CN103183762A - Styrene-alpha-methylstyrene-acrylonitrile copolymer and rubber-modified styrene resin - Google Patents

Styrene-alpha-methylstyrene-acrylonitrile copolymer and rubber-modified styrene resin Download PDF

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CN103183762A
CN103183762A CN2012105661961A CN201210566196A CN103183762A CN 103183762 A CN103183762 A CN 103183762A CN 2012105661961 A CN2012105661961 A CN 2012105661961A CN 201210566196 A CN201210566196 A CN 201210566196A CN 103183762 A CN103183762 A CN 103183762A
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styrene
acrylic
monomer
unit
rubber
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CN103183762B (en
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高宜孝
林全明
许瑞熙
郭铭洲
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Chi Mei Corp
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Chi Mei Corp
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Abstract

A rubber modified styrene resin at least comprises 75-80 wt% of styrene-alpha-methylstyrene-acrylonitrile copolymer, 0-5 wt% of styrene-acrylonitrile copolymer and 20-25 wt% of rubber particles. Wherein the styrene-alpha-methylstyrene-acrylonitrile copolymer mainly comprises 48 to 60wt% of styrene monomer units, 15 to 27wt% of alpha-methylstyrene monomer units and 25 to 32wt% of acrylonitrile monomer units, and the content of dimers and trimers of the styrene monomer, the alpha-methylstyrene monomer or the acrylonitrile monomer units is less than 8500 ppm. The styrene-acrylonitrile copolymer comprises 65-76 wt% of styrene monomer units and 24-35 wt% of acrylonitrile monomer units, wherein the styrene-alpha-methylstyrene-acrylonitrile copolymer and the styrene-acrylonitrile copolymer form a continuous matrix phase. In addition, the rubber particles are dispersed in the continuous matrix phase.

Description

Styrene--acrylic copolymer and rubber modified styrene series resin
[technical field]
The present invention relates to a kind of rubber modified styrene series resin, particularly relate to a kind of styrene--acrylic copolymer of mainly being formed by styrene monomer unit, α-Jia Jibenyixidanti unit and acrylic monomeric unit.
[background technology]
Why phenylethylene resin series (as ABS resin etc.) is widely used on electrical equipment, electronics and the auto parts, mainly be that its processing forming, physical property and mechanical properties aspect all have good evaluation, a big characteristic especially on the good appearance of moulding product and the glossiness especially.
On the other hand, the industry of machine-shaping at present is to gradually adopt pin cast gate (Pin gate) to come ejection formation, this trend also to make the requirement of phenylethylene resin series on thermostability improve relatively in order to improve the cast gate outward appearance of ejection formed piece.Therefore, how making phenylethylene resin series improve the resin treatment thermostability, is field utmost point problem to be improved for this reason.
In addition, generally speaking, in the thermoplastic resin of being formed by styrenic monomers unit, α-Jia Jibenyixidanti unit and acrylic monomeric unit, when the content of its α-Jia Jibenyixidanti unit is more high, has the effect that promotes softening temperature.Though can make the thermotolerance qualitative change of thermoplastic resin good, the shortcoming that but has cost to rise.
[summary of the invention]
In view of this, purpose of the present invention is providing a kind of styrene--acrylic copolymer and rubber modified styrene series resin exactly, to improve the problem that resin thermotolerance and cost rise.
Therefore, for reaching above-mentioned purpose, according to a kind of styrene--acrylic copolymer of the present invention, mainly by the styrene monomer unit of 48 ~ 60wt%, the α-Jia Jibenyixidanti unit of 15 ~ 27wt%; And the acrylic monomeric unit of 25 ~ 32wt% is formed.Wherein, the dipolymer of being made up of styrene monomer, α-Jia Jibenyixidanti or acrylic monomer and trimeric content are less than 8500ppm.Wherein styrene--acrylic copolymer is formed by styrene monomer, α-Jia Jibenyixidanti and acrylonitrile monemer copolymerization, and wherein styrene--acrylic copolymer mainly is made up of styrene monomer unit, α-Jia Jibenyixidanti unit and acrylic monomeric unit.Namely, above-mentioned styrene monomer unit, α-Jia Jibenyixidanti unit and acrylic monomeric unit, after referring to styrene monomer, α-Jia Jibenyixidanti and acrylic monomer copolymerizable respectively, the tectonic element in styrene--acrylic copolymer.
Again, the present invention further proposes a kind of styrene--acrylic copolymer, mainly by the styrene monomer unit of 48 ~ 60wt%, the α-Jia Jibenyixidanti unit of 15 ~ 27wt%; And the acrylic monomeric unit of 25 ~ 32wt% is formed.Wherein the weight-average molecular weight of this styrene--acrylic copolymer is lower than 50,000 molecule less than 25%.
Wherein, in above-mentioned styrene--acrylic copolymer, the acrylic monomeric unit is preferably vinyl cyanide or Alpha-Methyl vinyl cyanide.In addition, the sulphur content in styrene--acrylic copolymer is 50-300ppm, is preferably 110-250ppm.
In addition, the present invention also proposes a kind of rubber modified styrene series resin, comprise: styrene--acrylic copolymer of 75 ~ 80wt% (A1), styrene--acrylic copolymer (A1) mainly is made up of the styrene monomer unit of 48 ~ 60wt%, the α-Jia Jibenyixidanti unit of 15 ~ 27wt% and the acrylic monomeric unit of 25 ~ 32wt%, and wherein the dipolymer of being made up of styrene monomer, α-Jia Jibenyixidanti or acrylic monomer and trimeric content are less than 8500ppm; 0 ~ 5wt% styrene-acrylonitrile based copolymer (A2), contain the styrenic monomers unit of 65 ~ 76wt% and the acrylic monomeric unit of 24 ~ 35wt%, wherein styrene--acrylic copolymer and styrene-acrylonitrile based copolymer are formed continuous matrix phase, and the rubber particles of 20 ~ 25wt% (B), wherein rubber particles is disperse phase, and is dispersed in the continuous matrix phase.In addition, aforesaid rubber particles is preferably selected from the polymkeric substance of at least a 1,3 divinyl, isoprene or its mixture, and the weight average particle diameter of rubber particles is preferably 0.22 ~ 0.6 μ m, and the acrylic monomeric unit is preferably vinyl cyanide or Alpha-Methyl vinyl cyanide.
Effect of the present invention is to use less α-Jia Jibenyixidanti unit can make styrene--acrylic copolymer and rubber modified styrene series resin reach higher softening temperature, reduces cost thus.In addition, the present invention also can reduce residual dipolymer and trimeric content, and then improves the amount of being fuming of course of processing when ejection formation (for example) or the mold fouling that causes.In addition, the sulphur content of styrene--acrylic copolymer is 50 ~ 300ppm, is preferably 110 ~ 250ppm and can makes styrene--acrylic copolymer reach higher heat resisting temperature (the thermogravimetric loss is lower).
For above-mentioned and other purposes of the present invention, feature and advantage can be become apparent more, hereinafter the spy enumerates preferred implementation, is described in detail below:
[embodiment]
Styrene--acrylic copolymer of the present invention is mainly by the styrene monomer unit of 48 ~ 60wt%, the α-Jia Jibenyixidanti unit of 15 ~ 27wt%; And the acrylic monomeric unit of 25 ~ 32wt% is formed.Wherein, the dipolymer of being made up of styrene monomer, α-Jia Jibenyixidanti or acrylic monomer and trimeric content are less than 8500ppm.
Again, the present invention also proposes another kind of styrene--acrylic copolymer, mainly be made up of the styrene monomer unit of 48 ~ 60wt%, the α-Jia Jibenyixidanti unit of 15 ~ 27wt% and the acrylic monomeric unit of 25 ~ 32wt%, wherein the weight-average molecular weight of this styrene--acrylic copolymer is lower than the quantity system of 50,000 molecule less than 25%.
