CN103183762B - 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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CN103183762B
CN103183762B CN201210566196.1A CN201210566196A CN103183762B CN 103183762 B CN103183762 B CN 103183762B CN 201210566196 A CN201210566196 A CN 201210566196A CN 103183762 B CN103183762 B CN 103183762B
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styrene
methylstyrene
acrylic
monomer
rubber
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CN103183762A (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-α-methylstyrene-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-α-methylstyrene-acrylic copolymer primarily of styrenic monomer units, α-methylstyrenemonomer unit and acrylic monomeric unit composition.
[background technology]
Why phenylethylene resin series (as ABS resin etc.) is widely used on electrical equipment, electronics and auto parts, mainly all there is good evaluation its processing forming, physical property and mechanical properties aspect, especially a large characteristic especially in the good appearance of products formed and glossiness.
On the other hand, current machine-shaping industry is in order to improve the cast gate outward appearance of ejection formed piece, and be gradually adopt pin cast gate (Pin gate) to carry out ejection formation, this trend also makes the requirement of phenylethylene resin series in thermostability relatively improve.Therefore, how making phenylethylene resin series improve resin treatment thermostability, is the problem that pole, field is to be improved for this reason.
In addition, generally speaking, in the thermoplastic resin be made up of styrenic monomer unit, α-methylstyrenemonomer unit and acrylic monomeric unit, when the content of its α-methylstyrenemonomer unit is higher, there is the effect promoting softening temperature.Although the thermotolerance qualitative change of thermoplastic resin can be made good, but there is the shortcoming of cost increase.
[summary of the invention]
In view of this, object of the present invention is providing a kind of styrene-α-methylstyrene-acrylic copolymer and rubber modified styrene series resin, exactly to improve the problem of resin thermotolerance and cost increase.
Therefore, for reaching above-mentioned purpose, according to a kind of styrene-α-methylstyrene-acrylic copolymer of the present invention, primarily of the styrenic monomer units of 48 ~ 60wt%, the α-methylstyrenemonomer unit of 15 ~ 27wt%; And the acrylic monomeric unit composition of 25 ~ 32wt%.Wherein, the dipolymer be made up of styrene monomer, α-methylstyrenemonomer or acrylic monomer and trimeric content are less than 8500ppm.Wherein styrene-α-methylstyrene-acrylic copolymer is formed by styrene monomer, α-methylstyrenemonomer and acrylonitrile monemer copolymerization, and wherein styrene-α-methylstyrene-acrylic copolymer forms primarily of styrenic monomer units, α-methylstyrenemonomer unit and acrylic monomeric unit.Namely, above-mentioned styrenic monomer units, α-methylstyrenemonomer unit and acrylic monomeric unit, after referring to styrene monomer, α-methylstyrenemonomer and acrylic monomer copolymerizable respectively, the tectonic element in styrene-α-methylstyrene-acrylic copolymer.
Again, the present invention proposes a kind of styrene-α-methylstyrene-acrylic copolymer further, primarily of the styrenic monomer units of 48 ~ 60wt%, the α-methylstyrenemonomer unit of 15 ~ 27wt%; And the acrylic monomeric unit of 25 ~ 32wt% formed.Wherein this styrene-α-methylstyrene-acrylic copolymer weight-average molecular weight lower than 50,000 molecule be less than 25%.
Wherein, in above-mentioned styrene-α-methylstyrene-acrylic copolymer, acrylic monomeric unit is preferably vinyl cyanide or Alpha-Methyl vinyl cyanide.In addition, the sulphur content in styrene-α-methylstyrene-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: the styrene-α-methylstyrene-acrylic copolymer (A1) of 75 ~ 80wt%, styrene-α-methylstyrene-acrylic copolymer (A1) formed primarily of the acrylic monomeric unit of the styrenic monomer units of 48 ~ 60wt%, the α-methylstyrenemonomer unit of 15 ~ 27wt% and 25 ~ 32wt%, and the dipolymer be wherein made up of styrene monomer, α-methylstyrenemonomer or acrylic monomer and trimeric content are less than 8500ppm; 0 ~ 5wt% styrene-acrylonitrile based copolymer (A2), the acrylic monomeric unit of the styrenic monomer unit containing 65 ~ 76wt% and 24 ~ 35wt%, wherein styrene-α-methylstyrene-acrylic copolymer and styrene-acrylonitrile based copolymer form continuous matrix phase, and the rubber particles of 20 ~ 25wt% (B), wherein rubber particles is disperse phase, and be dispersed in continuous matrix mutually in.In addition, aforesaid rubber particles is preferably selected from least one 1, the polymkeric substance of 3 divinyl, isoprene or its mixture, and the weight average particle diameter of rubber particles is preferably 0.22 ~ 0.6 μm, and acrylic monomeric unit is preferably vinyl cyanide or Alpha-Methyl vinyl cyanide.
Effect of the present invention is the softening temperature using less α-methylstyrenemonomer unit that styrene-α-methylstyrene-acrylic copolymer and rubber modified styrene series resin can be made to reach higher, reduces costs thus.In addition, the present invention also can reduce residual dipolymer and trimeric content, and then the amount of being fuming improving the course of processing (such as during ejection formation) or the mold fouling caused.In addition, the sulphur content of styrene-α-methylstyrene-acrylic copolymer is 50 ~ 300ppm, is preferably the heat resisting temperature (thermogravimetric weight loss is lower) that 110 ~ 250ppm can make styrene-α-methylstyrene-acrylic copolymer reach higher.
For above and other object of the present invention, feature and advantage can more be become apparent, hereafter spy enumerates preferred implementation, is described in detail below:
[embodiment]
The styrenic monomer units of styrene-α-methylstyrene-acrylic copolymer of the present invention primarily of 48 ~ 60wt%, the α-methylstyrenemonomer unit of 15 ~ 27wt%; And the acrylic monomeric unit of 25 ~ 32wt% formed.Wherein, the dipolymer be made up of styrene monomer, α-methylstyrenemonomer or acrylic monomer and trimeric content are less than 8500ppm.
Again, the present invention also proposes another kind of styrene-α-methylstyrene-acrylic copolymer, acrylic monomeric unit primarily of the styrenic monomer units of 48 ~ 60wt%, the α-methylstyrenemonomer unit of 15 ~ 27wt% and 25 ~ 32wt% formed, and wherein the weight-average molecular weight of this styrene-α-methylstyrene-acrylic copolymer is less than 25% lower than the quantity system of the molecule of 50,000.
When the content of acrylic monomeric unit is greater than 32wt%, then the hue difference of styrene-α-methylstyrene-acrylic copolymer; And when the content of acrylic monomeric unit is less than 25wt%, then styrene-α-methylstyrene-acrylic copolymer endurance is not good.In addition, when α-methylstyrenemonomer unit content is greater than 27wt%, then the problem having cost high produces; If when α-methylstyrenemonomer unit content is less than 15wt%, then the thermotolerance of thermoplastic resin can decline.
