression of product to descend.
And Japanese kokai publication hei 4-180907 application for a patent for invention case, provide 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 kind method can be improved the transparency and the physical strength of resin, can't satisfy the good demand of the practical transparency.
Summary of the invention
This case contriver is through finding after the research with keen determination, in the multipolymer external phase of forming by styrenic monomers, (methyl) acrylic ester monomer and copolymerizable monomer (A), cooperate and contain the rubber particles disperse phase (B) that rubbery copolymer forms, and cooperate specific formation of this external phase and disperse phase and synthetic resin rubber particles change condition before and after annealing, and the surface roughness of synthetic resin, can make rubber-modified polystyrene resin have the transparent transitivity of preferable practicality.
The objective of the invention is at the transparent rubber modified polystyrene resin that the good practical transparency of a kind of tool and impact strength are provided.
Transparent rubber modified polystyrene resin of the present invention is by rubber particles disperse phase (A) that the rubbery copolymer of 1～25 weight % forms, and the multipolymer external phase (B) of 99～75 weight % is formed, wherein multipolymer external phase (B) is to be measured styrenic monomers 20～70 weight parts, (methyl) acrylic ester monomer 30～80 weight parts of 100 weight parts by total, and copolymerizable monomer 0～40 weight part forms.
Transparent rubber modified polystyrene resin of the present invention is fixed with the surface roughness instrumentation through the moulding product that the minute surface mould penetrates, the height difference of measuring is Δ H, wherein Zui Da height difference DELTA Hmax is less than 3200 , and average height difference DELTA Have is less than 2000 , and following 1.8～2.2 μ m depths on aforementioned moulding product surface, in the rubber particles of major diameter with the electron microscope observation rubber particles greater than 0.3 μ m, under the annealing conditions of 120 ℃ * 40min, the mean ratio (A2) of rubber particles major diameter a/ minor axis b after rubber particles major diameter a/ minor axis b mean ratio (A1) before it is unannealed and the annealing, wherein the ratio of A1/A2 is 1.08～2.35.
Composition according to above-mentioned resin can obtain the transparent rubber modified polystyrene resin with the transparent transitivity of good practicality required for the present invention.
Embodiment
Rubbery copolymer used in the present invention can be: in the presence of organic solvent, use organolithium compound to be used as initiator, and with styrenic monomers, diene monomer, and proper amount of solvent is carried out the segmented copolymer that anionic polymerisation forms, wooden Buddhist nun (Moony) viscosity (ML of above-mentioned multipolymer
1+4) be 20～80, soltion viscosity is 3～60cps (following at 25 ℃, the styrene solution viscosity of rubbery copolymer 5 weight %), and 1 in the diolefin series unit, 2-vinyl structure amount accounts for more than the 8 weight %, and the block structure of above-mentioned rubbery copolymer can be: homopolymer block (block) structure, part disorderly structure, the composition part cumulative block (taper-block) of row's (random) block are constructed.Rubbery copolymer can be aligned structure or difference structure etc. in addition.
Rubbery copolymer of the present invention is except using above-mentioned block copolymerization beyond the region of objective existence, also can in a small amount of segmented copolymer, account for disorderly row's styrene butadiene rubbers of butadiene-based homopolymer below 20 weight parts or solution polymerization process and use with respect to 100 weight parts, above-mentioned butadiene-based homopolymer is low cis (Low-cis) structure, the typical weight compositing range of cis/vinyl in the structure (cis-vinyl) is 30%～40%/5%～40%, soltion viscosity is 5～400cps (at 25 ℃ following, the styrene solution viscosity of rubbery copolymer 5 weight %).The manufacture method of rubbery copolymer of the present invention is a technique known, detailed method is stated from: No. the 2nd, 975,160, U.S., the 3rd, 094, No. 514, the 3rd, 135, No. 716, the 3rd, 244, No. 664, the 3rd, patent cases such as 318, No. 862, and in patent case such as Japanese Patent Publication 48-875 number, Japanese Patent Publication 48-46691 number, Japanese Patent Publication 49-36957 number, Japanese kokai publication sho 55-40734 number, Japanese kokai publication sho 57-40513 number or the patent application case.
In the rubbery copolymer of the present invention, still can and use in addition to the foregoing: 1, the 2-contents of ethylene can obtain the transparent rubber modified polystyrene resin that the practical transparency is good and impact strength is good at the styrene-butadiene copolymer of 25～50 weight %.
The concrete example of the styrenic monomers of rubbery copolymer of the present invention, for example: 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 concrete example of the present invention, for example: 1,3-butadiene, 2-methyl isophthalic acid, 3-divinyl, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 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 2-methyl isophthalic acid, 3-divinyl 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, its concrete example as: 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. one or more mix and use.
The rate of polymerization, 1 of rubbery copolymer of the present invention when polymerization, the 2-contents of ethylene, and the reactivity of diene monomer and styrenic monomers random row state when, can change agent by polar compound or random row (random) and adjust, above-mentioned polar compound or random rowization agent can be selected from: the potassium or the sodium salt of ethers, amine (amine), thioether class, alkylbenzene, sulphur (sulfon) acids, trialkylphosphine oxide.
In the transparent rubber modified polystyrene resin of the present invention, its rubbery copolymer content is 1～25 weight %, is preferably 8～25 weight %, and the best is 12～25 weight %; When this content during greater than 1 weight %, the impact strength of resin forming product is good, and content is lower than 25 weight %, and the transparency and the formability of resin forming product are good.
In addition, multipolymer external phase of the present invention (B) is (methyl) acrylic ester monomer by the styrenic monomers of 20～70 weight parts, 30～80 weight parts, and the copolymerizable monomer of 0～40 weight part forms, wherein, the object lesson of styrenic monomers is the styrenic monomers of rubbery copolymer as described above, no longer repeats to enumerate explanation.
And the monomeric concrete example of aforementioned (methyl) acrylic ester, for example: methyl acrylic ester and esters of acrylic acid, wherein, methyl acrylic ester can be for example: methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate, methacrylic acid 2-hydroxyl ethyl ester, glycidyl 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 n-butyl acrylate again.
There is no particular restriction for the kind of the copolymerizable monomer of multipolymer external phase of the present invention (B), the content ratio that can adjust each copolymerization monomer according to need is to reach the flexion rate of adjusting, it is transparent in necessary that last resin is reached, and the concrete example of above-mentioned copolymerizable monomer can be: the unsaturated fatty acids of methylene-succinic acid, toxilic acid, fumaric acid, butenoic acid, styracin, vinylformic acid, methacrylic acid etc.; Vinyl cyanide such as vinyl cyanide, methacrylonitrile monomer; Unsaturated carboxylic acid anhydrides classes such as maleimide monomer, maleic anhydride, itaconic anhydride, citraconic anhydride.Be preferable wherein with vinyl cyanide.
Above-mentioned maleimide monomer can be selected from: N-methyl maleimide, N-sec.-propyl maleimide, the N-butyl maleimide, N-hexyl maleimide, N-octyl group maleimide, N-dodecyl maleimide, N-cyclohexyl maleimide, N-phenylmaleimide, N-2,3-xylyl maleimide, N-2,4-xylyl maleimide, N-2,3-diethyl phenyl maleimide, N-2,4-diethyl phenyl maleimide, N-2,3-two butylbenzene base maleimides, N-2,4-two butylbenzene base maleimides, N-2,6-xylyl maleimide, N-2,3-dichlorophenyl maleimide, N-2,4-dichlorophenyl maleimide, N-2,3-dibromo phenyl maleimide, N-2,4-dibromo phenyl maleimide etc.; Wherein, be good with, N-phenylmaleimide.
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 structure can obtain the rerum natura balance of better impact strength and processibility (flowability).The multipolymer external phase (B) of above-mentioned difference shape structure can be by when the polymerization, adopts or add one or more to contain multi-functional unsaturated group monomer, multi-functional initiator, multi-functional chain transfer agent and reach.