When the content of acrylic monomeric unit during greater than 32wt%, the hue difference of styrene--acrylic copolymer then; And when the content of acrylic monomeric unit during less than 25wt%, then styrene--acrylic copolymer endurance is not good.In addition, when α-Jia Jibenyixidanti unit content during greater than 27wt%, then there is the high problem of cost to produce; If α-Jia Jibenyixidanti unit content is during less than 15wt%, then the thermotolerance of thermoplastic resin can descend.
In addition, the physical property measurement standard of embodiments of the invention and comparative example is as follows:
One, melt flow index (Melt Flow Rate, MFR, MI, MVR): according to JIS K-7210 regulation, with 220 ℃ * 10kg test, and represent with g/10min.
Two, izod (IZOD) shock strength: according to the test of ASTM D-256 regulation, represent with Kg cm/cm.
Three, weight-average molecular weight (weight-average molecular weight, Mw): the inspection amount line that utilizes known available standard vinylbenzene to make is tried to achieve weight-average molecular weight, to have gel dialysis chromatograph (the Gel Permeation Chromatogrpahy of the monitoring of differential tortuosity ratio and two functions of scattering of light monitoring, GPC, Waters Company supply) measure.
Four, the dipolymer of styrenic monomers and/or acrylic monomer and trimeric total content testing method: get 1 gram embodiment A 1-1 ~ A1-4 and Comparative examples A 2-1 ~ A2-2 respectively and be dissolved in the acetone, this resin combination solution re-uses the numbering 7890A of Hewlett Packard company with the gas chromatograph of the flame ion analyzer mensuration that performs an analysis.
Five, softening point temperature refers to vicat softening point temperature (Vicat Softening Temperature): according to the test of ASTM D-1525 regulation, unit is with a ℃ expression.
Six, thermogravimetric loss: use the TAQ5000 thermogravimetric analyzer, prepare the weight loss of 5 milligrams of samples, 30 minutes following working samples of 300 ℃ of constant temperature under the environment of nitrogen.
Seven, sulphur content: prepare 10 milligrams of samples, after High Temperature Furnaces Heating Apparatus (AQF-100 of Mitsubishi) is with 900 ~ 1000 ℃ of processing, (the absorption liquid collocation method is the potassium primary phosphate (KH that gets 1c.c. to inject the 5c.c absorption liquid through gas phase absorptive unit (Gas Absorption Unit, the GA-100 of Mitsubishi supply) 2PO 4) with the hydrogen peroxide (H of 100ml 2O 2), quantitatively become 1L with pure water; This moment PO 4 3-Concentration is 1ppm) and measure with ion chromatograph (DIONEX ICS-1500), during measurement with PO 4 3-For interior mark 1ppm, with 1000ppm sulfate radical (SO 4 2-) solution is standard substance, disposes different concentration known [SO with standard substance 4 2-] standard measure, record corresponding survey area, to formulate [SO 4 2-] inspection amount line.Inspection amount line [SO 4 2-] the concentration calculation formula is { [sample area]-[background value area] } * 5000/ sample heavy (ppm of unit).Testing sample records [sample area] substitution inspection afterwards amount line can obtain corresponding [SO 4 2-], afterwards with [S]=[SO 4 2-Convert and get in]/3 (ppm of unit).
Again, the present invention also proposes a kind of rubber modified styrene series resin, comprise: styrene--acrylic copolymer of 75 ~ 80wt% (A1), wherein styrene--acrylic copolymer (A1) is mainly by the styrene monomer unit of 48 ~ 60wt%, the α-Jia Jibenyixidanti unit of 15 ~ 27wt% and the acrylic monomeric unit of 25 ~ 32wt% are formed, wherein by styrene monomer, the dipolymer that α-Jia Jibenyixidanti or acrylic monomer are formed and trimeric content are less than 8500ppm, 0 ~ 5wt% styrene-acrylonitrile based copolymer (A2), styrene-acrylonitrile based copolymer (A2) contains the styrenic monomers unit of 65 ~ 76wt% and the acrylic monomeric unit of 24 ~ 35wt%, wherein styrene--acrylic copolymer and styrene-acrylonitrile based copolymer are formed continuous matrix phase, and the rubber particles of 20 ~ 25wt% (B), wherein rubber particles is disperse phase, and is dispersed in this continuous matrix phase.
Below will be elaborated to styrene--acrylic copolymer (A1), styrene-acrylonitrile based copolymer (A2) and rubber particles (B) one by one:
[styrene--acrylic copolymer (A1)]
Styrene--acrylic copolymer (A1) is mainly obtained through solution polymerization by first monomer component that styrene monomer, α-Jia Jibenyixidanti and acrylic monomer are formed.
Preferably, the total amount of first monomer component of being formed with styrene monomer, α-Jia Jibenyixidanti, acrylic monomer is that 100wt% calculates, and in this first monomer component, the content range of styrene monomer can for example be 47wt%～59wt%; 48.5wt%～53.5wt% more preferably.In addition, in this first monomer component, the content range of α-Jia Jibenyixidanti is 14wt%～26wt%; 16.5wt%～21.5wt% more preferably.
The acrylic monomer can be used alone or as a mixture, and the acrylic monomer is including but not limited to vinyl cyanide or Alpha-Methyl vinyl cyanide etc.Preferably, the acrylic monomer can for example be vinyl cyanide.Preferably, be that 100wt% calculates with the total amount of styrene monomer, α-Jia Jibenyixidanti, acrylic monomer, in this first monomer component, the content range of acrylic monomer can for example be 27wt%～34wt%; 29wt%～32wt% more preferably.
In solution polymerization, optionally can add the polymerization initiator.The polymerization initiator can for example be selected from simple function polymerization initiator, multi-functional polymerization initiator, or their combination.Simple function polymerization initiator can be used alone or as a mixture, and simple function polymerization initiator can be for example including but not limited to dibenzoyl peroxide (benzoyl peroxide), dicumyl peroxide (dicumyl peroxide), tert-butyl peroxide (t-butyl peroxide), tert-butyl hydroperoxide (t-butyl hydroperoxide), hydrogen phosphide cumene (cumene hydroperoxide), tert butyl peroxy benzoate (t-butyl-peroxy benzoate), two-2-ethylhexyl peroxy dicarbonate (bis-2-ethylhexyl peroxy dicarbonate), tert-butyl hydroperoxide sec.-propyl carbonic ether (tert-butyl peroxy isopropyl carbonate, be called for short BPIC), cyclohexanone peroxide (cyclohexanone peroxide), 2,2'-azo-two-isopropyl cyanide (2,2 '-azo-bis-isobutyronitrile, be called for short AIBN), 1,1 '-azo bis cyclohexane-1-carbonyl nitrile (1,1'-azo-biscyclohexane-1-carbonitrile), or 2,2'-azo-two-2-methylbutyronitrile (2,2'-azo-bis-2-methyl butyronitrile) etc.Wherein the polymerization initiator can for example be dibenzoyl peroxide, 2,2'-azo-two-isopropyl cyanide.