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 JISK-7210 regulation, test with 220 DEG C × 10kg, and represent with g/10min.
Two, izod (IZOD) shock strength: specify test according to ASTM D-256, represent with Kg cm/cm.
Three, weight-average molecular weight (weight-average molecular weight, Mw): the calibration curve utilizing known available standard vinylbenzene to be made tries to achieve weight-average molecular weight, there is the monitoring of differential tortuosity ratio and gel permeation chromatograph (the Gel Permeation Chromatogrpahy of two functions is monitored in scattering of light, GPC, Waters Company supplies) measure.
Four, the dipolymer of styrenic monomers and/or acrylic monomer and trimeric total content testing method: get 1 gram of embodiment A 1-1 ~ A1-4 and Comparative examples A 2-1 ~ A2-2 respectively in acetone molten, this resin composition solution re-uses Hewlett Packard company numbering 7890A and to perform an analysis mensuration with the gas chromatograph of flame ion analyzer.
Five, softening point temperature, refers to vicat softening point temperature (Vicat SofteningTemperature): specify test according to ASTM D-1525, and unit is DEG C to represent.
Six, thermogravimetric weight loss: use TAQ5000 thermogravimetric analyzer, prepare the weight loss of 5 milligrams of samples, 300 DEG C of constant temperature, 30 minutes lower working samples under the environment of nitrogen.
Seven, sulphur content: prepare 10 milligrams of samples, through High Temperature Furnaces Heating Apparatus (Mitsubishi AQF-100) with after 900 ~ 1000 DEG C of process, (absorption liquid collocation method is the potassium primary phosphate (KH getting 1c.c. to inject 5c.c absorption liquid through gas phase adsorption unit (Gas Absorption Unit, Mitsubishi GA-100 supply) 2pO 4) with the hydrogen peroxide (H of 100ml 2o 2), quantitatively become 1L with pure water; Now PO 4 3-concentration is 1ppm) and measure, with PO during measurement with ion chromatograph (DIONEX ICS-1500) 4 3-for interior mark 1ppm, with 1000ppm sulfate radical (SO 4 2-) solution is standard substance, configures different concentration known [SO with standard substance 4 2-] standard measure, record corresponding survey area, to formulate [SO 4 2-] calibration curve.Calibration curve [SO 4 2-] concentration calculation formula is { [sample area]-[background value area] } * 5000/ sample heavy (unit ppm).Substitute into calibration curve after testing sample records [sample area] and corresponding [SO can be obtained 4 2-], afterwards with [S]=[SO 4 2-convert and obtain in]/3 (unit ppm).
Again, the present invention also proposes a kind of rubber modified styrene series resin, comprise: the styrene-α-methylstyrene-acrylic copolymer (A1) of 75 ~ 80wt%, wherein styrene-α-methylstyrene-acrylic copolymer (A1) is primarily of the styrenic monomer units of 48 ~ 60wt%, the α-methylstyrenemonomer unit of 15 ~ 27wt% and the acrylic monomeric unit of 25 ~ 32wt% formed, wherein by styrene monomer, the dipolymer that α-methylstyrenemonomer or acrylic monomer form and trimeric content are less than 8500ppm, 0 ~ 5wt% styrene-acrylonitrile based copolymer (A2), the styrenic monomer unit of styrene-acrylonitrile based copolymer (A2) containing 65 ~ 76wt% and the acrylic monomeric unit of 24 ~ 35wt%, wherein styrene-α-methylstyrene-acrylic copolymer and styrene-acrylonitrile based copolymer form continuous matrix phase, and the rubber particles of 20 ~ 25wt% (B), wherein rubber particles is disperse phase, and be dispersed in this continuous matrix mutually in.
Below will be described in detail to styrene-α-methylstyrene-acrylic copolymer (A1), styrene-acrylonitrile based copolymer (A2) and rubber particles (B) one by one:
[styrene-α-methylstyrene-acrylic copolymer (A1)]
The first monomer component that styrene-α-methylstyrene-acrylic copolymer (A1) forms primarily of styrene monomer, α-methylstyrenemonomer and acrylic monomer is obtained by the solution polymerization.
Preferably, the total amount of the first monomer component formed with styrene monomer, α-methylstyrenemonomer, acrylic monomer calculates for 100wt%, and in this first monomer component, the content range of styrene monomer can be such as 47wt% ~ 59wt%; Be more preferably 48.5wt% ~ 53.5wt%.In addition, in this first monomer component, the content range of α-methylstyrenemonomer is 14wt% ~ 26wt%; Be more preferably 16.5wt% ~ 21.5wt%.
Acrylic monomer can be used alone or as a mixture, and acrylic monomer is including but not limited to vinyl cyanide or Alpha-Methyl vinyl cyanide etc.Preferably, acrylic monomer can be such as vinyl cyanide.Preferably, with the total amount of styrene monomer, α-methylstyrenemonomer, acrylic monomer for 100wt% calculates, in this first monomer component, the content range of acrylic monomer can be such as 27wt% ~ 34wt%; Be more preferably 29wt% ~ 32wt%.
In solution polymerization, optionally polymerization initiators can be added.Polymerization initiators such as can be selected from mono-functional's polymerization initiators, multi-functional polymerization initiators, or their combination.Mono-functional's polymerization initiators can be used alone or as a mixture, and mono-functional's polymerization initiators can such as 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-peroxybenzoate), two-2-ethylhexyl peroxy dicarbonate (bis-2-ethylhexyl peroxydicarbonate), t-butylperoxyisopropyl carbonic ether (tert-butyl peroxy isopropylcarbonate, be called for short BPIC), cyclohexanone peroxide (cyclohexanone peroxide), 2, 2'-azo-bis--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-bis--2-methylbutyronitrile (2, 2'-azo-bis-2-methyl butyronitrile) etc.Wherein polymerization initiators can be such as dibenzoyl peroxide, 2,2'-azos-bis--isopropyl cyanide.
Multi-functional polymerization initiators can be used alone or as a mixture, and multi-functional polymerization initiators can such as including but not limited to 1, 1-pair-tert-butyl hydroperoxide hexanaphthene (1, 1-bis-t-butyl peroxycyclohexane, 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-ethylhexanoxyperoxy) 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)-hexane [2 of 5-, 5-dimethyl-2, 5-bis-(benzoylperoxy) hexane], two-tert-butyl hydroperoxide-six hydrogen-terephthalate (di-t-butylperoxy-hexahydro-terephthalate, be called for short BPHTH), or 2, 2-two (4, 4-bis--tert-butyl hydroperoxide) cyclohexyl propane [2, 2-bis-(4, 4-di-t-butyl peroxy) cyclohexyl propane, be called for short PX-12] etc.