The weight average molecular weight of the multipolymer external phase (B) of resin of the present invention is also without particular limitation, is generally 50,000～300,000, is preferably 60,000～200,000, is more preferred from 70,000～150,000.The amount of multipolymer external phase of the present invention (B) is 99～75 weight %, is preferably 92～75 weight %, and the best is 88～75 weight %.In the rubber particles disperse phase (A) of transparent rubber modified polystyrene resin of the present invention, the weight average particle diameter of rubber particles is 0.18～1 μ m, is preferably 0.2～0.6 μ m again, the best be 0.23～0.5 μ m between.Rubber particles footpath in the resin of the present invention is preferable greater than the particle content of 0.78 μ m with 0～25 weight % that accounts for whole rubber particles, is more preferred from 0～17 weight %, and the best is 1～15 weight %.When the weight average particle diameter of rubber particles or rubber particles footpath when the particle distribution amount of 0.78 μ m is in aforementioned range, the resin that can obtain having the preferable practical transparency, transparency and impact strength.
The weight average particle diameter of above-mentioned rubber particles and rubber particles footpath is measured greater than the particle content of 0.78 μ m, be with ultrathin sectioning with resin slicer, record weight average particle diameter again with the observation of infiltration type electron micrograph, and 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 of the present invention, is generally 2～40 weight %, is preferably 8～35 weight %, is more preferred from 12～30 weight %.In addition, the swelling index of resin of the present invention does not have special restriction yet, is generally 2～25, is preferably 3～20, is more preferred from 5～15.
The insoluble part content (weight %) and the swelling exponential of above-mentioned resin are measured mode, be that resin 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, get insoluble part weight after its subnatant obtains swelling then, again with insoluble part with 80 ℃ of vacuum-dryings 12 hours, obtain dry insoluble part weight, calculate insoluble part content (weight %) thereafter with following formula.
Swelling index of the present invention is to calculate with the following formula formula:
Transparent rubber modified polystyrene resin of the present invention, maximum height difference DELTA Hmax and average height difference DELTA Have are defined as follows: the mode of mensuration is the Akume No.2 standard minute surface mould that adopts Akume company ejection formation to use (the grinding benchmark of (2) encapsulation molding of " Plastic mould handbook " the 4th chapter 4.8.2 that published in 1989 referring to Nikkan Kogyo Shimbun), and the surface roughness of measuring the minute surface mould with the Ra method of JIS B0601 is 0.1 μ m.With resin with the thick 3mm of aforementioned minute surface mould ejection formation, the circular test piece of diameter 5.5cm, penetrate temperature (cylinder temperature) in the ejaculation condition of above-mentioned test piece and be generally 180 ℃～300 ℃, be preferably 200 ℃～280 ℃, and die temperature (mold temperature) is generally 20 ℃～100 ℃, be preferably 40 ℃～90 ℃, measure moulding product surfacing zone in surface roughness (surface profiler) then, each useful range (length) is 1,000 μ m, measure the height number (H) in this scope, the height number of the maximum in this scope (Hmax), with the difference of the height number (Hmin) of minimum be Δ Hi (height difference), i.e. Δ Hi=Hmax-Hmin.Each Δ Hi and average is measured in the different location in mensuration moulding product surfacing zone 20 times, gets an average height difference DELTA Have (i.e. the mean value of 20 times Δ Hi).Choose measure for 20 times in maximum Δ Hi claim this maximum Δ Hi to be maximum height difference DELTA Hmax, wherein Zui Da height difference DELTA Hmax should be less than 3200 , as Δ Hmax during greater than 3200 , can cause the practical transparent variation of resin, and average height difference DELTA Have of the present invention should be less than 2000 , as average height difference DELTA Have during, can cause the shortcoming of practical transparency difference equally greater than 2000 .
Following 1.8～2.2 μ m depths on aforementioned moulding product surface, in the rubber particles of major diameter with the electron microscope observation rubber particles greater than 0.3 μ m, under the annealing conditions of 120 ℃ * 40min, the mean value (A2) of rubber particles major diameter a/ minor axis b after rubber particles major diameter a/ minor axis b mean ratio (A1) before it is unannealed and the annealing, wherein the ratio of A1/A2 is 1.08～2.35, be preferably 1.08～2.2, the best is 1.1～2.0.When the ratio of A1/A2 was in above-mentioned scope, the practical transparency and the impact strength of resin were good.
There is no particular restriction for the manufacture method of rubber modified polystyrene resin of the present invention, but to adopt bulk or solution polymerization process is preferable, when adopting bulk or solution polymerization process, can obtain preferable transparency and preferable processibility, for example: the good and low mold fouling of heat-resistant quality etc.
The manufacture method of rubber modified polystyrene resin of the present invention, in the presence of rubbery copolymer, with styrenic monomers, (methyl) acrylic ester monomer and according to need and the copolymerizable monomer of adding is criticized formula or continous way bulk/solution graft copolymerization polyreaction, wherein, can obtain the more stable transparency and the rerum natura of impact strength with the continous way method for making again.With the continuous solution polymerization is example, at first with above-mentioned rubbery copolymer, monomer reaches optionally and adding appropriate solvent formation raw material mixing solutions, the aforementioned base materials mixing solutions can have high shear stress in tradition, dissolve in the dissolving tank of high stirring velocity, this dissolving tank can use: have ribbon spiral formula paddle, propeller formula paddle, perhaps other can produce the paddle of high shear stress etc., under time enough, above-mentioned rubbery copolymer can be dissolved into fully the state of rubber solutions (being feedstock solution), carry out with the operation that makes things convenient for pumping to be delivered 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 continuously stirring formula reactor (CSTR), or the embolism flow reactor (Plug flowreactor, PFR), or same a kind of or different types of combination of static(al) hybrid (static mixing reactor) reactor.Its temperature of reaction is controlled at 70～230 ℃.
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), connect second and/or follow-up reactor afterwards again, above-mentioned subsequent reactor can be continuously stirring formula reactor, embolism flow reactor or static(al) mixing reactor etc.With regard to obtaining the good practical transparency, adopt continuously stirring formula reactor (CSTR) with the 1st reactor, and last reactor employing embolism flow reactor is preferable, is more preferred from the 1st～3 and all adopts CSTR, the 4th is adopted the embolism flow reactor.
Generally speaking, the monomer conversion of first reactor is preferably 2～35 weight % about 1～40 weight %, is more preferred from 3～30 weight %.And the monomer conversion of aforementioned first reactor is selected, adjusts according to difference such as employed rubbery copolymer content kind, viscosity.The final transformation efficiency of monomer during polymerization of the present invention is generally 60～98%, and with regard to obtaining the good practical transparency, preferable final transformation efficiency is 70～98%, is more preferred from 82～97%.
Transparent rubber modified polystyrene resin 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-hexane, hexanaphthene, just-aliphatic hydrocarbons such as heptane are the some of solvent.
Transparent rubber modified polystyrene resin of the present invention in the mill, the addition of spendable initiator is monomeric 0～2 weight part with respect to 100 weight parts, be preferably 0.001～0.7 weight part, and the kind of initiator is as follows:
(I) peroxidation alkanes (alkyl peroxide): the tributyl-peroxidation cumic aldehyde (t-butylcumyl peroxide, hereinafter to be referred as Per butyl C), α, α '-two (peroxidation tributyl) diisopropyl benzene [α, α '-bis-(t-butyl peroxy) diisopropyl benzene, hereinafter to be referred as Per butyl P], 1, two (peroxidation the tributyl)-diisopropyl benzenes [1 of 3-, 3-bis-(t-butyl peroxy) diisopropyl benzene is hereinafter to be referred as PX-14].