Multi-functional polymerization initiator can be used alone or as a mixture, and multi-functional polymerization initiator can be for example including but not limited to 1,1-pair-tert-butyl hydroperoxide hexanaphthene (1,1-bis-t-butyl peroxy cyclohexane, be called for short TX-22), 1,1-pair-tert-butyl hydroperoxide-3,3,5-trimethyl-cyclohexane (1,1-bis-t-butylperoxy-3,3,5-trimethyl cyclohexane, be called for short TX-29A), 2,5-dimethyl-2,5-pair-(2-ethyl peroxidation hexanoyl) hexane [2,5-dimethyl-2,5-bis-(2-ethylhexanoxy peroxy) hexane], 4-(tert-butyl hydroperoxide carbonyl)-3-hexyl-6-[7-(tert-butyl hydroperoxide carbonyl) heptyl] hexanaphthene 4-(t-butyl peroxy carbonyl)-3-hexyl-6-[7-(t-butyl peroxy carbonyl) heptyl] cyclohexane}, two-tertiary butyl diperoxy azelate (di-t-butyl-diperoxyazelate), 2,5-dimethyl-2, two (benzoyl the peroxidation)-hexanes [2 of 5-, 5-dimethyl-2,5-bis-(benzoyl peroxy) hexane], two-tert-butyl hydroperoxide-six hydrogen-terephthalate (di-t-butyl peroxy-hexahydro-terephthalate, be called for short BPHTH), or 2,2-two (4,4-two-tert-butyl hydroperoxide) cyclohexyl propane [2,2-bis-(4,4-di-t-butyl peroxy) cyclohexyl propane is called for short PX-12] etc.
In solution polymerization, optionally can add chain-transfer agent.Chain-transfer agent can be used alone or as a mixture; and chain-transfer agent can be for example including but not limited to just-lauryl mercaptan (n-dodecyl mercaptan; abbreviation NDM), stearyl-mercaptan (stearyl mercaptan), uncle-lauryl mercaptan (t-dodecyl mercaptan; be called for short TDM), just-propyl group mercaptan, n-octyl mercaptan, uncle-octyl mercaptan, uncle-nonyl mercaptan, or terpinolene (terpinolene) etc.
Preferably, the operating temperature range of solution polymerization can for example be 90 ℃～130 ℃; More preferably, the operating temperature range of solution polymerization can for example be 100 ℃～120 ℃.
[styrene-acrylonitrile based copolymer (A2)]
One of method for making of styrene-acrylonitrile based copolymer (A2) is can be by comprising styrenic monomers (i-1) and acrylic monomer (i-2), and it is obtained through solution polymerization to reach second monomer component that optionally adds other copolymerizable vinyl monomers (i-3).The styrene-acrylonitrile based copolymer (A2) of the not grafting that produces when in addition, styrene-acrylonitrile based copolymer (A2) can also be for the rubber particles (B) in making the emulsion polymerization rubber graft copolymer.
Styrenic monomers (i-1) can be used alone or as a mixture, and styrenic monomers (i-1) can be for example including but not limited to vinylbenzene, alpha-methyl styrene, right-t-butyl styrene, p-methylstyrene, neighbour-vinyl toluene ,-vinyl toluene, 2,4-dimethyl styrene, ethyl styrene, Alpha-Methyl-p-methylstyrene, or bromstyrol etc.Preferably, styrenic monomers (i-1) can for example be selected from vinylbenzene, alpha-methyl styrene, or their combination.Preferably, be that 100wt% calculates with the total amount of (i-1), (i-2), (i-3), the content range of styrenic monomers (i-1) can for example be 50wt%～90wt%; More preferably, be 55wt%～85wt%; Again more preferably, be 58wt%～80wt%.
Acrylic monomer (i-2) can be used alone or as a mixture, and acrylic monomer (i-2) can be for example including but not limited to vinyl cyanide or Alpha-Methyl vinyl cyanide etc.Preferably, acrylic monomer (i-2) can for example be vinyl cyanide.Preferably, be that 100wt% calculates with the total amount of (i-1), (i-2), (i-3), the content range of acrylic monomer (i-2) can for example be 10wt%～50wt%; More preferably, can for example be 15wt%～45wt%; Again more preferably, can for example be 20wt%～42wt%.
Other copolymerizable vinyl monomers (i-3) can be used alone or as a mixture, and other copolymerizable vinyl monomers (i-3) can be monomer, Maleic Acid, Anhydrous or methacrylate ester monomer etc. including but not limited to acrylic monomer, metha crylic monomer, acrylic ester monomer, maleimide for example.Preferably, be that 100wt% calculates with the total amount of (i-1), (i-2), (i-3), the content range of other copolymerizable vinyl monomers (i-3) can for example be 0wt%～40wt%; More preferably, can for example be 1wt%～34wt%; Again more preferably, can for example be 3wt%～30wt%.
Acrylic monomer can be for example including but not limited to vinylformic acid etc.The metha crylic monomer can be for example including but not limited to methacrylic acid etc.The acrylic ester monomer can be for example including but not limited to methyl acrylate, ethyl propenoate, isopropyl acrylate, or butyl acrylate etc.Preferably, the acrylic ester monomer can for example be butyl acrylate.
The methacrylate ester monomer can be for example including but not limited to methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, the methacrylic acid benzene methyl, N-Hexyl methacrylate, cyclohexyl methacrylate, methacrylic acid dodecane ester, methacrylic acid 2-hydroxyl ethyl ester, glytidyl methacrylate, glycidyl methacrylate, Dimethylaminoethyl Methacrylate (dimethylaminoethyl methacrylate), ethylene glycol dimethacrylate (ethylene dimethacrylate), or dimethacrylate peopentyl ester (neopentyl dimethacrylate) etc.Preferably, the methacrylate ester monomer can for example be selected from methyl methacrylate or butyl methacrylate.
Maleimide is that monomer can for example be: maleimide, N-methyl maleimide, N-sec.-propyl maleimide, the N-butyl maleimide, N-hexyl maleimide, N-octyl group maleimide, N-dodecyl maleimide, N-cyclohexyl maleimide, N-phenylmaleimide, N-2,3-tolyl maleimide, N-2,4-tolyl maleimide, N-2,3-ethylbenzene base maleimide, N-2,4-ethylbenzene base maleimide, N-2,3-butylbenzene base maleimide, N-2,4-butylbenzene base maleimide, N-2,6-tolyl maleimide, N-2,3-chloro-phenyl-maleimide, N-2,4-chloro-phenyl-maleimide, N-2,3-bromophenyl Malaysia imide, N-2,4-bromophenyl Malaysia imides etc. are most preferred with N-phenylmaleimide again wherein.
The kind of polymerization initiator and chain-transfer agent is as the polymerization initiator in above-mentioned preparation styrene--acrylic copolymer (A1) and the kind of chain-transfer agent, so repeat no more.
Preferably, the operating temperature range of solution polymerization can for example be 70 ℃～140 ℃; More preferably, the operating temperature range of solution polymerization can for example be 90 ℃～130 ℃.
[rubber particles (B)]
The made graft copolymer of this rubber particles (B) is for example in the presence of rubber latex (solid content) 40 ~ 90wt%, obtained through graft polymerization reaction with functional monomer's component of 10 ~ 60wt%, wherein, functional monomer's component comprises can be for example by styrenic monomers 50 ~ 90wt%, acrylic monomer 10 ~ 50%wt%, and the monomer mixture of other copolymerizable vinyl monomer 0 ~ 40wt% combinations.
Preferably, functional monomer's component can for example comprise the styrenic monomers of 58wt%～80wt%, the acrylic monomer of 20wt%～42wt%, and other copolymerizable monomer of 0wt%～22wt%.
In graft polymerization reaction, optionally can add additive, and additive comprises but is not limited to emulsifying agent, polymerization initiator or chain-transfer agent etc.Optionally can be again after emulsion polymerization reaction via condense, dehydration, drying and other steps handle.Comprise rubber particles (B) and styrene-acrylonitrile based copolymer (A2) in the prepared emulsion polymerization rubber graft copolymer.Behind the graft polymerization reaction, be among the 100wt% based on the total amount of emulsion polymerization rubber graft copolymer (I), the content range of styrene-acrylonitrile based copolymer is below the 10wt%.
Rubber latex is obtained through emulsion polymerization method by rubber components, perhaps further gives loose processing (agglomerating treatment) again after the emulsion polymerization reaction, and optionally adds other copolymerizable monomer in the emulsion polymerization reaction.Preferably, rubber components can for example be selected from diene series rubber, polyacrylic ester is rubber, or polysiloxane series rubber.