In solution polymerization, optionally chain-transfer agent can be added.Chain-transfer agent can be used alone or as a mixture; and chain-transfer agent can such as including but not limited to n-lauryl mercaptan (n-dodecylmercaptan; be called for short NDM), stearyl-mercaptan (stearyl mercaptan), uncle-lauryl mercaptan (t-dodecyl mercaptan; be called for short TDM), n-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 be such as 90 DEG C ~ 130 DEG C; More preferably, the operating temperature range of solution polymerization can be such as 100 DEG C ~ 120 DEG C.
[styrene-acrylonitrile based copolymer (A2)]
One of method for making of styrene-acrylonitrile based copolymer (A2) is can by comprising styrenic monomers (i-1) and acrylic monomer (i-2), and the second comonomer component of optionally adding other copolymerizable vinyl monomers (i-3) is obtained by the solution polymerization.Separately, styrene-acrylonitrile based copolymer (A2) can also for the styrene-acrylonitrile based copolymer (A2) of non-grafting produced when manufacturing rubber particles (B) in emulsion polymerization rubber graft copolymer.
Styrenic monomers (i-1) can be used alone or as a mixture, and styrenic monomers (i-1) can such as including but not limited to vinylbenzene, alpha-methyl styrene, p-t-butyl styrene, p-methylstyrene, o-vinyl toluene, m-vinyl toluene, 2,4-dimethyl styrene, ethyl styrene, Alpha-Methyl-p-methylstyrene, or bromstyrol etc.Preferably, styrenic monomers (i-1) can such as 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 be such as 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 such as including but not limited to vinyl cyanide or Alpha-Methyl vinyl cyanide etc.Preferably, acrylic monomer (i-2) can be such as 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 be such as 10wt% ~ 50wt%; More preferably, can be such as 15wt% ~ 45wt%; Again more preferably, can be such as 20wt% ~ 42wt%.
Other copolymerizable vinyl monomers (i-3) can be used alone or as a mixture, and other copolymerizable vinyl monomers (i-3) can such as including but not limited to acrylic monomer, methacrylic monomers, acrylic ester monomer, maleimide system monomer, Maleic Acid, Anhydrous or methacrylate ester monomer etc.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 be such as 0wt% ~ 40wt%; More preferably, can be such as 1wt% ~ 34wt%; Again more preferably, can be such as 3wt% ~ 30wt%.
Acrylic monomer can such as including but not limited to vinylformic acid etc.Methacrylic monomers can such as including but not limited to methacrylic acid etc.Acrylic ester monomer can such as including but not limited to methyl acrylate, ethyl propenoate, isopropyl acrylate, or butyl acrylate etc.Preferably, acrylic ester monomer can be such as butyl acrylate.
Methacrylate ester monomer can such as including but not limited to methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, butyl methacrylate, benzyl methacrylate, N-Hexyl methacrylate, cyclohexyl methacrylate, lauryl ester, HEMA, glytidyl methacrylate, glycidyl methacrylate, Dimethylaminoethyl Methacrylate (dimethylaminoethyl methacrylate), ethylene glycol dimethacrylate (ethylenedimethacrylate), or dimethacrylate peopentyl ester (neopentyl dimethacrylate) etc.Preferably, methacrylate ester monomer can such as be selected from methyl methacrylate or butyl methacrylate.
Maleimide system monomer can be such as: maleimide, N-methylmaleimido, N-isopropylmaleimide, N-butyl maleimide, N-hexyl maleimide, N-octyl group maleimide, N-dodecyl maleimide, N-N-cyclohexylmaleimide, N-phenylmaleimide, N-2, 3-tolylmaleimide, N-2, 4-tolylmaleimide, N-2, 3-ethylbenzene maleimide, N-2, 4-ethylbenzene maleimide, N-2, 3-fourth phenyl maleimide, N-2, 4-fourth phenyl maleimide, N-2, 6-tolylmaleimide, N-2, 3-chlorophenylmaleimide, N-2, 4-chlorophenylmaleimide, N-2, 3-bromophenyl maleimide, N-2, 4-bromophenyl maleimide etc., be wherein most preferred with N-phenylmaleimide again.
The kind of polymerization initiators and chain-transfer agent as the above-mentioned kind preparing polymerization initiators in styrene-α-methylstyrene-acrylic copolymer (A1) and chain-transfer agent, therefore repeats no more.
Preferably, the operating temperature range of solution polymerization can be such as 70 DEG C ~ 140 DEG C; More preferably, the operating temperature range of solution polymerization can be such as 90 DEG C ~ 130 DEG C.
[rubber particles (B)]
Graft copolymer made by this rubber particles (B) is such as under rubber latex (solid content) 40 ~ 90wt% exists, with functional monomer's component of 10 ~ 60wt% obtained by the graft polymerization reaction, wherein, functional monomer's component comprises can such as by styrenic monomers 50 ~ 90wt%, acrylic monomer 10 ~ 50%wt%, and the monomer mixture that other copolymerizable vinyl monomer 0 ~ 40wt% combine.
Preferably, functional monomer's component such as can 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 additive can be added, and additive is including but not limited to emulsifying agent, polymerization initiators or chain-transfer agent etc.Optionally can again via condensation, dehydration, drying and other steps process after emulsion polymerization reaction.Rubber particles (B) and styrene-acrylonitrile based copolymer (A2) is comprised in obtained emulsion polymerization rubber graft copolymer.After graft polymerization reaction, the total amount based on emulsion polymerization rubber graft copolymer (I) is in 100wt%, and the content range of styrene-acrylonitrile based copolymer is below 10wt%.
Rubber latex obtained through emulsion polymerization method by rubber components, or after emulsion polymerization reaction, give loose process (agglomerating treatment) more further, and optionally in emulsion polymerization reaction, add other copolymerizable monomer.Preferably, rubber components such as can be selected from diene series rubber, polyacrylic ester system rubber, or polysiloxane series rubber.