(II) peroxyesters (peroxyester): two-peroxidation tributyl-six hydrogen-terephthalate (di-t-butyl-peroxy-hexahydro-terephthalate is called for short BPHTP) etc.
(III) peroxycarbonates class (peroxycarbonate): Diethylene Glycol-two-(the tributyl peroxycarbonates] [Di-ethylene glycol-bis (t-butyl-peroxycarbonate), the Japanese chemical drug カ ヤ レ of company Application O-50] etc.
(IV) acyl peroxide class (Diacyl peroxide) :-mixture (m-toluoyl and benzoyl peroxide is called for short Nyper BMT-K40) of methyl benzoyl and benzoyl mistake oxygen thing etc.
(V) ketal peroxide class (peroxy ketals): 4,4 '-two-peroxidation, the tributyl-valeric acid-positive butyl ester (4,4 '-di-t-butyl peroxy valeric acid-n-butyl ester is called for short TX-17) etc.
In order to obtain the resin of the preferable practical transparency, be preferably and merge two kinds used in the aforementioned 5 class initiators or more than two kinds, be more preferred from 3 kinds or 3 kinds above and usefulness, particularly (I), (II), (IV) three kinds and with being the best.
Transparent rubber modified polystyrene resin of the present invention in the mill, the addition of spendable chain transfer agent is monomeric 0～2 weight part with respect to 100 weight parts, be preferably 0.01～0.7 weight part, concrete example is as methyl sulphur
Alcohol, n-butyl mercaptan, cyclohexyl mercaptan, just-mercaptan (mercaptan) classes such as lauryl mercaptan, stearyl-mercaptan (stearylmercaptan), the 3rd-lauryl mercaptan (t-dodeyl mercaptan is called for short TDM), just-propyl group mercaptan, n-octyl mercaptan, the 3rd-octyl mercaptan, the 3rd-nonyl mercaptan.
Other is for example: pentaphenylethane (pentaphenylethane), α-Jia Jibenyixierjuwu (α-methyl styrene dimer), terpinolene (terpinolene).
Transparent rubber modified polystyrene resin of the present invention in the mill, can add multi-functional unsaturated group monomer according to need and carry out copolymerization, its addition is monomeric 0～1 weight part with respect to 100 weight parts, is preferably 0.005～0.6 weight part, its concrete example as:
(I) 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).
(II) ethylene glycol bisthioglycolate methyl acrylate (ethylene glycol dimethacrylate), Diethylene Glycol diacrylate methyl esters (di ethylene glycol dimethacrylate), three-ethylene glycol bisthioglycolate methyl acrylate (tri-ethyleneglycol dimethacrylate), polyoxyethylene glycol diacrylate methyl esters (polyethylene glycoldimethacrylate), 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 glycol dimethacrylate), 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].
(III) three methyl acrylate classes of trimethylolpropane tris methyl acrylate (trimethylol propane trimethacrylate), trihydroxyethyl ethane three methyl acrylates (triethylol ethane trimethacrylate) etc.
(IV) 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 glycoldiacrylate), neopentyl alcohol diacrylate (neopentyl glycol diacrylate, be called for short PGDA), propylene glycol diacrylate (di propylene glycol diacrylate), polypropyleneglycol diacrylate (polypropylene glycol diacrylate), 2, two (the 4-propylene acyloxy-propoxy--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 ethoxy phenyl) propane] of 2-etc.
(V) the triacrylate class of Viscoat 295 (trimethylol propane triacrylate), trihydroxyethyl ethane triacrylate (triethylol ethane triacrylate) etc.
(VI) the tetraacrylate class of tetramethylol methane tetraacrylate (tetramethylol methane tetraacrylate) etc.
From reactor, take out after the aforementioned polyreaction, low-volatiles such as unreacted monomer, solvent are removed, after polymer recovery, can make transparent rubber modified polystyrene resin of the present invention through preheater and devolatilization device.
Above-mentioned preheater temperature is controlled at 200～280 ℃, for obtaining the good practical transparency and form and aspect, is good with 245～270 ℃.And the devolatilization device can be: devolatilization groove and/or single shaft and/or twin shaft are with the extruder of devolatilization mouth, and can in extruder, add the devolatilization auxiliary agent according to need, as: water, hexanaphthene, carbonic acid gas etc., the general about 10 weight % of devolatilization auxiliary agent usage quantity following (with respect to the inlet amount 100 weight % of extruder).And extruder also can be provided with according to need and pinches confounding section (kneading zone), pushes section (pumpingzone) etc., screw speed is 120～350rpm, the temperature of extruder is 160～300 ℃, based on the preferable practical transparency and form and aspect, is good with 240～260 ℃.For the present invention, be good with twin shaft with the extruder of devolatilization mouth.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 180～320 ℃, is preferably 200～300 ℃, for obtaining the good practical transparency and form and aspect, is the best with 235～260 ℃.And the vacuum degree control of devolatilization groove is preferably below 200 Torr below 300 Torr, is more preferred from below 100 Torr; Other devolatilization equipment such as thin-film evaporator (thin film evaportor) also can adopt.
Via the processing of aforementioned devolatilization device, fugitive constituents such as residual monomer in the resin, solvent are reduced to below the 1 weight %, be preferably below the 0.8 weight %, for obtaining the good practical transparency, being the best below the 0.25 weight %.
In addition, carry out extrusion once more in the resin adding extruder that the present invention also can finish aforementioned devolatilization step according to need, can for example add according to need during extrusion: additives such as antioxidant, lubrication prescription, particularly add 0～0.5 weight % (with respect to the resin of 100 weight %), during superoxide that the 3rd amyl group (t-amyl) that is preferably 0.001～0.2 weight % is, the transparent rubber modified polystyrene resin that can obtain having the good practical transparency and form and aspect.
The superoxide that aforementioned the 3rd amyl group is, its object lesson is as two-peroxidation the 3rd amyl group compound (di-t-amyl peroxy), 1,1-two-(peroxidation the 3rd amyl group) hexanaphthene [1,1-di-(t-amylperoxy)-cyclohexane], 2,2-two-(peroxidation the 3rd amyl group) propane [2,2-di-(t-amylperoxy) propane], ethyl-3,3-two-(peroxidation the 3rd amyl group) butyrates [Ethylene-3,3-di-(t-amylperoxy) butyrate], be good wherein with two-peroxidation the 3rd amyl group compound.
The present invention desires to reach the purpose that practical transparency is good and impact strength is good, can create conditions via the following at least 2 kinds polymerization of regulation and control and reach:
(A) at least 2 kinds of polymerization initiators and use: the initiator kind is as peroxidation alkanes, peroxyesters, peroxycarbonates class, acyl peroxide class, ketal peroxide class.
(B) specific aggregation reactor or the selection of final transformation efficiency and the arrangement of polymerization reactor: general reactor is good with 3～6 continuously stirring formula reactors, be preferably the 1st reactor and adopt continuously stirring formula reactor (CSTR), last 1 reactor is adopted embolism flow reactor (Plug flow reactor, PFR), be more preferred from the 1st～3 reactor and adopt CSTR, last 1 reactor is adopted the embolism flow reactor.And final transformation efficiency is 60～98%, is preferable with 70～98%, is more preferred from 82～97%.
(C) resin of finishing devolatilization is with extruder extrusion again: particularly adding the 3rd amyl group is that superoxide and resin are mixed together extrusion.
(D) specific devolatilization processing procedure and residual volatile component:
(D
1) specific devolatilization preheater temperature: being generally 200～280 ℃, is good with 245～270 ℃.
(D
2) specific devolatilization groove temperature: generally with 180～320 ℃, preferable with 235～260 ℃.
(D
3) containing the extruder devolatilization of devolatilization mouth: 160～300 ℃ of general temperature be good with 240～260 ℃, and above-mentioned devolatilization mouth pressure is preferably the devolatilization auxiliary agent that adds below the 10 weight %, for example: water below 300Torr.