Diene series rubber can be used alone or as a mixture, and diene series rubber can be for example including but not limited to divinyl rubber, synthetic polyisoprene, neoprene, ethylene-propylene-diolefin series ter-polymer rubber (ethylene propylene diene terpolymer, be called for short EPDM), or vinylbenzene-diene series rubber or vinyl cyanide-diene series rubber etc.Wherein, divinyl rubber can be for example including but not limited to the divinyl rubber of high-cis (Hi-Cis) content and the divinyl rubber of low cis (Low-Cis) content.The typical weight of the cis in the divinyl rubber of high-cis content (Cis)/vinyl (Vinyl) consists of (94～98wt%)/(1～5wt%), all the other compositions then are trans (Trans) structure, and Buddhist nun's viscosity (mooney viscosity) is not between 20～120, molecular weight ranges is with 100,000～800,000 is good.The typical weight compositing range of the cis/vinyl in the divinyl rubber of low cis content (20～40wt%)/(1～20wt%), all the other are transconfiguration, and Buddhist nun's viscosity is not between 20～120, and molecular weight ranges is with 100,000～800, and 000 is good.Vinylbenzene-diene series rubber can be for example including but not limited to styrene butadiene rubbers, styrene isoprene rubber etc., and vinylbenzene-diene series rubber can for example be block copolymerization zoarium, random copolymers (random) or star formula multipolymer (star type), wherein, in the styrene butadiene rubbers, the part by weight scope of vinylbenzene and divinyl can for example be 5:95～80:20, and molecular weight ranges is preferably 50,000～600,000.Preferably, vinylbenzene-diene series rubber can for example be styrene butadiene rubbers.Other copolymerizable monomer can be for example including but not limited to styrenic monomers, acrylic monomer and (methyl) acrylic ester monomer etc.The diene series rubber emulsion can be for example including but not limited to being polyhutadiene, butadiene-styrene copolymer, perbutan, divinyl-methylmethacrylate copolymer, or isoprene-butyl acrylate copolymer etc.
Loose processing can be adopted the loose method of general freezing loose method, mechanical loose method or additive.The additive that uses in the loose method of additive can be for example including but not limited to (1) acidic substance: acetic anhydride, hydrogenchloride, sulfuric acid etc.; (2) salt-base substances: sodium-chlor, Repone K, calcium chloride etc.; (3) contain carboxylic acid group's polymer coagulant: (methyl) vinylformic acid-(methyl) acrylate copolymer (as methacrylic acid-butyl acrylate copolymer, EUDRAGIT L100-55) etc.
For instance, the manufacture method of diene series rubber emulsion can use diene monomer (for example divinyl) with the emulsion polymerization method polymerization, perhaps, with the emulsion polymerization method polymerization, can obtain weight average particle diameter is the diene series rubber emulsion of 0.05 μ m～0.6 μ m with monomers such as the vinylbenzene of the diene monomer of 50 ~ 100wt% and 0 ~ 50wt% and/or vinyl cyanide.After also aforementioned monomer can being made the small particle size diene series rubber emulsion of weight average particle diameter 0.05 μ m～0.20 μ m with emulsion polymerization method, again to give loose the processing, with the big particle diameter diene series rubber emulsion of the loose one-tenth of aforementioned small particle size diene series rubber emulsion weight average particle diameter 0.22 μ m～0.6 μ m.Wherein, if rubber particles less than 0.22 μ m, under identical rubber particles weight, because rubber particles is too small, and makes impact-resistant strength degradation; Otherwise, if rubber particles greater than 0.6 μ m, under identical rubber particles weight, owing to the quantity decline of rubber particles, and makes impact-resistant strength degradation.
The kind of the made employed styrenic monomers of graft copolymer, acrylic monomer and the copolymerizable monomer of rubber particles (B), polymerization initiator, chain-transfer agent, illustrate identically with monomer in the styrene-acrylonitrile based copolymer (A2), do not repeat them here.
In preparation rubber modified styrene series resin process of the present invention, can add various additives in case of necessity, and additive can for example be selected from antioxidant, plasticizer, processing aid, ultra-violet stabilizer, UV light absorber, weighting agent, reinforcer, tinting material, lubrication prescription, charged preventor, incombustible agent, difficult combustion auxiliary agent, thermo-stabilizer, coupler, or their combination.Above-mentioned additive can be respectively in the polyreaction of above-mentioned styrene--acrylic copolymer (A1), styrene-acrylonitrile based copolymer (A2) or rubber particles (B), after the polyreaction, the preceding interpolation of condensing, or above-mentioned additive can extrude the processing of mixing, and adds in the process of preparation rubber modified styrene series resin.
Antioxidant can be used alone or as a mixture, and antioxidant can be that antioxidant, thioether are antioxidant including but not limited to phenol for example, or phosphorous antioxidant etc.Preferably, be that 100wt% calculates with the total amount of rubber modified styrene series resin, the content range of antioxidant is below the 2wt%.
Phenol is that antioxidant can be used alone or as a mixture, and phenol is that antioxidant can be for example including but not limited to 3,5-two (1, the 1-dimethyl ethyl)-4-hydroxy phenyl propionic acid stearyl [3,5-bis (1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid octadecyl ester Xing ︰ antioxidant IX-1076], triethylene glycol two [3-(the 3-tertiary butyl-5-methyl-4-hydroxyphenyl) propionic ester], four [methylene base-3-(3,5-dual-tert-butyl-4-hydroxyphenyl) propionic ester] methane, the 2-tertiary butyl-6-(the 3-tertiary butyl-2-hydroxy-5-methyl base phenmethyl)-4-aminomethyl phenyl acrylate, 2,2'-methylene base-two (4-methyl-6-tert butyl phenol) [2,2'-methylenebis (4-methyl-6-tert-butylphenol) Xing ︰ antioxidant 2246], 2,2'-sulphur two (4-methyl-6-tert butyl phenol), 2,2'-sulfo--diethylene base-two [3-(3,5-dual-tert-butyl-4-hydroxyphenyl) propionic ester], or 2,2'-oxalamide-two [ethyl-3-(3,5-couple-tertiary butyl-4-hydroxyphenyl) propionic ester] etc.
Thioether is that antioxidant can be used alone or as a mixture, and thioether is that antioxidant can be for example including but not limited to distearyl thiodipropionic acid ester, two palmityl thiodipropionic acid esters, five tetrahydroxybutanes-four-(β-ten dimethyl-sulphur propionic ester), or two octadecyl thioethers etc.
Phosphorous antioxidant can be used alone or as a mixture, and the phosphorous antioxidant of the phosphorous antioxidant of the optional self-contained phosphorous acid ester of phosphorous antioxidant or phosphorous acid esters.The phosphorous antioxidant that contains phosphorous acid ester can be for example including but not limited to three (nonyl phenyl) phosphorous acid ester, dodecyl phosphorous acid ester, 4,4'-butylidene two (3-methyl-6-tert butyl phenyl-double tridecyl phosphorous acid ester), three (2,4-tert-butyl-phenyl) phosphorous acid ester etc.The phosphorous antioxidant of phosphorous acid esters can be for example including but not limited to four (2,4-tert-butyl-phenyls)-4, and 4'-stretches the xenyl phosphoric acid ester, or 9,10-dihydro-9-oxy-10-phosphoric acid phenanthrene-10-oxygen support etc.
Lubrication prescription can be used alone or as a mixture, and lubrication prescription can be for example including but not limited to the compound of the metallic soaps of calcium stearate, Magnesium Stearate, lithium stearate etc., ethylene distearyl acid amides (ethylene bis-stearamide is called for short EBA), methylene distearyl acid amides, palmitic amide, butyl stearate, stearic acid palm ester, tetramethylolmethane four fatty acid esters, poly-propionic acid alcohol tristearate, behenic acid, stearic acid etc., polyethylene wax, octocosoic acid wax, carnauba wax (carnuba wax), petroleum wax etc.Preferably, be that 100wt% calculates with the total amount of rubber modified styrene series resin, the content range of lubrication prescription is below the 2wt%.