Diene series rubber can be used alone or as a mixture, and diene series rubber can such as including but not limited to divinyl rubber, synthetic polyisoprene, neoprene, ethylene propylene diene ter-polymer rubber (ethylene propylene diene terpolymer, be called for short EPDM), or styrenic-diene system rubber or vinyl cyanide-diene series rubber etc.Wherein, divinyl rubber can such as 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 (Cis) in the divinyl rubber of high cis-contents/vinyl (Vinyl) consists of (94 ~ 98wt%)/(1 ~ 5wt%), all the other compositions are then trans (Trans) structure, and not Buddhist nun's viscosity (mooney viscosity) 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 is at (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 ~ 800,000 is good.Styrenic-diene system rubber can such as including but not limited to styrene butadiene rubbers, styrene isoprene rubber etc., and styrenic-diene system rubber can be such as block copolymerization zoarium, random copolymers (random) or planetary multipolymer (star type), wherein, in styrene butadiene rubbers, the part by weight scope of vinylbenzene and divinyl can be such as 5:95 ~ 80:20, and molecular weight ranges is preferably 50,000 ~ 600,000.Preferably, styrenic-diene system rubber can be such as styrene butadiene rubbers.Other copolymerizable monomer can such as including but not limited to styrenic monomers, acrylic monomer and (methyl) acrylic ester monomer etc.Diene series rubber emulsion can such as including but not limited to being polyhutadiene, butadiene-styrene copolymer, perbutan, divinyl-methylmethacrylate copolymer, or isoprene-butyl acrylate copolymer etc.
Loose process can adopt the loose method of general freezing loose method, mechanical loose method or additive.The additive used in the loose method of additive can such as 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) containing the polymer coagulant of carboxylic acid group: (methyl) vinylformic acid-(methyl) acrylate copolymer (as methacrylic acid-acrylic acid acrylate copolymer, EUDRAGIT L100-55) etc.
For example, the manufacture method of diene series rubber emulsion can use diene monomer (such as divinyl) to be polymerized with emulsion polymerization method, or, the diene monomer of 50 ~ 100wt% is polymerized with emulsion polymerization method with monomers such as the vinylbenzene of 0 ~ 50wt% and/or vinyl cyanide, the diene series rubber emulsion that weight average particle diameter is 0.05 μm ~ 0.6 μm can be obtained.Also after aforementioned monomer can being obtained the small particle size diene series rubber emulsion of weight average particle diameter 0.05 μm ~ 0.20 μm with emulsion polymerization method, again to give loose process, aforementioned small particle size diene series rubber emulsion hypertrophy is become the Large stone diene series rubber emulsion of weight average particle diameter 0.22 μm ~ 0.6 μm.Wherein, if rubber particles is less than 0.22 μm, under identical rubber particles weight, because rubber particles is too small, and make impact-resistant strength degradation; Otherwise, if rubber particles is greater than 0.6 μm, under identical rubber particles weight, because the quantity of rubber particles declines, and make impact-resistant strength degradation.
The kind of the styrenic monomers that the graft copolymer made by rubber particles (B) uses, acrylic monomer and copolymerizable monomer, polymerization initiators, chain-transfer agent, illustrate identical with the monomer in styrene-acrylonitrile based copolymer (A2), do not repeat them here.
In preparation rubber modified styrene series resin process of the present invention, various additive can be added if desired, and additive such as can 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 respectively in the polyreaction of above-mentioned styrene-α-methylstyrene-acrylic copolymer (A1), styrene-acrylonitrile based copolymer (A2) or rubber particles (B), interpolation after polyreaction, before condensation, or above-mentioned additive carrying out extruding process of mixing, can be prepared in the process of rubber modified styrene series resin and adding.
Antioxidant can be used alone or as a mixture, and antioxidant can such as including but not limited to phenol system antioxidant, thioether system antioxidant, or phosphorous antioxidant etc.Preferably, with the total amount of rubber modified styrene series resin for 100wt% calculates, the content range of antioxidant is below 2wt%.
Phenol system antioxidant can be used alone or as a mixture, and phenol system antioxidant can such as including but not limited to 3, 5-two (1, 1-dimethyl ethyl)-4-hydroxy-phenylpropionic 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-bis-(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--diethyl support group-bis-[3-(3, 5-dual-tert-butyl-4-hydroxyphenyl) propionic ester], or 2, 2'-oxalamide-bis-[ethyl-3-(3, 5-pair-tertiary butyl-4-hydroxyphenyl) propionic ester] etc.
Thioether system antioxidant can be used alone or as a mixture, and thioether system antioxidant can such as including but not limited to distearyl thiodipropionic acid ester, two palmityl thiodipropionic acid esters, five tetrahydroxybutane-four-(β-ten dimethyl-sulphur propionic esters), or two octadecyl thioethers etc.
Phosphorous antioxidant can be used alone or as a mixture, and the optional phosphorous antioxidant of self-contained phosphorous acid ester of phosphorous antioxidant or the phosphorous antioxidant of phosphate ester-containing.Phosphorous antioxidant containing phosphorous acid ester can such as 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 phosphate ester-containing such as can stretch biphenyl phosphate including but not limited to four (2,4-tert-butyl-phenyls)-4,4'-, or the support of 9,10-dihydro-9-oxy-10-phosphoric acid phenanthrene-10-oxygen etc.
Lubrication prescription can be used alone or as a mixture, and lubrication prescription can such as including but not limited to the compound, polyethylene wax, octocosoic acid wax, carnauba wax (carnuba wax), petroleum wax etc. 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 ester, poly-propionic acid alcohol tristearate, behenic acid, stearic acid etc.Preferably, with the total amount of rubber modified styrene series resin for 100wt% calculates, the content range of lubrication prescription is below 2wt%.
In preparation rubber modified styrene series resin process of the present invention, various polymkeric substance can be added if desired, and polymkeric substance can such as including but not limited to polycarbonate, polymeric amide, polyethylene terephthalate, polybutylene terephthalate, poly-stretch phenyl ether, polyvinyl chloride, polymethylmethacrylate, ethylene methyl methacrylate multipolymer, polypropylene, styrene butadiene block copolymer, hydrogenated acrylonitrile-butadienecopolymer, hydrogenated styrene-butadiene block copolymer etc.Preferably, with the total amount of rubber modified styrene series resin for 100wt% calculates, the content range of polymkeric substance is 5wt% ~ 200wt%.
The products formed of rubber modified styrene series resin of the present invention, by rubber modified styrene series resin as above through mixing obtained by machine-shaping process.Machine-shaping process of mixing can adopt manner known in the art, therefore repeats no more.
The present invention will be described further with regard to following examples, but it is to be understood that these embodiments are only the use illustrated, and should not be interpreted as restriction of the invention process.
< embodiment >
< embodiment A 1-1>
With the speed of 27kg/hr by α-methylstyrenemonomer 21.5wt%, styrenic monomers 48.5wt%, the raw material of acrylic monomer 30wt% is mixed, again by ethylbenzene 3.0kg/hr, 620ppm Diisopropyl azodicarboxylate (AIBN), uncle 550ppm-lauryl mercaptan (TDM), and the Ethylene recov that the fugitive constituent that removes of aftermentioned reaction is formed after condensation merges as feeding feeding, 130 DEG C are remained on and the continous way still type reactive tank with agitator of volume 40 liters to be fed into interior temperature, and make the ethylbenzene ratio in reaction solution remain on 16%, and transformation efficiency remains on 55%, and (amount of monomer in groove is 45%, the amount of polymkeric substance is 55%).