(D
4) control of resin residue fugitive constituent: below 1 weight %, be the best generally with 0.25 weight %.
(E) the polymeric selection of specific rubber-like: for example low viscous styrene butadiene based block copolymer, disorderly arrange styrene-butadiene copolymer, particularly 1,2-contents of ethylene height is (for example more than at least 25%, be preferably more than 28%) the use of polystyrene-butadiene-based multipolymer, or aforementioned several rubber and use.
Transparent rubber modified polystyrene resin of the present invention is when polymerization, in the operational condition of above-mentioned (A), (B), (C), (D), (E), at least adopt 3, in order to obtain having the transparent rubber polystyrene resin of the good practical transparency, to adopt more than 4 or 4 to preferable, particularly (A), (C), (D) or (A), (B), (D), (E) be combined as the best.
In the scope that is not showing the effect that undermines resin of the present invention, adjustable other composition, this type of other composition be for example: the additive of tinting material, 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: the ester of mineral oil, for example butyl stearate is that plasticizer, polyester are that organopolysiloxane, higher fatty acid and metal-salt thereof, 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) of plasticizer or mineral oil generally at 0～5 weight %, be preferably 0.05～2 weight %, and the usage quantity of organopolysiloxane is preferably 0.002～0.2 weight % generally at 0～0.5 weight %.
In addition, do not showing under the transparent situation that undermines resin of the present invention, can further allocate other resin, and addible other resin is 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 with aforementioned multipolymer with the diene series rubber upgrading, for example: polystyrene-diolefin series-(methyl) acrylic ester-propylene
Based copolymer, polystyrene-diolefin series-(methyl) acrylic-maleimide based copolymer, polystyrene-diolefin series-(methyl) acrylic ester-maleimide based copolymer, (methyl) acrylic ester-diolefin series-maleimide based copolymer etc.
The aforementioned resin usage quantity is 0～200 weight part with respect to transparent rubber modified polystyrene resin 100 weight parts, and it can adjust or improve thermotolerance, rigidity and the flow processability of resin.
The purposes of transparent rubber phenylethylene resin series 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 mixing of aforementioned other composition or resin can be mixed by the general mixing muller of Bradley Bender plastometer, Ban Baili muller, kneading-mixing machine, roller press, single shaft or twin shaft extruder etc. and be made.After mixing such as common these extruders of mat are mixed; the extrusion thing of again signature being made is 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, transparency and the practical transparency (mist degree, Haze): with the test piece of resin ejection formed thick 3mm, diameter 5.5cm, penetrating temperature in the condition that penetrates is 220 ℃, die temperature is 50 ℃, then according to ASTM D-1003 standard test transparency, the line of observation is 90 degree (promptly observing test piece by directly over vertical) with the angle of test piece (horizontal plane), the transparency that records is Haze (90 °), the angle of the line of observation and test piece (horizontal plane) is 30 degree (promptly observing test piece by oblique side 30 degree), and the transparency of mensuration is Haze (30 °).The practical transparency is Haze (30 °)-both differences of Haze (90 °), when difference is littler, represents the practical transparency better.
Two, the synthetic resin surface roughness is measured: the AkumeNo.2 standard minute surface mould that adopts Akume company ejection formation to use, the rugosity that the surface of its minute surface mould is measured with the Ra method of JIS B0601 is 0.1 μ m.With resin with aforementioned minute surface mould ejection formation, get the round test piece of thick 3mm, diameter 5.5cm, in surface roughness (surface profiler, type Tencor Alpha step 500) round surface roughness of measurement test piece is totally 20 times, obtains maximum height difference DELTA Hmax and average height difference DELTA Have.
Three, shock-resistance (IZOD): measure Emhorn shock strength (23 ℃ of 1/4 o'clock thick test films) with breach according to ASTM D-256.
Four, the weight average particle diameter of rubber particles and rubber particles footpath is measured greater than the particle content of 0.78 μ m: with resin slicer with the penetrating type electron microscope take the photo that obtains 25,000 times (12cm * 9.5cm), calculate according to following formula:
Ni is the number of the rubber particles of particle diameter Di.In addition, in 12cm * 9.5cm photo, calculate the rubber particles footpath and account for the content (weight %) of whole rubber particles,, calculate particle diameter with (major diameter+minor axis)/2 of rubber particles if when aforementioned rubber particles is non-circular greater than the rubber particles of 0.78 μ m.
Five, the mensuration of the residual volatile component in the resin (being residual monomer and solvent): after getting DMF (dimethyl amide, the Di methyl formamide) dissolving that 1 g of resin particle adds 10ml, measure with GC.
Six, the forward and backward rubber particles A1/A2 ratio determination method of moulding product annealing: the synthetic resin test piece that preceding second physical property measurement uses, utilize TEM (transmission electron microscope) and ultrathin sectioning to measure moulding product surface 1.8～2.2 μ m down, obtain 25000 times photo (12cm * 9.5cm) with electron micrograph, all choose the rubber particles of the major diameter of rubber particles greater than 0.3 μ m in the rubber particles of photo, measure the ratio of its major diameter a and minor axis b, calculating its mean ratio is A1, promptly
A wherein
iBe the major diameter of rubber particles, b
iBe the minor axis of rubber particles, n is the rubber particles number of major diameter greater than 0.3 μ m.In addition with above-mentioned moulding product under the 120 ℃ * 40mins condition annealing after, with the aforementioned ultrathin sectioning of utilizing, obtain with electron micrograph in the rubber particles of 25000 times of photos, choose the rubber particles of the major diameter of all rubber particles greater than 0.3 μ m, measure the ratio of major diameter a and minor axis b, calculating mean value with aforementioned formula is A2.Get the ratio that aforementioned A1, A2 can get A1/A2.So-called herein major diameter is meant the length of distance two-end-point formation major axis (straight line) farthest on the same rubber particles, minor axis be meant with the vertical direction of aforementioned major axis on, minor axis (straight line) length that the distance of rubber particles two-end-point farthest forms.With the oval rubber particles of ideal, the line of apsides of rubber particles i.e. this oval-shaped line of apsides.
The form of aforementioned rubber particles is to measure on the parallel surface on moulding product surface, promptly utilize ultrathin sectioning, successively cutting out with the surperficial parallel direction of moulding product, the thickness of every layer of section is between 0.05～0.09 μ m, mode is cut to the depths of 1.8～2.2 μ m according to this, gets after the slicing treatment at this place with the electron microscope observation rubber particles.
[embodiment 1]
Rubbery copolymer 14.1 weight parts [styrene-butadiene block copolymer, phenylethylene/butadiene content=25/75 weight %, 1,2-vinyl structure content=15%, wooden Buddhist nun's viscosity=47 (ML
1+4100 ℃)]; styrene monomer 40 weight parts; methyl methacrylate 57 weight parts; vinyl cyanide 3.0 weight parts; ethylbenzene 38 weight parts; n-dodecyl mercaptan 0.15 weight part; and the tributyl of 0.018 weight part-peroxidation cumic aldehyde (Japanese grease Perbutyl C); 0.002 between weight part-mixture (Japanese grease Nyper BMT-K40) of methyl benzoyl and benzoyl peroxide; 0.095 the formed feedstock solution of the two-peroxidation tributyl-six hydrogen-terephthalate of weight part (di-t-butyl peroxy hexahydro terephthalate); speed with 35Kg/hr is continuously pumped into 4 placed in-line continuously stirring formula reactors (CSTR); the capacity of reactor is all 40 liters; the temperature of reaction of each reactor is 100 ℃; 106 ℃; 120 ℃; 130 ℃; stirring velocity is 300rpm; 200rpm; 150rpm; 90rpm; the monomer conversion of the polymers soln of the 4th reactor outlet is 65%; aforementioned polymer solution heats through preheater; temperature is 250 ℃; again through devolatilization groove with vacuum apparatus; its devolatilization groove temperature is controlled at 240 ℃; obtain particulate resins; prepared particulate resins adds 0.02 weight %, two-peroxidation the 3rd amyl group compound again; with extruder mixing extrusion, can obtain transparent rubber modified polystyrene resin of the present invention.