In preparation rubber modified styrene series resin process of the present invention, can add various polymkeric substance in case of necessity, and polymkeric substance can be for example including but not limited to polycarbonate, polymeric amide, polyethylene terephthalate, polybutylene terephthalate, poly-phenyl ether, polyvinyl chloride, polymethylmethacrylate, ethylene-methyl methacrylate methyl terpolymer, polypropylene, styrene butadiene block copolymer, hydrogenated acrylonitrile-butadienecopolymer, the hydrogenated styrene-divinyl block copolymer etc. stretched.Preferably, be that 100wt% calculates with the total amount of rubber modified styrene series resin, the content range of polymkeric substance is 5wt%～200wt%.
The moulding product of rubber modified styrene series resin of the present invention are handled obtained by aforesaid rubber modified styrene series resin through the machine-shaping of mixing.The machine-shaping of mixing is handled can adopt manner known in the art, so repeat no more.
The present invention will be described further with regard to following examples, but will be appreciated that, these embodiment are the usefulness for illustrating only, and should not be interpreted as restriction of the invention process.
＜embodiment 〉
＜embodiment A 1-1 〉
With the speed of 27kg/hr with α-Jia Jibenyixidanti 21.5wt%, styrenic monomers 48.5wt%, the raw material of acrylic monomer 30wt% is mixed, again with ethylbenzene 3.0kg/hr, 620ppm Diisopropyl azodicarboxylate (AIBN), uncle 550ppm-lauryl mercaptan (TDM), and fugitive constituent formed recovery liquid after condensation that the aftermentioned reaction is removed merges as feeding feeding, remain on the continous way still type reactive tank with agitator of 40 liters of 130 ℃ and volumes with temperature in being fed into, and make the ethylbenzene ratio in the reaction solution remain on 16%, and transformation efficiency remains on 55% (amount of monomer in the groove is 45%, and the amount of polymkeric substance is 55%).
After reaction solution is removed fugitive constituent by the devolatilization device, can obtain the particle (pellet) of styrene--acrylic copolymer.Wherein, contain the α-Jia Jibenyixidanti unit of 22.5wt%, the styrene monomer unit of 49wt% and the acrylonitrile monemer unit of 28.5wt% in the particle of styrene--acrylic copolymer.On the other hand, the volatilization composition of removing is condensing as reclaiming liquid with condenser, and mixes with the aforementioned base materials mixed solution continuously and re-use it; This method is adjusted speed of response by the amount of Diisopropyl azodicarboxylate (AIBN), or adjust the amount of uncle-lauryl mercaptan (TDM), be styrene--acrylic copolymer (A1-1) of 1.8 and make melt flow index with the speed of about 27kg/hr.
In addition, the weight-average molecular weight of embodiment A 1-1 is 10.6 ten thousand, the content of oligopolymer (Oligomer) is that 8500ppm and softening temperature are 113.3 ℃.Sulphur content is 114ppm.Thermogravimetric loss at 300 ℃ is 5.1%.
＜embodiment A 1-2 〉
With the speed of 27kg/hr with α-Jia Jibenyixidanti 21.5wt%, styrene monomer 48.5wt%, the raw material of acrylonitrile monemer 30wt% is mixed, again with ethylbenzene 3.0kg/hr, 650ppm Diisopropyl azodicarboxylate (AIBN), uncle 650ppm-lauryl mercaptan (TDM), and fugitive constituent formed recovery liquid after condensation that the aftermentioned reaction is removed merges as feeding feeding, remain on the continous way still type reactive tank with agitator of 40 liters of 120 ℃ and volumes with temperature in being fed into, and make the ethylbenzene ratio in the reaction solution remain on 16%, and percent polymerization remains on 55% (amount of monomer in the groove is 45%, and the amount of polymkeric substance is 55%).
After reaction solution is removed fugitive constituent by the devolatilization device, can obtain the particle (pellet) of styrene--acrylic copolymer.Wherein, contain the α-Jia Jibenyixidanti unit of 22.5wt%, the styrene monomer unit of 49wt% and the acrylonitrile monemer unit of 28.5wt% in the particle of styrene--acrylic copolymer.On the other hand, the volatilization composition of removing is condensing as reclaiming liquid with condenser, and mixes with the aforementioned base materials mixed solution continuously and re-use it; This method is adjusted speed of response by the amount of Diisopropyl azodicarboxylate (AIBN), or adjust the amount of uncle-lauryl mercaptan (TDM), be styrene--acrylic copolymer (A1-2) of 1.8 and make melt flow index with the speed of about 27kg/hr.
In addition, the weight-average molecular weight of embodiment A 1-2 is 11.0 ten thousand, weight-average molecular weight is that 6500ppm and softening temperature are 113.7 ℃ less than the content that 50,000 polymkeric substance accounts for 23.8wt%, oligopolymer (Oligomer).Sulphur content is 132ppm.Thermogravimetric loss at 300 ℃ is 4.8%.
＜embodiment A 1-3 〉
With the speed of 27kg/hr with α-Jia Jibenyixidanti 16.5wt%, styrene monomer 53.5wt%, the raw material of acrylonitrile monemer 30wt% is mixed, again with ethylbenzene 3.0kg/hr, 710ppm Diisopropyl azodicarboxylate (AIBN), uncle 800ppm-lauryl mercaptan (TDM), and fugitive constituent formed recovery liquid after condensation that the aftermentioned reaction is removed merges as feeding feeding, remain on the continous way still type reactive tank with agitator of 40 liters of 130 ℃ and volumes with temperature in being fed into, and make the ethylbenzene ratio in the reaction solution remain on 16%, and percent polymerization remains on 55% (amount of monomer in the groove is 45%, and the amount of polymkeric substance is 55%).
After reaction solution is removed fugitive constituent by the devolatilization device, can obtain the particle (pellet) of styrene--acrylic copolymer.Wherein, contain the α-Jia Jibenyixidanti unit of 17.5wt%, the styrene monomer unit of 54wt% and the acrylonitrile monemer unit of 28.5wt% in the particle of styrene--acrylic copolymer.On the other hand, the volatilization composition of removing is condensing as reclaiming liquid with condenser, and mixes with the aforementioned base materials mixed solution continuously and re-use it; This method is adjusted speed of response by the amount of Diisopropyl azodicarboxylate (AIBN), or adjust the amount of uncle-lauryl mercaptan (TDM), be styrene--acrylic copolymer (A1-3) of 1.8 and make melt flow index with the speed of about 27kg/hr.
In addition, the weight-average molecular weight of embodiment A 1-3 is 11.3 ten thousand, the content of oligopolymer (Oligomer) is that 6000ppm and softening temperature are 113.5 ℃.Sulphur content is 182ppm.Thermogravimetric loss at 300 ℃ is 4.1%.
＜embodiment A 1-4 〉
With the speed of 27kg/hr with α-Jia Jibenyixidanti 16.5wt%, styrene monomer 53.5wt%, the raw material of acrylonitrile monemer 30wt% is mixed, again with ethylbenzene 3.0kg/hr, 770ppm Diisopropyl azodicarboxylate (AIBN), uncle 1000ppm-lauryl mercaptan (TDM), and fugitive constituent formed recovery liquid after condensation that the aftermentioned reaction is removed merges as feeding feeding, remain on the continous way still type reactive tank with agitator of 40 liters of 120 ℃ and volumes with temperature in being fed into, and make the ethylbenzene ratio in the reaction solution remain on 16%, and percent polymerization remains on 55% (amount of monomer in the groove is 45%, and the amount of polymkeric substance is 55%).