After reaction solution is by devolatilizer removing fugitive constituent, the particle (pellet) of styrene-α-methylstyrene-acrylic copolymer can be obtained.Wherein, the α-methylstyrenemonomer unit containing 22.5wt% in the particle of styrene-α-methylstyrene-acrylic copolymer, the styrenic monomer units of 49wt% and the acrylonitrile monomer unit of 28.5wt%.On the other hand, the volatilization composition removed is condensing as Ethylene recov using condenser, and mixes with aforementioned base materials mixed solution continuously and re-use it; This method adjusts speed of response by the amount of Diisopropyl azodicarboxylate (AIBN), or the amount of adjustment uncle-lauryl mercaptan (TDM), and make with the speed of about 27kg/hr styrene-α-methylstyrene-acrylic copolymer (A1-1) that melt flow index is 1.8.
In addition, the weight-average molecular weight of embodiment A 1-1 is 10.6 ten thousand, the content of oligopolymer (Oligomer) be 8500ppm and softening temperature is 113.3 DEG C.Sulphur content is 114ppm.Be 5.1% at the thermogravimetric weight loss of 300 DEG C.
< embodiment A 1-2>
With the speed of 27kg/hr by α-methylstyrenemonomer 21.5wt%, styrene monomer 48.5wt%, the raw material of acrylonitrile monemer 30wt% is mixed, again by ethylbenzene 3.0kg/hr, 650ppm Diisopropyl azodicarboxylate (AIBN), uncle 650ppm-lauryl mercaptan (TDM), and the Ethylene recov that the fugitive constituent that removes of aftermentioned reaction is formed after condensation merges as feeding feeding, 120 DEG C are remained on and the continous way still type reactive tank with agitator of volume 40 liters to be fed into interior temperature, and make the ethylbenzene ratio in reaction solution remain on 16%, and percent polymerization remains on 55%, and (amount of monomer in groove is 45%, the amount of polymkeric substance is 55%).
After reaction solution is by devolatilizer removing fugitive constituent, the particle (pellet) of styrene-α-methylstyrene-acrylic copolymer can be obtained.Wherein, the α-methylstyrenemonomer unit containing 22.5wt% in the particle of styrene-α-methylstyrene-acrylic copolymer, the styrenic monomer units of 49wt% and the acrylonitrile monomer unit of 28.5wt%.On the other hand, the volatilization composition removed is condensing as Ethylene recov using condenser, and mixes with aforementioned base materials mixed solution continuously and re-use it; This method adjusts speed of response by the amount of Diisopropyl azodicarboxylate (AIBN), or the amount of adjustment uncle-lauryl mercaptan (TDM), and make with the speed of about 27kg/hr styrene-α-methylstyrene-acrylic copolymer (A1-2) that melt flow index is 1.8.
In addition, the weight-average molecular weight of embodiment A 1-2 is 11.0 ten thousand, the weight-average molecular weight polymkeric substance that is less than 50,000 accounts for 23.8wt%, the content of oligopolymer (Oligomer) be 6500ppm and softening temperature is 113.7 DEG C.Sulphur content is 132ppm.Be 4.8% at the thermogravimetric weight loss of 300 DEG C.
< embodiment A 1-3>
With the speed of 27kg/hr by α-methylstyrenemonomer 16.5wt%, styrene monomer 53.5wt%, the raw material of acrylonitrile monemer 30wt% is mixed, again by ethylbenzene 3.0kg/hr, 710ppm Diisopropyl azodicarboxylate (AIBN), uncle 800ppm-lauryl mercaptan (TDM), and the Ethylene recov that the fugitive constituent that removes of aftermentioned reaction is formed after condensation merges as feeding feeding, 130 DEG C are remained on and the continous way still type reactive tank with agitator of volume 40 liters to be fed into interior temperature, and make the ethylbenzene ratio in reaction solution remain on 16%, and percent polymerization remains on 55%, and (amount of monomer in groove is 45%, the amount of polymkeric substance is 55%).
After reaction solution is by devolatilizer removing fugitive constituent, the particle (pellet) of styrene-α-methylstyrene-acrylic copolymer can be obtained.Wherein, the α-methylstyrenemonomer unit containing 17.5wt% in the particle of styrene-α-methylstyrene-acrylic copolymer, the styrenic monomer units of 54wt% and the acrylonitrile monomer unit of 28.5wt%.On the other hand, the volatilization composition removed is condensing as Ethylene recov using condenser, and mixes with aforementioned base materials mixed solution continuously and re-use it; This method adjusts speed of response by the amount of Diisopropyl azodicarboxylate (AIBN), or the amount of adjustment uncle-lauryl mercaptan (TDM), and make with the speed of about 27kg/hr styrene-α-methylstyrene-acrylic copolymer (A1-3) that melt flow index is 1.8.
In addition, the weight-average molecular weight of embodiment A 1-3 is 11.3 ten thousand, the content of oligopolymer (Oligomer) be 6000ppm and softening temperature is 113.5 DEG C.Sulphur content is 182ppm.Be 4.1% at the thermogravimetric weight loss of 300 DEG C.
< embodiment A 1-4>
With the speed of 27kg/hr by α-methylstyrenemonomer 16.5wt%, styrene monomer 53.5wt%, the raw material of acrylonitrile monemer 30wt% is mixed, again by ethylbenzene 3.0kg/hr, 770ppm Diisopropyl azodicarboxylate (AIBN), uncle 1000ppm-lauryl mercaptan (TDM), and the Ethylene recov that the fugitive constituent that removes of aftermentioned reaction is formed after condensation merges as feeding feeding, 120 DEG C are remained on and the continous way still type reactive tank with agitator of volume 40 liters to be fed into interior temperature, and make the ethylbenzene ratio in reaction solution remain on 16%, and percent polymerization remains on 55%, and (amount of monomer in groove is 45%, the amount of polymkeric substance is 55%).
After reaction solution is by devolatilizer removing fugitive constituent, the particle (pellet) of styrene-α-methylstyrene-acrylic copolymer can be obtained.Wherein, the α-methylstyrenemonomer unit containing 17.5wt% in the particle of styrene-α-methylstyrene-acrylic copolymer, the styrenic monomer units of 54.5wt% and the acrylonitrile monomer unit of 28.0wt%.On the other hand, the volatilization composition removed is condensing as Ethylene recov using condenser, and mixes with aforementioned base materials mixed solution continuously and re-use it; This method adjusts speed of response by the amount of Diisopropyl azodicarboxylate (AIBN), or the amount of adjustment uncle-lauryl mercaptan (TDM), and make with the speed of about 27kg/hr styrene-α-methylstyrene-acrylic copolymer (A1-4) that melt flow index is 1.8.