The residual volatile component of resulting transparent rubber modified polystyrene resin is 0.12 weight %, the rerum natura of mensuration, transparency, practical transparency Haze (30 °)-Haze (90 °) and impact strength as shown in Table 1.
[embodiment 2]
Rubbery copolymer 13.7 weight parts [styrene-butadiene block copolymer, phenylethylene/butadiene content=25/75 weight %, 1,2-vinyl structure content=25%, wooden Buddhist nun's viscosity=49 (ML
1+4, 100 ℃)], styrene monomer 37 weight parts, methyl methacrylate 60 weight parts, propylene
3.0 weight part; ethylbenzene 38 weight parts; n-dodecyl mercaptan 0.12 weight part; and the tributyl of 0.006 weight part-peroxidation cumic aldehyde (Japanese grease Perbutyl C); 0.1 between weight part-mixture (Japanese grease Nyper BMT-K40) of methyl benzoyl and benzoyl mistake oxygen thing; 0.02 the formed feedstock solution of the two-peroxidation tributyl-six hydrogen-terephthalate of weight part (di-t-butyl peroxy hexahydro terephthalate); speed with 35Kg/hr is continuously pumped into 4 placed in-line continuously stirring formula reactors (CSTR); the capacity of reactor is all 40 liters; the temperature of reaction of each reactor is 90 ℃; 100 ℃; 120 ℃; 130 ℃; stirring velocity is 250rpm; 200rpm; 150rpm; 90rpm; the monomer conversion of the polymers soln of the 4th reactor outlet is 66%; aforementioned polymer solution heats through preheater; temperature is 250 ℃; again through devolatilization groove with vacuum apparatus; its devolatilization groove temperature is controlled at 230 ℃; obtain particulate resins; prepared particulate resins adds 0.03 weight %, two-peroxidation the 3rd amyl group compound again; with extruder mixing extrusion, can obtain transparent rubber modified polystyrene resin of the present invention.The residual volatile component of resulting transparent rubber modified polystyrene resin is 0.142 weight %, and the rerum natura of mensuration, transparency, practical transparency and impact strength are as shown in Table 1.
[embodiment 3]
Rubbery copolymer 14.4 weight parts [, are comprised: (1) styrene-butadiene block copolymer, SM/BD=25/75,1,2-vinyl structure content with the weight ratio of (1)/(2)/(3)=95/3/2 and with forming by following (1), (2), (3) three kinds of rubber
=15%, wooden Buddhist nun's viscosity=47 (ML
1+4, 100 ℃).(2) styrene-butadiene block copolymer, SM/BD=68/32,1,2-vinyl structure content=13 weight %, solution viscosity=5.5cps (multipolymer content is the toluene solution of 5 weight %, 25 ℃).(3) styrene butadiene rubbers, SM/BD=25/75,1,2-vinyl structure content=13%, solution viscosity=85cps,, the company's T ufdene 2100R of Asahi Chemical Industry], styrene monomer 41 weight parts, methyl methacrylate 55 weight parts, propylene
4.0 weight part; ethylbenzene 38 weight parts; n-dodecyl mercaptan 0.12 weight part; and the tributyl of 0.02 weight part-peroxidation cumic aldehyde (Japanese grease Perbutyl C); 0.09 between weight part-methyl benzoyl and benzoyl mistake oxygen thing mixture (Japanese grease Nyper BMT-K40); 0.02 the formed feedstock solution of the two-peroxidation tributyl-six hydrogen-terephthalate of weight part (di-t-butyl peroxy hexahydro terephthalate); speed with 35Kg/hr is continuously pumped into 4 placed in-line continuously stirring formula reactors (CSTR); the capacity of reactor is all 40 liters; the temperature of reaction of each reactor is 90 ℃; 100 ℃; 120 ℃; 127 ℃; stirring velocity is 300rpm; 200rpm; 150rpm; 120rpm; the monomer conversion of the polymers soln of the 4th reactor outlet is 68%; aforementioned polymer solution heats through preheater; temperature is 260 ℃; again through devolatilization groove with vacuum apparatus; its devolatilization groove temperature is controlled at 250 ℃; obtain particulate resins; prepared particulate resins adds 0.015 weight %, two-peroxidation the 3rd amyl group compound again; with extruder mixing extrusion, can obtain transparent rubber modified polystyrene resin of the present invention.The residual volatile component of resulting transparent rubber modified polystyrene resin is 0.16 weight %, and the rerum natura of mensuration, transparency, practical transparency and anti-impact strength are as shown in Table 1.
[embodiment 4]
Rubbery copolymer 19.3 weight parts are [by following (1), (2) two kinds of rubber with the weight ratio of (1)/(2)=93/7 and with forming, comprise: (1) styrene-butadiene block copolymer, SM/BD=25/75,1,2-vinyl structure content=15%, wooden Buddhist nun's viscosity=47 (ML
1+4, 100 ℃).(2) styrene butadiene rubbers, SM/BD=25/75,1,2-vinyl structure content=30%, wooden Buddhist nun's viscosity=55 (ME
1+4, 100 ℃), the company's T ufdene of Asahi Chemical Industry 2330], styrene monomer 38 weight parts, methyl methacrylate 58 weight parts, propylene
4.0 weight part; ethylbenzene 80 weight parts; n-dodecyl mercaptan 0.14 weight part; and the α of 0.009 weight part; α '-two (peroxidation tributyl) diisopropyl benzene (Japanese grease Perbutyl P); 0.135 between weight part-mixture (Japanese grease NyperBMT-K40) of methyl benzoyl and benzoyl mistake oxygen thing; 0.005 the formed feedstock solution of the two-peroxidation tributyl-six hydrogen-terephthalate of weight part (di-t-butylperoxy hexahydro terephthalate); speed with 35Kg/hr is continuously pumped into reactor; reactor system is in series by 4; wherein the 1st～3 reactor is continuously stirring formula reactor (CSTR); the 4th reactor is embolism flow reactor (PFR); the capacity of reactor is all 40 liters; the temperature of reaction of each reactor is 90 ℃; 100 ℃; 125 ℃; 128 ℃ of (inlet)～155 ℃ (outlet); stirring velocity is 300rpm; 200rpm; 150rpm; 30rpm; the monomer conversion of the polymers soln of the 4th reactor outlet is 90%; aforementioned polymer solution is 230 ℃ through the preheater Heating temperature; again through devolatilization groove with vacuum apparatus; its devolatilization groove temperature is controlled at 220 ℃; after with the twin shaft extruder extrusion of devolatilization mouth; the extrusion temperature is controlled at 250 ℃, can obtain transparent rubber modified polystyrene resin of the present invention.The residual volatile component of resulting transparent rubber modified polystyrene resin is 0.22 weight %, and the rerum natura of mensuration, transparency, practical transparency and impact strength are as shown in Table 1.