After reaction solution is removed fugitive constituent by the devolatilization device, can obtain the particle (pellet) of styrene--acrylic copolymer.Wherein, contain the α-Jia Jibenyixidanti unit of 17.5wt%, the styrene monomer unit of 54.5wt% and the acrylonitrile monemer unit of 28.0wt% in the particle of styrene--acrylic copolymer.On the other hand, the volatilization composition of removing is condensing as reclaiming liquid with condenser, and mixes with the aforementioned base materials mixed solution continuously and re-use it; This method is adjusted speed of response by the amount of Diisopropyl azodicarboxylate (AIBN), or adjust the amount of uncle-lauryl mercaptan (TDM), be styrene--acrylic copolymer (A1-4) of 1.8 and make melt flow index with the speed of about 27kg/hr.
In addition, the weight-average molecular weight of embodiment A 1-4 is 11.9 ten thousand, weight molecular weight is that 4200ppm and softening temperature are 114 ℃ less than the content that 50,000 polymkeric substance accounts for 22.5wt%, oligopolymer (Oligomer).Sulphur content is 211ppm.Thermogravimetric loss at 300 ℃ is 3.6%.
＜Comparative examples A 2-1 〉
With the speed of 27kg/hr with styrene monomer 68wt%, the raw material of acrylonitrile monemer 32wt% is mixed, again with ethylbenzene 3.0kg/hr, 150ppm Diisopropyl azodicarboxylate (AIBN), uncle 1500ppm-lauryl mercaptan (TDM), and fugitive constituent formed recovery liquid after condensation that the aftermentioned reaction is removed merges as feeding feeding, remain on the continous way still type reactive tank with agitator of 40 liters of 130 ℃ and volumes with temperature in being fed into, and make the ethylbenzene ratio in the reaction solution remain on 7%, and percent polymerization remains on 55% (amount of monomer in the groove is 45%, and the amount of polymkeric substance is 55%).
After reaction solution was removed fugitive constituent by the devolatilization device, extrusion granulator can obtain the particle (pellet) of styrene-acrylonitrile based copolymer.Wherein, contain the styrene monomer unit of 72wt% and the acrylonitrile monemer unit of 28.0wt% in the particle of styrene-acrylonitrile based copolymer.On the other hand, the volatilization composition of removing is condensing as reclaiming liquid with condenser, and mixes with the aforementioned base materials mixed solution continuously and re-use it; This method is adjusted speed of response by the amount of Diisopropyl azodicarboxylate (AIBN), or adjusts the amount of uncle-lauryl mercaptan (TDM), is 1.8 styrene-acrylonitrile based copolymer (A2-1) and make melt flow index with the speed of about 27kg/hr.
In addition, the weight-average molecular weight of Comparative examples A 2-1 is 14.7 ten thousand, the content of oligopolymer (Oligomer) is that 7700ppm and softening temperature are 110 ℃.
＜Comparative examples A 2-2 〉
With the speed of 27kg/hr with α-Jia Jibenyixidanti 32wt%, styrene monomer 34wt%, the raw material of acrylonitrile monemer 34wt% is mixed, again with ethylbenzene 3.0kg/hr, 520ppm Diisopropyl azodicarboxylate (AIBN), uncle 1000ppm-lauryl mercaptan (TDM), and fugitive constituent formed recovery liquid after condensation that the aftermentioned reaction is removed merges as feeding feeding, remain on the continous way still type reactive tank with agitator of 40 liters of 130 ℃ and volumes with temperature in being fed into, and make the ethylbenzene ratio in the reaction solution remain on 16%, and percent polymerization remains on 55% (amount of monomer in the groove is 45%, and the amount of polymkeric substance is 55%).
After reaction solution is removed fugitive constituent by the devolatilization device, can obtain the particle (pellet) of styrene--acrylic copolymer.Wherein, contain the α-Jia Jibenyixidanti unit of 36wt%, the styrene monomer unit of 36wt% and the acrylonitrile monemer unit of 28.0wt% in the particle of styrene--acrylic copolymer.On the other hand, the volatilization composition of removing is condensing as reclaiming liquid with condenser, and mixes with the aforementioned base materials mixed solution continuously and re-use it; This method is adjusted speed of response by the amount of Diisopropyl azodicarboxylate (AIBN), or adjust the amount of uncle-lauryl mercaptan (TDM), and make the comparative example that melt flow index is styrene--acrylic copolymer (A2-2) of 1.8 with the speed of about 27kg/hr.
In addition, the weight-average molecular weight of Comparative examples A 2-2 is 10.5 ten thousand, weight molecular weight is that 14000ppm and softening temperature are 114.1 ℃ less than the content that 50,000 polymkeric substance accounts for 26wt%, oligopolymer (Oligomer).Sulphur content is 8ppm.Thermogravimetric loss at 300 ℃ is 6.1%.
＜synthesis example B1 〉
At first, prepare 1,3-butadiene 95.0 weight parts, vinyl cyanide 5.0 weight parts, Potassium Persulphate 1% solution 15.0 weight parts, potassium oleate 2 weight parts, distilled water 140.0 weight parts, uncle-lauryl mercaptan 0.2 weight part.
Under 65 ℃ of temperature of reaction, reacted 12 hours according to above prescription, obtain transformation efficiency and be 94%, solids content is about 36%, weight average particle diameter is the synthetic rubber latex of 0.1 μ m.
In addition, the polymer coagulant that contains the carboxylic acid group with the following ingredients manufacturing:
Ethyl propenoate 85 weight parts, vinylformic acid 15 weight parts, uncle-lauryl mercaptan 0.3 weight part, potassium oleate 2.0 weight parts, dioctyl sodium sulphosuccinate 1.0 weight parts, isopropyl benzene hydrogen peroxidase 10 .4 weight part, sodium formaldehyde sulphoxylate 0.3 weight part, distilled water 200 weight parts.
Reacted 5 hours under 75 ℃ of temperature of reaction according to above prescription, obtain the polymer coagulant that contains the carboxylic acid group of transformation efficiency 95%, pH value 6.0.
Then, utilize the synthetic rubber latex (dry weight) of next loose 100 weight parts of the polymer coagulant that contains the carboxylic acid group (dry weight) of 3 weight parts, the pH value of resulting enlarged rubber emulsion is 8.5, and weight average particle diameter is 0.30 μ m.
At last, carry out graft polymerization reaction with the enlarged rubber emulsion according to following prescription again, to make rubber particles of the present invention (B):
Heavy (dry weight) 100.0 weight parts of enlarged rubber latax, vinylbenzene 25.0 weight parts, vinyl cyanide 8.3 weight parts, potassium oleate 1.2 weight parts, uncle-lauryl mercaptan 0.2 weight part, isopropyl benzene hydrogen peroxidase 10 .5 weight part, copperas solution (0.2wt%) 3.0 weight parts, formaldehyde sodium sulfoxylate solution (10wt%) 3.0 weight parts, ethylene dinitrilotetra-acetic acid solution (0.25wt%) 20.0 weight parts, distilled water 200.0 weight parts.
Styrene/acrylonitrile in the above-mentioned prescription was added polymerization in the reactive system with continuous addition manner in 5 hours, prepared grafting rubbers emulsion is with calcium chloride (CaCl 2) condense, dewater after, be dried to moisture content again below 2%, just can make the rubber particles of wanting required for the present invention (B).Utilize tetrahydrofuran (THF) dissolving＜synthesis example B1〉and filter after, methyl alcohol is added in the filtrate, make rubber particles (B) separate out and filter, can calculate prepared＜synthesis example B1〉comprise the styrene-acrylonitrile based copolymer (A2) of 7wt%, and the rubber particles (B) of 93wt%, the weight average particle diameter of its rubber particles is 0.30 μ m.Wherein, styrene-acrylonitrile based copolymer (A2) contains the styrene monomer unit of 65 ~ 76wt% and the acrylonitrile monemer unit of 24 ~ 35wt%.