In addition, the weight-average molecular weight of embodiment A 1-4 is 11.9 ten thousand, the weight molecular weight polymkeric substance that is less than 50,000 accounts for 22.5wt%, the content of oligopolymer (Oligomer) be 4200ppm and softening temperature is 114 DEG C.Sulphur content is 211ppm.Be 3.6% at the thermogravimetric weight loss of 300 DEG C.
< Comparative examples A 2-1>
With the speed of 27kg/hr by styrene monomer 68wt%, the raw material of acrylonitrile monemer 32wt% is mixed, again by ethylbenzene 3.0kg/hr, 150ppm Diisopropyl azodicarboxylate (AIBN), uncle 1500ppm-lauryl mercaptan (TDM), and the Ethylene recov that the fugitive constituent that removes of aftermentioned reaction is formed after condensation merges as feeding feeding, 130 DEG C are remained on and the continous way still type reactive tank with agitator of volume 40 liters to be fed into interior temperature, and make the ethylbenzene ratio in reaction solution remain on 7%, and percent polymerization remains on 55%, and (amount of monomer in groove is 45%, the amount of polymkeric substance is 55%).
After reaction solution is by devolatilizer removing fugitive constituent, extrusion granulator can obtain the particle (pellet) of styrene-acrylonitrile based copolymer.Wherein, containing the styrenic monomer units of 72wt% and the acrylonitrile monomer unit of 28.0wt% in the particle of styrene-acrylonitrile based copolymer.On the other hand, the volatilization composition removed is condensing as Ethylene recov using condenser, and mixes with aforementioned base materials mixed solution continuously and re-use it; This method adjusts speed of response by the amount of Diisopropyl azodicarboxylate (AIBN), or the amount of adjustment uncle-lauryl mercaptan (TDM), and make with the speed of about 27kg/hr the styrene-acrylonitrile based copolymer (A2-1) that melt flow index is 1.8.
In addition, the weight-average molecular weight of Comparative examples A 2-1 is 14.7 ten thousand, the content of oligopolymer (Oligomer) be 7700ppm and softening temperature is 110 DEG C.
< Comparative examples A 2-2>
With the speed of 27kg/hr by α-methylstyrenemonomer 32wt%, styrene monomer 34wt%, the raw material of acrylonitrile monemer 34wt% is mixed, again by ethylbenzene 3.0kg/hr, 520ppm Diisopropyl azodicarboxylate (AIBN), uncle 1000ppm-lauryl mercaptan (TDM), and the Ethylene recov that the fugitive constituent that removes of aftermentioned reaction is formed after condensation merges as feeding feeding, 130 DEG C are remained on and the continous way still type reactive tank with agitator of volume 40 liters to be fed into interior temperature, and make the ethylbenzene ratio in reaction solution remain on 16%, and percent polymerization remains on 55%, and (amount of monomer in groove is 45%, the amount of polymkeric substance is 55%).
After reaction solution is by devolatilizer removing fugitive constituent, the particle (pellet) of styrene-α-methylstyrene-acrylic copolymer can be obtained.Wherein, the α-methylstyrenemonomer unit containing 36wt% in the particle of styrene-α-methylstyrene-acrylic copolymer, the styrenic monomer units of 36wt% and the acrylonitrile monomer unit of 28.0wt%.On the other hand, the volatilization composition removed is condensing as Ethylene recov using condenser, and mixes with aforementioned base materials mixed solution continuously and re-use it; This method adjusts speed of response by the amount of Diisopropyl azodicarboxylate (AIBN), or the amount of adjustment uncle-lauryl mercaptan (TDM), and make with the speed of about 27kg/hr the comparative example that melt flow index is the styrene-α-methylstyrene-acrylic copolymer (A2-2) of 1.8.
In addition, the weight-average molecular weight of Comparative examples A 2-2 is 10.5 ten thousand, the weight molecular weight polymkeric substance that is less than 50,000 accounts for 26wt%, the content of oligopolymer (Oligomer) be 14000ppm and softening temperature is 114.1 DEG C.Sulphur content is 8ppm.Be 6.1% at the thermogravimetric weight loss of 300 DEG C.
< synthesis example B1>
First, 1,3-butadiene 95.0 weight part, vinyl cyanide 5.0 weight part, Potassium Persulphate 1% solution 15.0 weight part, potassium oleate 2 weight part, distilled water 140.0 weight part, uncle-lauryl mercaptan 0.2 weight part is prepared.
According to reaction 12 hours of filling a prescription above under 65 DEG C of temperature of reaction, obtain that transformation efficiency is 94%, solids content is about 36%, synthetic rubber latex that weight average particle diameter is 0.1 μm.
In addition, with the polymer coagulant of following ingredients manufacture containing carboxylic acid group:
Ethyl propenoate 85 weight part, vinylformic acid 15 weight part, uncle-lauryl mercaptan 0.3 weight part, potassium oleate 2.0 weight part, dioctyl sodium sulphosuccinate 1.0 weight part, cumine hydroperoxide 0.4 weight part, sodium formaldehyde sulphoxylate 0.3 weight part, distilled water 200 weight part.
According to reaction 5 hours of fill a prescription above under 75 DEG C of temperature of reaction, obtain the polymer coagulant containing carboxylic acid group of transformation efficiency 95%, pH value 6.0.
Then, utilize the polymer coagulant (dry weight) containing carboxylic acid group of 3 weight parts to carry out the synthetic rubber latex (dry weight) of loose 100 weight parts, the pH value of the enlarged rubber emulsion obtained is 8.5, and weight average particle diameter is 0.30 μm.
Finally, then with enlarged rubber emulsion graft polymerization reaction is carried out, to manufacture rubber particles of the present invention (B) according to following formula:
Enlarged rubber latax heavy (dry weight) 100.0 weight part, vinylbenzene 25.0 weight part, vinyl cyanide 8.3 weight part, potassium oleate 1.2 weight part, uncle-lauryl mercaptan 0.2 weight part, cumine hydroperoxide 0.5 weight part, copperas solution (0.2wt%) 3.0 weight part, formaldehyde sodium sulfoxylate solution (10wt%) 3.0 weight part, ethylene dinitrilotetra-acetic acid solution (0.25wt%) 20.0 weight part, distilled water 200.0 weight part.