[embodiment 5]
Rubbery copolymer 18.1 weight parts are [by following (1), (2) two kinds of rubber with (1)/(2)=93/7 weight ratio and with forming, comprise: (1) styrene-butadiene block copolymer, SM/BD=25/75,1,2-vinyl structure content=15%, wooden Buddhist nun's viscosity=47 (ML
1+4, 100 ℃).(2) styrene butadiene rubbers, SM/BD=25/75,1,2-vinyl structure content=30%, wooden Buddhist nun's viscosity=55 (ML
1+4100 ℃); the company's T ufdene of Asahi Chemical Industry 2330]; styrene monomer 36 weight parts; methyl methacrylate 61 weight parts; vinyl cyanide 3.0 weight parts; ethylbenzene 63.6 weight parts; n-dodecyl mercaptan 0.16 weight part; and the α of 0.005 weight part; α '-two (peroxidation tributyl) diisopropyl benzene (Japanese grease Perbutyl P); 0.002 between weight part-mixture (Japanese grease NyperBMT-K40) of methyl benzoyl and benzoyl peroxide; 0.13 the formed feedstock solution of the two-peroxidation tributyl-six hydrogen-terephthalate of weight part (di-t-butylperoxy hexahydro terephthalate); speed with 35Kg/hr is continuously pumped into reactor; reactor is to be in series by 4; wherein the 1st～3 reactor is continuously stirring formula reactor (CSTR); the 4th reactor is embolism flow reactor (PFR); the capacity of reactor is all 40 liters; the temperature of reaction of each reactor is 98 ℃; 105 ℃; 126 ℃; 128 ℃ of (inlet)～150 ℃ (outlet); stirring velocity is 310rpm; 210rpm; 150rpm; 30rpm; the monomer conversion of the polymers soln of the 4th reactor outlet is 85%; aforementioned polymer solution heats through preheater; temperature is 260 ℃; again through devolatilization groove with vacuum apparatus; its devolatilization groove temperature is controlled at 240 ℃; after with the twin shaft extruder extrusion of devolatilization mouth; the extrusion temperature is controlled at 225 ℃; and the water that adds 1 weight % in the extruder can obtain transparent rubber modified polystyrene resin of the present invention as the extrusion auxiliary agent.The residual volatile component of resulting transparent rubber modified polystyrene resin is 0.14 weight %, and the rerum natura of mensuration, transparency, practical transparency and impact strength are as shown in Table 1.
[embodiment 6]
Rubbery copolymer 18.3 weight parts are [by following (1), (2) two kinds of rubber with (1)/(2)=93/7 weight ratio and with forming, comprise: (1) styrene-butadiene block copolymer, SM/BD=25/75,1,2-vinyl structure monomer=15%, wooden Buddhist nun's viscosity=47 (ML
1+4, 100 ℃).(2) styrene butadiene rubbers, SM/BD=25/75,1,2-vinyl structure content=30%, wooden Buddhist nun's viscosity=55 (ML
1+4100 ℃); the company's T ufdene of Asahi Chemical Industry 2330]; styrene monomer 39 weight parts; methyl methacrylate 58 weight parts; vinyl cyanide 3 weight parts; ethylbenzene 50.7 weight parts; n-dodecyl mercaptan 0.1 5 weight parts; and the α of 0.025 weight part; α '-two (peroxidation tributyl) diisopropyl benzene (Japanese grease Perbutyl P); 0.002 between weight part-mixture (Japanese grease NyperBMT-K40) of methyl benzoyl and benzoyl mistake oxygen thing; 0.1 the formed feedstock solution of two-peroxidation tributyl-six hydrogen-terephthalate (di-t-butylperoxyhexahydro terephthalate) of weight part; speed with 35Kg/hr is continuously pumped into reactor; reactor is to be in series by 4; wherein the 1st～3 reactor is continuously stirring formula reactor (CSTR); the 4th reactor is embolism flow reactor (PFR); the capacity of reactor is all 40 liters; the temperature of reaction of each reactor is 100 ℃; 106 ℃; 124 ℃; 126 ℃ of (inlet)～151 ℃ (outlet); stirring velocity is 300rpm; 200rpm; 150rpm; 30rpm; the monomer conversion 85% of the polymers soln of the 4th reactor outlet; aforementioned polymer solution heats through preheater; temperature is 240 ℃; again through devolatilization groove with vacuum apparatus; its devolatilization groove temperature is controlled at 220 ℃; after with the twin shaft extruder extrusion of devolatilization mouth; the extrusion temperature is controlled at 230 ℃; and the water that adds 0.5 weight % can obtain transparent rubber modified polystyrene resin of the present invention as the extrusion auxiliary agent.The residual volatile component of resulting transparent rubber modified polystyrene resin is 0.15 weight %, and the rerum natura of mensuration, transparency, practical transparency and impact strength are as shown in Table 1.
[embodiment 7]
With embodiment 1 prepared transparent rubber modified polystyrene resin 100 weight parts, and the methyl methacrylate butadiene rubber-phenylethene grafted copolymer of 8 weight parts (emulsion process manufacturing, powdery, the KCB650L of Wu Yu company), both mix after the extrusion, the residual volatile component of resulting transparent rubber modified polystyrene resin is 0.1 weight %, and the rerum natura of mensuration, transparency, practical transparency and impact strength are as shown in Table 1.
[embodiment 8]
Rubbery copolymer 18.3 weight parts are [by following (1), (2) two kinds of rubber with (1)/(2)=93/7 weight ratio and with forming, comprise: (1) styrene-butadiene block copolymer, SM/BD=25/75,1,2-vinyl structure monomer=15%, wooden Buddhist nun's viscosity=47 (ML
1+4, 100 ℃).(2) styrene butadiene rubbers, SM/BD=25/75,1,2-vinyl structure content=30%, wooden Buddhist nun's viscosity=55 (ML
1+4100 ℃); the company's T ufdene of Asahi Chemical Industry 2330]; styrene monomer 40.5 weight parts; methyl methacrylate 58 weight parts; just-butyl acrylate 1.5 weight parts; ethylbenzene 50.7 weight parts; n-dodecyl mercaptan 0.15 weight part; and the α of 0.025 weight part; α '-two (peroxidation tributyl) diisopropyl benzene (Japanese grease Perbutyl P); 0.002 between weight part-mixture (Japanese grease Nyper BMT-K40) of methyl benzoyl and benzoyl mistake oxygen thing; 0.1 the formed feedstock solution of the two-peroxidation tributyl-six hydrogen-terephthalate of weight part (di-t-butyl peroxy hexahydro terephthalate); speed with 35Kg/hr is continuously pumped into reactor; reactor is to be in series by 4; wherein the 1st～3 reactor is continuously stirring formula reactor (CSTR); the 4th reactor is embolism flow reactor (PFR); the capacity of reactor is all 40 liters; the temperature of reaction of each reactor is 100 ℃; 106 ℃; 125 ℃; 127 ℃ of (inlet)～151 ℃ (outlet); stirring velocity is 300rpm; 200rpm; 150rpm; 30rpm; the monomer conversion 86% of the polymers soln of the 4th reactor outlet; aforementioned polymer solution heats through preheater; temperature is 240 ℃; again through devolatilization groove with vacuum apparatus; its devolatilization groove temperature is controlled at 220 ℃; after with the twin shaft extruder extrusion of devolatilization mouth; the extrusion temperature is controlled at 235 ℃; and the water that adds 0.5 weight % can obtain transparent rubber modified polystyrene resin of the present invention as the extrusion auxiliary agent.The residual volatile component of resulting transparent rubber modified polystyrene resin is 0.152 weight %, and the rerum natura of mensuration, transparency, practical transparency and impact strength are as shown in Table 1.
[comparative example 1]
Rubbery copolymer 13 weight parts [styrene-butadiene block copolymer, SM/BD=25/75,1,2-vinyl structure content=15%, wooden Buddhist nun's viscosity=47 (ML
1+4100 ℃)], styrene monomer 38 weight parts, methyl methacrylate 58 weight parts, vinyl cyanide 4 weight parts, ethylbenzene 37.7 weight parts, n-dodecyl mercaptan 0.15 weight part, and the formed feedstock solution of the two-peroxidation tributyl-six hydrogen-terephthalate of 0.1 weight part (di-t-butyl peroxy hexahydro terephthalate), speed with 35Kg/hr is continuously pumped into 3 placed in-line continuously stirring formula reactors (CSTR), the capacity of reactor is all 40 liters, the temperature of reaction of each reactor is 95 ℃, 105 ℃, 125 ℃, stirring velocity is 300rpm, 200rpm, 150rpm, the monomer conversion of the polymers soln of the 3rd reactor outlet is 62%, aforementioned polymer solution heats through preheater, temperature is 240 ℃, again through devolatilization groove with vacuum apparatus, its devolatilization groove temperature is controlled at 220 ℃, can obtain transparent rubber modified polystyrene resin.The residual volatile component of resulting transparent rubber modified polystyrene resin is 0.38 weight %, and the rerum natura of mensuration, transparency, practical transparency and impact strength are as shown in Table 1.