＜Embodiment C 1-1 〉
Will by styrene--acrylic copolymer (A1) 76wt% of＜embodiment A 1-1＞make with mixed by＜synthesis example B1＞24wt%, add the lubrication prescription of 0.7 weight part, and 0.3 weight part comprise the mixture that phenol is antioxidant and phosphorous antioxidant, and with the forcing machine (Werner﹠amp of ventage; Pfleiderer ZSK35) gives the melting mixing extrusion granulator.Can obtain the rubber-modified styrene resin composition (C1-1) of rubber particles (B) content 22 weight ratios.
Then, with the emission forming machine that shakes the male factory number SM-90 of company in 220 ℃ penetrate test piece after, can obtain the moulding product of rubber modified styrene series resin, it is analyzed the transitivity evaluation result and sees Table two, and the melt flow index of Embodiment C 1-1 (MI) is that 7.9g/10min, izod impact strength (IZOD) are that 22Kg cm/cm and softening temperature are 113 ℃.
＜Embodiment C 1-2 〉
Will by styrene--acrylic copolymer (A1) 76wt% of＜embodiment A 1-2＞make with mixed by＜synthesis example B1＞24wt%, add the lubrication prescription of 0.7 weight part, and 0.3 weight part comprise the mixture that phenol is antioxidant and phosphorous antioxidant, and with the forcing machine (Werner﹠amp of ventage; Pfleiderer ZSK35) gives the melting mixing extrusion granulator.Can obtain the rubber-modified styrene resin composition (C1-2) of rubber particles (B) content 22 weight percents.
Then, with the emission forming machine that shakes the male factory number SM-90 of company in 220 ℃ penetrate test piece after, can obtain the moulding product of rubber modified styrene series resin, it is analyzed the transitivity evaluation result and sees Table two, and the melt flow index of Embodiment C 1-2 (MI) is that 7.9g/10min, izod impact strength (IZOD) are that 22.1Kg cm/cm and softening temperature are 113.8 ℃.
＜Embodiment C 1-3 〉
Will by styrene--acrylic copolymer (A1) 76wt% of＜embodiment A 1-3＞make with mixed by＜synthesis example B1＞24wt%, add the lubrication prescription of 0.7 weight part, and 0.3 weight part comprise the mixture that phenol is antioxidant and phosphorous antioxidant, and with the forcing machine (Werner﹠amp of ventage; Pfleiderer ZSK35) gives the melting mixing extrusion granulator.Can obtain the rubber-modified styrene resin composition (C1-3) of rubber particles (B) content 22 weight percents.
Then, with the emission forming machine that shakes the male factory number SM-90 of company in 220 ℃ penetrate test piece after, can obtain the moulding product of rubber modified styrene series resin, it is analyzed the transitivity evaluation result and sees Table two, and the melt flow index of Embodiment C 1-3 (MI) is that 6.5g/10min, izod impact strength (IZOD) are that 22.9Kg cm/cm and softening temperature are 113.5 ℃.
＜Embodiment C 1-4 〉
Will by styrene--acrylic copolymer (A1) 76wt% of＜embodiment A 1-4＞make with mixed by＜synthesis example B＞24wt%, add the lubrication prescription of 0.7 weight part, and 0.3 weight part comprise the mixture that phenol is antioxidant and phosphorous antioxidant, and with the forcing machine (Werner﹠amp of ventage; Pfleiderer ZSK35) gives the melting mixing extrusion granulator.Can obtain the rubber-modified styrene resin composition (C1-4) of rubber particles (B) content 22 weight percents.
Then, with the emission forming machine that shakes the male factory number SM-90 of company in 220 ℃ penetrate test piece after, can obtain the moulding product of rubber modified styrene series resin, it is analyzed the transitivity evaluation result and sees Table two, and the melt flow index of Embodiment C 1-4 (MI) is that 6.8g/10min, izod impact strength (IZOD) are that 24Kg cm/cm and softening temperature are 114 ℃.
＜comparative example z1-1 〉
Will by the styrene-acrylonitrile copolymer 76wt% of＜Comparative examples A 2-1＞make with mixed by＜synthesis example B1＞24wt%, add the lubrication prescription of 0.7 weight part, and 0.3 weight part comprise the mixture that phenol is antioxidant and phosphorous antioxidant, and with the forcing machine (Werner﹠amp of ventage; Pfleiderer ZSK35) gives the melting mixing extrusion granulator.Can obtain the comparative example of the rubber-modified styrene resin composition (z1-1) of rubber particles (B) content 22 weight ratios.
Then, with the emission forming machine that shakes the male factory number SM-90 of company in 220 ℃ penetrate test piece after, can obtain the moulding product of rubber modified styrene series resin, it is analyzed the transitivity evaluation result and sees Table two, and the melt flow index of comparative example z1-1 (MI) is that 5.7g/10min, izod impact strength (IZOD) are that 28Kg cm/cm and softening temperature are 110 ℃.
＜comparative example z1-2 〉
Will by styrene--acrylic copolymer 76wt% of＜Comparative examples A 2-2＞make with mixed by＜synthesis example B1＞24wt%, add the lubrication prescription of 0.7 weight part, and 0.3 weight part comprise the mixture that phenol is antioxidant and phosphorous antioxidant, and with the forcing machine (Werner﹠amp of ventage; Pfleiderer ZSK35)) give the melting mixing extrusion granulator.Can obtain the comparative example of the rubber-modified styrene resin composition (z1-2) of rubber particles (B) content 22 weight ratios.
Then, with the emission forming machine that shakes the male factory number SM-90 of company in 220 ℃ penetrate test piece after, can obtain the moulding product of rubber modified styrene series resin, it is analyzed the transitivity evaluation result and sees Table two, and the melt flow index of comparative example z1-2 (MI) is that 7.7g/10min, izod impact strength (IZOD) are that 21.7Kg cm/cm and softening temperature are 114 ℃.
Since＜synthesis example B1＞in, the styrene-acrylonitrile based copolymer (A2) that produces part accounts for＜synthesis example B1＞7wt% (be rubber particles (B) account for＜synthesis example B1＞93%).Wherein, styrene-acrylonitrile based copolymer (A2) contains the styrenic monomers unit of 75wt% and the acrylic monomeric unit of 25wt%.In other words, when forming Embodiment C 1-1 to C1-4 respectively when out of the ordinary the mixing with the synthesis example B1 of 24wt% of the embodiment A 1-1 to A1-4 of 76wt%, styrene-acrylonitrile based copolymer (A2) accounts for the 1.7wt% of rubber modified styrene series resin of the present invention.
Please refer to table one and table two, table one is the embodiment A 1-1 to A1-4 of styrene--acrylic copolymer of the present invention and the comparison sheet of Comparative examples A 2-1 to A2-2.Wherein, charging (Feed) is formed main first monomer component of being made up of acrylonitrile monemer, styrene monomer, α-Jia Jibenyixidanti of expression and is reacted the preceding weight ratio of forming; Particle (Pellet) is formed and is represented that first monomer component forms the composition weight ratio of the acrylonitrile monemer unit of particle, styrene monomer unit, α-Jia Jibenyixidanti unit after polyreaction; A α S rerum natura is represented the rerum natura of each embodiment or each comparative example; AN/SM/ α MS represents that acrylic monomeric unit/styrenic monomers unit/vinyl toluene is monomeric unit shared wt% out of the ordinary; EB represents that the ethylbenzene ratio in the reaction solution keeps ratio; Mw represents the molecular-weight average of each embodiment or each comparative example; Molecular weight is less than 50,000 per-cent in Mw＜50,000 each embodiment of expression or each comparative example; Oligopolymer is represented dipolymer and the trimeric content be made up of styrene monomer, α-Jia Jibenyixidanti or acrylonitrile monemer; SP represents softening point temperature; Sulphur content represents that sulphur content is represented with ppm in each embodiment or each comparative example; And TGA represents thermogravimetric loss, i.e. the weight loss per-cent of 30 minutes following samples of 300 ℃ of constant temperature under nitrogen.Table two is the Embodiment C 1-1 to C1-4 of rubber modified styrene series resin of the present invention and the comparison sheet of comparative example z1-1 to z1-2.Wherein, ABS composition/rerum natura is represented the composition/rerum natura of each embodiment and each comparative example; BP (B) refers to＜synthesis example B1〉employed ratio; MI represents melt flow index; And IZOD izod impact strength.