Added in reactive system in 5 hours with continuous addition manner by styrene/acrylonitrile in above-mentioned formula and be polymerized, obtained grafting rubbers emulsion is with calcium chloride (CaCl 2) condensation, after dehydration, then be dried to moisture content less than 2%, just can obtain the rubber particles (B) wanted required for the present invention.Tetrahydrofuran (THF) is utilized to dissolve < synthesis example B1> and after filtering, methyl alcohol is added in filtrate, rubber particles (B) is made to separate out and filter, the styrene-acrylonitrile based copolymer (A2) that obtained < synthesis example B1> comprises 7wt% can be calculated, and the rubber particles of 93wt% (B), the weight average particle diameter of its rubber particles is 0.30 μm.Wherein, styrene-acrylonitrile based copolymer (A2), the styrenic monomer units containing 65 ~ 76wt% and the acrylonitrile monomer unit of 24 ~ 35wt%.
< Embodiment C 1-1>
Styrene-α-methylstyrene-acrylic copolymer (A1) 76wt% obtained by < embodiment A 1-1 > is mixed with by < synthesis example B1 > 24wt%, add the lubrication prescription of 0.7 weight part, and 0.3 weight part comprise the mixture of phenol system antioxidant and phosphorous antioxidant, and give melting mixing extrusion granulator with the forcing machine (Werner & Pfleiderer ZSK35) with ventage.The rubber-modified styrene resin composition (C1-1) of rubber particles (B) content 22 weight ratio can be obtained.
Then, with the emission forming machine of Zhen Xiong company factory number SM-90 after 220 DEG C of injection test pieces, the products formed of rubber modified styrene series resin can be obtained, it analyzes transitivity evaluation result in table two, the melt flow index (MI) of Embodiment C 1-1 is 7.9g/10min, izod impact strength (IZOD) for 22Kg cm/cm and softening temperature be 113 DEG C.
< Embodiment C 1-2>
Styrene-α-methylstyrene-acrylic copolymer (A1) 76wt% obtained by < embodiment A 1-2 > is mixed with by < synthesis example B1 > 24wt%, add the lubrication prescription of 0.7 weight part, and 0.3 weight part comprise the mixture of phenol system antioxidant and phosphorous antioxidant, and give melting mixing extrusion granulator with the forcing machine (Werner & Pfleiderer ZSK35) with ventage.The rubber-modified styrene resin composition (C1-2) of rubber particles (B) content 22 weight percent can be obtained.
Then, with the emission forming machine of Zhen Xiong company factory number SM-90 after 220 DEG C of injection test pieces, the products formed of rubber modified styrene series resin can be obtained, it analyzes transitivity evaluation result in table two, the melt flow index (MI) of Embodiment C 1-2 is 7.9g/10min, izod impact strength (IZOD) for 22.1Kg cm/cm and softening temperature be 113.8 DEG C.
< Embodiment C 1-3>
Styrene-α-methylstyrene-acrylic copolymer (A1) 76wt% obtained by < embodiment A 1-3 > is mixed with by < synthesis example B1 > 24wt%, add the lubrication prescription of 0.7 weight part, and 0.3 weight part comprise the mixture of phenol system antioxidant and phosphorous antioxidant, and give melting mixing extrusion granulator with the forcing machine (Werner & Pfleiderer ZSK35) with ventage.The rubber-modified styrene resin composition (C1-3) of rubber particles (B) content 22 weight percent can be obtained.
Then, with the emission forming machine of Zhen Xiong company factory number SM-90 after 220 DEG C of injection test pieces, the products formed of rubber modified styrene series resin can be obtained, it analyzes transitivity evaluation result in table two, the melt flow index (MI) of Embodiment C 1-3 is 6.5g/10min, izod impact strength (IZOD) for 22.9Kg cm/cm and softening temperature be 113.5 DEG C.
< Embodiment C 1-4>
Styrene-α-methylstyrene-acrylic copolymer (A1) 76wt% obtained by < embodiment A 1-4 > is mixed with by < synthesis example B > 24wt%, add the lubrication prescription of 0.7 weight part, and 0.3 weight part comprise the mixture of phenol system antioxidant and phosphorous antioxidant, and give melting mixing extrusion granulator with the forcing machine (Werner & Pfleiderer ZSK35) with ventage.The rubber-modified styrene resin composition (C1-4) of rubber particles (B) content 22 weight percent can be obtained.
Then, with the emission forming machine of Zhen Xiong company factory number SM-90 after 220 DEG C of injection test pieces, the products formed of rubber modified styrene series resin can be obtained, it analyzes transitivity evaluation result in table two, the melt flow index (MI) of Embodiment C 1-4 is 6.8g/10min, izod impact strength (IZOD) for 24Kg cm/cm and softening temperature be 114 DEG C.
< comparative example z1-1>
The styrene-acrylonitrile copolymer 76wt% obtained by < Comparative examples A 2-1 > is mixed with by < synthesis example B1 > 24wt%, add the lubrication prescription of 0.7 weight part, and 0.3 weight part comprise the mixture of phenol system antioxidant and phosphorous antioxidant, and give melting mixing extrusion granulator with the forcing machine (Werner & PfleidererZSK35) with ventage.The comparative example of the rubber-modified styrene resin composition (z1-1) of rubber particles (B) content 22 weight ratio can be obtained.
Then, with the emission forming machine of Zhen Xiong company factory number SM-90 after 220 DEG C of injection test pieces, the products formed of rubber modified styrene series resin can be obtained, it analyzes transitivity evaluation result in table two, the melt flow index (MI) of comparative example z1-1 is 5.7g/10min, izod impact strength (IZOD) for 28Kg cm/cm and softening temperature be 110 DEG C.
< comparative example z1-2>
Styrene-α-methylstyrene-acrylic copolymer the 76wt% obtained by < Comparative examples A 2-2 > is mixed with by < synthesis example B1 > 24wt%, add the lubrication prescription of 0.7 weight part, and 0.3 weight part comprise the mixture of phenol system antioxidant and phosphorous antioxidant, and with the forcing machine (Werner & Pfleiderer ZSK35) with ventage) give melting mixing extrusion granulator.The comparative example of the rubber-modified styrene resin composition (z1-2) of rubber particles (B) content 22 weight ratio can be obtained.
Then, with the emission forming machine of Zhen Xiong company factory number SM-90 after 220 DEG C of injection test pieces, the products formed of rubber modified styrene series resin can be obtained, it analyzes transitivity evaluation result in table two, the melt flow index (MI) of comparative example z1-2 is 7.7g/10min, izod impact strength (IZOD) for 21.7Kg cm/cm and softening temperature be 114 DEG C.