[comparative example 2]
Rubbery copolymer 14.3 weight parts [styrene-butadiene block copolymer, SM/BD=25/75,1,2-vinyl structure content=15%, wooden Buddhist nun's viscosity=47 (ML
1+4100 ℃)], styrene monomer 38 weight parts, methyl methacrylate 60 weight parts, vinyl cyanide 2 weight parts, ethylbenzene 38.1 weight parts, n-dodecyl mercaptan 0.15 weight part, and the formed feedstock solution of the two-peroxidation tributyl-six hydrogen-terephthalate of 0.115 weight part (di-t-butyl peroxy hexahydro terephthalate), speed with 35Kg/hr is continuously pumped into 4 placed in-line continuously stirring formula reactors (CSTR), the capacity of reactor is all 40 liters, the temperature of reaction of each reactor is 100 ℃, 106 ℃, 124 ℃, 134 ℃, stirring velocity is 300rpm, 200rpm, 150rpm, 120rpm, the monomer conversion of the polymers soln of the 4th reactor outlet is 66%, aforementioned polymer solution heats through preheater, temperature is 230 ℃, again through devolatilization groove with vacuum apparatus, its devolatilization groove temperature is controlled at 220 ℃, after with the twin shaft extruder extrusion of devolatilization mouth, the extrusion temperature is controlled at 225 ℃, and the water that adds 1 weight % in the extruder can obtain transparent rubber modified polystyrene resin as the extrusion auxiliary agent.The residual volatile component of resulting transparent rubber modified polystyrene resin is 0.15 weight %, and the rerum natura of mensuration, transparency, practical transparency and impact strength are as shown in Table 1.
[comparative example 3]
Rubbery copolymer 17.8 weight parts are [by following (1), (2) two kinds of rubber with (1)/(2)=90/10 weight ratio and with forming, comprise: (1) styrene-butadiene block copolymer, SM/BD=25/75,1,2-vinyl structure content=15%, wooden Buddhist nun's viscosity=47 (ML
1+4, 100 ℃).(2) divinyl rubber, 1.2-vinyl structure content=11%, wooden Buddhist nun's viscosity=47 (ML
1+4100 ℃); cis-structure is 35%; the PR-255 of Qi Mei company]; styrene monomer 36 weight parts; methyl methacrylate 61 weight parts; vinyl cyanide 3 weight parts; ethylbenzene 39.3 weight parts; n-dodecyl mercaptan 0.12 weight part; and the tributyl of 0.005 weight part-peroxidation cumic aldehyde (Japanese grease Perbutyl C); 0.08 between weight part-the formed feedstock solution of mixture (Japanese grease Nyper BMT-K40) of methyl benzoyl and benzoyl mistake oxygen thing; speed with 35Kg/hr is continuously pumped into reactor; reactor is to be in series by 4; wherein the 1st～3 reactor is continuously stirring formula reactor (CSTR); the 4th reactor is embolism flow reactor (PFR); the capacity of reactor is all 40 liters; the temperature of reaction of each reactor is 90 ℃; 105 ℃; 124 ℃; 126 ℃ of (inlet)～150 ℃ (outlet); stirring velocity is 300rpm; 200rpm; 100rpm; 30rpm; the monomer conversion of the polymers soln of the 4th reactor outlet is 84%; aforementioned polymer solution heats through preheater; temperature is 260 ℃; again through devolatilization groove with vacuum apparatus; its devolatilization groove temperature is controlled at 255 ℃, can obtain rubber modified polystyrene resin.The residual volatile component of resulting rubber modified polystyrene resin is 0.24 weight %, and the rerum natura of mensuration, transparency, practical transparency and impact strength are as shown in Table 1.
[comparative example 4]
Rubbery copolymer 11.7 weight parts are [by following (1), (2), (3) three kinds of rubber with the weight ratio of (1)/(2)/(3)=60/35/5 and with forming, comprise: (1) styrene-butadiene block copolymer, SM/BD=25/75,1,2-vinyl structure content=15%, wooden Buddhist nun's viscosity=47 (ML
1+4, 100 ℃).(2) divinyl rubber, wooden Buddhist nun's viscosity=47 (ML
1+4, 100 ℃), 1,2-vinyl structure content is 11 weight %, Qi Mei company makes PR-255.(3) styrene-butadiene block copolymer, SM/BD=68/32,1.2-vinyl structure content=13%, (25 ℃ of soltion viscosity=5.5cps, multipolymer content is the toluene solution of 5 weight %)], styrene monomer 41 weight parts, methyl methacrylate 55 weight parts, vinyl cyanide 4.0 weight parts, ethylbenzene 37.2 weight parts, n-dodecyl mercaptan 0.15 weight part, 0.005 the dibenzoyl peroxide of weight part (benzoylperoxide), and the formed feedstock solution of the two-peroxidation tributyl-six hydrogen-terephthalate of 0.095 weight part (di-t-butylperoxy hexahydro terephthalate), speed with 35Kg/hr is continuously pumped into 4 placed in-line continuously stirring formula reactors (CSTR), the capacity of reactor is all 40 liters, the temperature of reaction of each reactor is 95 ℃, 100 ℃, 124 ℃, 132 ℃, stirring velocity is 200rpm, 150rpm, 100rpm, 90rpm, the monomer conversion of the polymers soln of the 4th reactor outlet is 55%, aforementioned polymer solution heats through preheater, temperature is 225 ℃, again through devolatilization groove with vacuum apparatus, its devolatilization groove temperature is controlled at 210 ℃, can obtain rubber modified polystyrene resin.The residual volatile component of resulting rubber modified polystyrene resin is 0.45 weight %, and the rerum natura of mensuration, transparency, practical transparency and impact strength are as shown in Table 1.
[comparative example 5]
Rubbery copolymer 12.4 weight part [styrene-butadiene block copolymers, SM/BD=68/32,1,2-vinyl structure content=13%, solution viscosity=5.5cps (multipolymer content is the toluene solution of 5 weight %)], styrene monomer 37 weight parts, methyl methacrylate 60 weight parts, vinyl cyanide 3 weight parts, ethylbenzene 56.2 weight parts, n-dodecyl mercaptan 0.16 weight part, and the formed feedstock solution of the two-peroxidation tributyl-six hydrogen-terephthalate of 0.115 weight part (di-t-butyl peroxy hexahydro terephthalate), speed with 35Kg/hr is continuously pumped into 4 placed in-line continuously stirring formula reactors (CSTR), the capacity of reactor is all 40 liters, the temperature of reaction of each reactor is 100 ℃, 106 ℃, 120 ℃, 130 ℃, stirring velocity is 300rpm, 250rpm, 150rpm, 120rpm, the monomer conversion of the polymers soln of the 4th reactor outlet is 65%, aforementioned polymer solution heats through preheater, temperature is 255 ℃, again through devolatilization groove with vacuum apparatus, its devolatilization groove temperature is controlled at 250 ℃, can obtain rubber modified polystyrene resin.The residual volatile component of resulting rubber modified polystyrene resin is 0.3 weight %, and the rerum natura of mensuration, transparency, practical transparency and impact strength are as shown in Table 1.