Table one
Figure BDA00002637306400181
Table two
Figure BDA00002637306400191
By embodiment A 1-1 to A1-4 and Comparative examples A 2-1 to A2-2 more as can be known, styrene--acrylic copolymer of the present invention has less α-Jia Jibenyixidanti unit composition (17.5% or 22.5%), but its softening point temperature can with have more α-Jia Jibenyixidanti unit composition (36%) and approach.In addition, the sulphur content of styrene--acrylic copolymer of the present invention is 50 ~ 300ppm, be preferably 110 ~ 250ppm, can make styrene--acrylic copolymer reach higher heat resisting temperature (300 ℃ of thermogravimetric losses are 3.6% ~ 5.1%, are lower than comparative example).In addition, according to the measured result of embodiment A 1-1 to A1-4, if 130 ℃ of temperature of reaction are reduced to 120 ℃, its softening point temperature also can promote.
Generally speaking, in order to improve the heat resisting temperature of heat stable resin, that is softening temperature (SP) temperature, needing usually to improve α-Jia Jibenyixidanti unit usage quantity, common usage quantity approximately is the ratio greater than the α-Jia Jibenyixidanti unit of 60wt%.By comparative example z1-1 and z1-2 as can be known, the softening point temperature that does not add the α-Jia Jibenyixidanti unit is 110 ℃, and the softening point temperature that adds the α-Jia Jibenyixidanti unit of 36wt% is 114 ℃, but its thermogravimetric loss at 300 ℃ reaches 6.1%.
In other words, if the argument of the general prior art of foundation if reduce the ratio of α-Jia Jibenyixidanti unit, should be able to make softening temperature descend.Yet, according to the prepared styrene--acrylic copolymer of the present invention of embodiment A 1-1 ~ A1-4, though the ratio of α-Jia Jibenyixidanti unit only has 22.5wt% and 17.5wt% respectively, its softening point temperature is between 113.3 to 114 ℃.Moreover this phenomenon also betides on the embodiment of C1-1 ~ C1-4.This shows, styrene--acrylic copolymer of the present invention and rubber modified styrene series resin have reduced the consumption of α-Jia Jibenyixidanti unit, and its softening temperature approaches or equal together the softening temperature of the thermoplastic resin of higher dosage α-Jia Jibenyixidanti unit.In other words, real possess can not expected effect for styrene--acrylic copolymer of the present invention and rubber modified styrene series resin.
Infer owing to reduced the consumption of α-Jia Jibenyixidanti in first monomer component, make the content of oligopolymer (Oligomer) descend, and then help the rising of softening temperature.Wherein, oligopolymer described herein is represented dipolymer and the trimer be made up of styrene monomer, α-Jia Jibenyixidanti or acrylonitrile monemer.
Continue, embodiment A 1-1 compares with A1-2, and its difference is the difference of temperature of reaction, and wherein, the temperature of reaction of embodiment A 1-1 is 130 ℃; The temperature of reaction of embodiment A 1-2 is 120 ℃.Compared as can be known by experimental data, the decline of temperature of reaction can reduce the content of oligopolymer, and therefore, the decline of temperature of reaction can make softening temperature rise.This phenomenon also occurs on embodiment A 1-3 and the A1-4, in addition, because Embodiment C 1-1 to C1-4 is made of with synthesis example B1 separately embodiment A 1-1 to A1-4, therefore, the softening temperature of Embodiment C 1-1 to C1-4 also has the effect because of the decline softening temperature rising of temperature of reaction.
The above only is illustrative, but not is restrictive.Anyly do not break away from spirit of the present invention and category, and to its equivalent modifications of carrying out or change, all should be contained in the appended claims.

Claims (10)

1. styrene--acrylic copolymer, mainly by
The styrene monomer unit of 48 ~ 60wt%;
The α-Jia Jibenyixidanti unit of 15 ~ 27wt%; And
The acrylic monomeric unit of 25 ~ 32wt% is formed,
Wherein the dipolymer of being made up of styrene monomer, α-Jia Jibenyixidanti or acrylic monomer and trimeric content are less than 8500ppm.
2. styrene--acrylic copolymer as claimed in claim 1, wherein the acrylic monomeric unit is vinyl cyanide or Alpha-Methyl vinyl cyanide.
3. styrene--acrylic copolymer as claimed in claim 1, wherein the sulphur content in styrene--acrylic copolymer is 50 ~ 300ppm.
4. styrene--acrylic copolymer, mainly by
The styrene monomer unit of 48 ~ 60wt%;
The α-Jia Jibenyixidanti unit of 15 ~ 27wt%; And
The acrylic monomeric unit of 25 ~ 32wt% is formed,
Wherein the weight-average molecular weight of styrene--acrylic copolymer is lower than the quantity of 50,000 molecule less than 25%.
5. styrene--acrylic copolymer as claimed in claim 4, wherein the acrylic monomeric unit is vinyl cyanide or Alpha-Methyl vinyl cyanide.
6. styrene--acrylic copolymer as claimed in claim 4, wherein the sulphur content in styrene--acrylic copolymer is 50 ~ 300ppm.
7. rubber modified styrene series resin comprises:
Styrene--acrylic copolymer of 75 ~ 80wt%, styrene--acrylic copolymer mainly is made up of the styrene monomer unit of 48 ~ 60wt%, the α-Jia Jibenyixidanti unit of 15 ~ 27wt% and the acrylic monomeric unit of 25 ~ 32wt%, and wherein the dipolymer of being made up of styrene monomer, α-Jia Jibenyixidanti or acrylic monomer and trimeric content are less than 8500ppm;
0 ~ 5wt% styrene-acrylonitrile based copolymer, contain the styrenic monomers unit of 65 ~ 76wt% and the acrylic monomeric unit of 24 ~ 35wt%, wherein styrene--acrylic copolymer and styrene-acrylonitrile based copolymer are formed continuous matrix phase; And
The rubber particles of 20 ~ 25wt%, wherein rubber particles is disperse phase, and is dispersed in the continuous matrix phase.
8. rubber modified styrene series resin as claimed in claim 7, wherein rubber particles is the polymkeric substance of 1,3-butadiene, isoprene or its mixture.
9. rubber modified styrene series resin as claimed in claim 7, wherein the weight average particle diameter of rubber particles is 0.22 ~ 0.6 μ m.
10. rubber modified styrene series resin as claimed in claim 7, wherein the acrylic monomeric unit is vinyl cyanide or Alpha-Methyl vinyl cyanide.
CN201210566196.1A 2011-12-29 2012-12-24 Styrene-alpha-methylstyrene-acrylonitrile copolymer and rubber-modified styrene resin Active CN103183762B (en)

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CN104448596A (en) * 2013-09-14 2015-03-25 奇美实业股份有限公司 Resin composition
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CN103613877A (en) * 2013-11-20 2014-03-05 上海锦湖日丽塑料有限公司 High heat-resistance ABS (acrylonitrile-butadiene-styrene) resin composition suitable for blow molding and preparation method thereof
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