[comparative example 6]
Rubbery copolymer 14.1 weight part [styrene-butadiene block copolymers, SM/BD=25/75,1,2-vinyl structure content=15%], styrene monomer 40 weight parts, methyl methacrylate 57 weight parts, vinyl cyanide 3 weight parts, ethylbenzene 38 weight parts, n-dodecyl mercaptan 0.15 weight part, and the dibenzoyl peroxide of 0.08 weight part, 0.155 two-peroxidation tributyl of the weight part-formed feedstock solution of six hydrogen-terephthalate, speed with 35Kg/hr is continuously pumped into 4 reactors, wherein the 1st～3 reactor is continuously stirring formula reactor (CSTR), the 4th reactor is embolism flow reactor (PFR), the capacity of each reactor is all 40 liters, the temperature of reaction of each reactor is 102 ℃, 108 ℃, 126 ℃, 128 ℃ of (inlet)～153 ℃ (outlet), stirring velocity is 300rpm, 200rpm, 150rpm, 30rpm, the monomer conversion of the polymers soln of the 4th reactor outlet is 88%, aforementioned polymer solution heats through preheater, temperature is 260 ℃, again through devolatilization groove with vacuum apparatus, its devolatilization groove temperature is controlled at 260 ℃, can obtain rubber modified polystyrene resin.The residual volatile component of resulting rubber modified polystyrene resin is 0.22 weight %, and the rerum natura of mensuration, transparency, practical transparency and impact strength are as shown in Table 1.
The above, it only is preferred embodiment of the present invention, can not limit scope of the invention process with this, promptly all simple equivalent of being done according to the present patent application claim and description of the invention content change and modify, and all should still belong in the scope that patent of the present invention contains.
Table one: the rerum natura deck watch of various embodiments of the present invention and comparative example.
Table one
| Experiment numbers | Embodiment | Comparative example | ||||||||||||||
| ?1 | ?2 | ?3 | ?4 | ?5 | ?6 | ?7 | ?8 | ?1 | ?2 | ?3 | ?4 | ?5 | ?6 | |||
| Disperse phase (A) | The weight average particle diameter of rubber particles (μ m) | ?0.38 | ?0.41 | ?0.46 | ?0.42 | ?0.35 | ?0.4 | ?0.36 | ?0.41 | ?0.47 | ?0.43 | ?0.5 | ?0.64 | ?0.17 | ?0.39 | |
| 0.78 the above rubber particles of μ m accounts for the weight % of whole rubber particles | ?6 | ?12 | ?20 | ?11 | ?0 | ?12 | ?4 | ?11 | ?22 | ?12 | ?30 | ?40 | ?0 | ?5 | ||
| Rubber content in the resin (weight %) | ?19 | ?18.3 | ?18.5 | ?18 | ?18.1 | ?18.2 | ?24 | ?18.1 | ?18.5 | ?19 | ?18 | ?19 | ?17 | ?18.2 | ||
| Rubber particles changes than (A1)/(A2) before and after the annealing | ?1.62 | ?1.41 | ?1.83 | ?1.58 | ?1.45 | ?1.32 | ?1.51 | ?1.30 | ?2.5 | ?2.22 | ?1.85 | ?2.7 | ?1.2 | ?1.06 | ||
| Surface roughness | ?ΔHmax() | ?1560 | ?1320 | ?2530 | ?1480 | ?1830 | ?1450 | ?1420 | ?1470 | ?4620 | ?3520 | ?3340 | ?5520 | ?850 | ?1380 | |
| ?ΔHave() | ?750 | ?1050 | ?1740 | ?820 | ?1370 | ?1210 | ?620 | ?1220 | ?2120 | ?1830 | ?2280 | ?3850 | ?650 | ?810 | ||
| Transparency | Haze (30 ° of horizontal sextant angles) | ?4.32 | ?4.66 | ?6.17 | ?4.88 | ?4.31 | ?3.74 | ?3.88 | ?3.70 | ?11.9 | ?8.72 | ?8.88 | ?20 | ?2.64 | ?5.21 | |
| Haze (90 ° of horizontal sextant angles) | ?3.57 | ?4.12 | ?5.24 | ?4.01 | ?3.70 | ?3.33 | ?3.21 | ?3.25 | ?8.79 | ?6.51 | ?6.99 | ?15.22 | ?2.29 | ?4.70 | ||
| The practical transparency | ?Haze(30°)-Haze(90°) | ?0.75 | ?0.54 | ?0.93 | ?0.87 | ?0.58 | ?0.41 | ?0.68 | ?0.45 | ?3.11 | ?2.21 | ?1.89 | ?4.78 | ?0.35 | ?0.51 | |
| Shock strength (Izod) | ?14.8 | ?14.5 | ?15.2 | ?15.4 | ?14.6 | ?14.1 | ?20.4 | ?14.9 | ?14.2 | ?15.3 | ?14.6 | ?15.6 | ?3.1 | ?4.6 | ||
Claims (5)
1. transparent rubber modified polystyrene resin, it is characterized in that this resin is by rubber particles disperse phase (A) that the rubbery copolymer of 1～25 weight % forms, and the multipolymer external phase (B) of 99～75 weight % is formed, wherein multipolymer external phase (B) is to be measured styrenic monomers 20～70 weight parts, methacrylate ester monomer 30～80 weight parts of 100 weight parts by total, and copolymerizable monomer 0～40 weight part forms:
Wherein, resin is fixed with the surface roughness instrumentation through the moulding product that the minute surface mould penetrates, the height difference of measuring is Δ H, wherein Zui Da height difference DELTA Hmax is less than 3200 , and average height difference DELTA Have is less than 2000 , and following 1.8～2.2 μ m depths on aforementioned moulding product surface, in the rubber particles of major diameter with the electron microscope observation rubber particles greater than 0.3 μ m, under 120 ℃ of following annealing conditions of 40 minutes of temperature, the mean ratio A2 of rubber particles major diameter a/ minor axis b after rubber particles major diameter a/ minor axis b mean ratio A1 before it is unannealed and the annealing, wherein the ratio of A1/A2 is 1.08～2.35.
2. according to the described transparent rubber modified polystyrene resin of claim 1, it is characterized in that rubber particles accounts for 0～25 weight % of whole rubber particles in the disperse phase greater than the particle of 0.78 μ m.
3. according to the described transparent rubber modified polystyrene resin of claim 1, it is characterized in that the rubber particles weight average particle diameter is 0.18～1 μ m.
4. according to the described transparent rubber modified polystyrene resin of claim 1, it is characterized in that the ratio of A1/A2 is 1.08～2.2.
5. according to claim 1 a described transparent rubber modified polystyrene resin, it is characterized in that the ratio of A1/A2 is 1.10～2.0.
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| TWI681006B (en) * | 2017-12-29 | 2020-01-01 | 奇美實業股份有限公司 | Resin composition, molded article, food contact appliance and food contact container |
| US11235563B2 (en) | 2017-12-29 | 2022-02-01 | Chimei Corporation | Resin composition, molded article, food contact appliance and food contact container |
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| CN113524611B (en) * | 2021-07-16 | 2023-05-02 | 扬州天启新材料股份有限公司 | Devolatilization process for SMA product production |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6515072B2 (en) * | 2000-07-11 | 2003-02-04 | Chi Mei Corporation | Transparent rubber-modified styrenic resin composition |
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| US6515072B2 (en) * | 2000-07-11 | 2003-02-04 | Chi Mei Corporation | Transparent rubber-modified styrenic resin composition |
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| TWI681006B (en) * | 2017-12-29 | 2020-01-01 | 奇美實業股份有限公司 | Resin composition, molded article, food contact appliance and food contact container |
| US11235563B2 (en) | 2017-12-29 | 2022-02-01 | Chimei Corporation | Resin composition, molded article, food contact appliance and food contact container |
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