Due in < synthesis example B1 >, the styrene-acrylonitrile based copolymer (A2) of generating portion accounts for the 7wt% of < synthesis example B1 > (namely rubber particles (B) accounts for 93% of < synthesis example B1 >).Wherein, the styrenic monomer unit of styrene-acrylonitrile based copolymer (A2) containing 75wt% and the acrylic monomeric unit of 25wt%.In other words, when the embodiment A 1-1 to A1-4 of 76wt% distinctly mixes with the synthesis example B1 of 24wt% and forms Embodiment C 1-1 to C1-4 respectively, 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-α-methylstyrene-acrylic copolymer of the present invention and the comparison sheet of Comparative examples A 2-1 to A2-2.Wherein, charging (Feed) composition represents the composition weight ratio before primarily of the first monomer component reaction of acrylonitrile monemer, styrene monomer, α-methylstyrenemonomer composition; Particle (Pellet) forms the composition weight ratio that expression first monomer component forms the acrylonitrile monomer unit of particle, styrenic monomer units, α-methylstyrenemonomer unit after polyreaction; A α S physical property represents the physical property of each embodiment or each comparative example; AN/SM/ α MS represents acrylic monomeric unit/styrenic monomer unit/vinyl toluene system monomeric unit shared wt% out of the ordinary; EB represents that the ethylbenzene ratio in reaction solution keeps ratio; Mw represents the molecular-weight average of each embodiment or each comparative example; Mw<5 ten thousand represents the per-cent that each embodiment or each comparative example middle-molecular-weihydroxyethyl are less than 50,000; Oligopolymer represents the dipolymer and trimeric content that are made up of styrene monomer, α-methylstyrenemonomer or acrylonitrile monemer; SP represents softening point temperature; Sulphur content represents that in each embodiment or each comparative example, sulphur content represents with ppm; And TGA represents thermogravimetric weight loss, i.e. the percent weight loss of 300 DEG C of constant temperature, 30 minutes lower samples under a 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/physical property represents the composition/physical property of each embodiment and each comparative example; BP (B) refers to the ratio that < synthesis example B1> uses; MI represents melt flow index; And IZOD izod impact strength.
Table one
Table two
Compared with Comparative examples A 2-1 to A2-2 from embodiment A 1-1 to A1-4, styrene-α-methylstyrene-acrylic copolymer of the present invention has less α-methylstyrenemonomer unit composition (17.5% or 22.5%), but its softening point temperature can with to have more α-methylstyrenemonomer unit composition (36%) close.In addition, the sulphur content of styrene-α-methylstyrene-acrylic copolymer of the present invention is 50 ~ 300ppm, be preferably 110 ~ 250ppm, the heat resisting temperature (300 DEG C of thermogravimetric weight loss are 3.6% ~ 5.1%, lower than comparative example) that styrene-α-methylstyrene-acrylic copolymer can be made to reach higher.In addition, according to the result measured by embodiment A 1-1 to A1-4, if temperature of reaction 130 DEG C is reduced to 120 DEG C, 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, usually need to improve α-methylstyrenemonomer unit usage quantity, common usage quantity is approximately the ratio of the α-methylstyrenemonomer unit being greater than 60wt%.From comparative example z1-1 and z1-2, the softening point temperature not adding α-methylstyrenemonomer unit is 110 DEG C, and the softening point temperature adding the α-methylstyrenemonomer unit of 36wt% is 114 DEG C, but it reaches 6.1% at the thermogravimetric weight loss of 300 DEG C.
In other words, if according to the argument of general prior art, if reduce the ratio of α-methylstyrenemonomer unit, softening temperature should be able to be made to decline.But, styrene-α-methylstyrene-acrylic copolymer of the present invention prepared by embodiment A 1-1 ~ A1-4, although the ratio of α-methylstyrenemonomer unit only has 22.5wt% and 17.5wt% respectively, its softening point temperature is between 113.3 to 114 DEG C.Moreover this phenomenon also betides in the embodiment of C1-1 ~ C1-4.As can be seen here, styrene-α-methylstyrene-acrylic copolymer of the present invention and rubber modified styrene series resin decrease the consumption of α-methylstyrenemonomer unit, and its softening temperature is close or the same softening temperature equaling the thermoplastic resin of higher dosage α-methylstyrenemonomer unit.In other words, real possess can not expected effect for styrene-α-methylstyrene-acrylic copolymer of the present invention and rubber modified styrene series resin.
Infer the consumption owing to reducing α-methylstyrenemonomer in the first monomer component, the content of oligopolymer (Oligomer) is declined, and then contributes to the rising of softening temperature.Wherein, oligopolymer described herein represents the dipolymer and trimer that are made up of styrene monomer, α-methylstyrenemonomer or acrylonitrile monemer.
Continue, embodiment A 1-1 and A1-2 compares, and its difference is the difference of temperature of reaction, and wherein, the temperature of reaction of embodiment A 1-1 is 130 DEG C; The temperature of reaction of embodiment A 1-2 is 120 DEG C.Compared from 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 A1-4, in addition, because Embodiment C 1-1 to C1-4 is made up 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 of the softening temperature rising because of the decline of temperature of reaction.
The foregoing is only illustrative, but not be restrictive.Anyly do not depart from spirit of the present invention and category, and to its equivalent modifications of carrying out or change, all should be contained in appended claims.

Claims (10)

1. styrene-α-methylstyrene-acrylic copolymer, primarily of
The styrenic monomer units of 48 ~ 60wt%;
The α-methylstyrenemonomer unit of 15 ~ 27wt%; And
The acrylic monomeric unit composition of 25 ~ 32wt%,
The dipolymer be wherein made up of styrene monomer, α-methylstyrenemonomer or acrylic monomer and trimeric content are less than 8500ppm.
2. styrene-α-methylstyrene-acrylic copolymer as claimed in claim 1, wherein acrylic monomeric unit is vinyl cyanide or Alpha-Methyl vinyl cyanide.
3. styrene-α-methylstyrene-acrylic copolymer as claimed in claim 1, the sulphur content wherein in styrene-α-methylstyrene-acrylic copolymer is 50 ~ 300ppm.
4. styrene-α-methylstyrene-acrylic copolymer, primarily of
The styrenic monomer units of 48 ~ 60wt%;
The α-methylstyrenemonomer unit of 15 ~ 27wt%; And
The acrylic monomeric unit composition of 25 ~ 32wt%,
Wherein the weight-average molecular weight of styrene-α-methylstyrene-acrylic copolymer is less than 25% lower than the quantity of the molecule of 50,000.
5. styrene-α-methylstyrene-acrylic copolymer as claimed in claim 4, wherein acrylic monomeric unit is vinyl cyanide or Alpha-Methyl vinyl cyanide.
6. styrene-α-methylstyrene-acrylic copolymer as claimed in claim 4, the sulphur content wherein in styrene-α-methylstyrene-acrylic copolymer is 50 ~ 300ppm.
7. a rubber modified styrene series resin, comprises:
Styrene-α-methylstyrene-the acrylic copolymer of 75 ~ 80wt%, styrene-α-methylstyrene-acrylic copolymer forms primarily of the acrylic monomeric unit of the styrenic monomer units of 48 ~ 60wt%, the α-methylstyrenemonomer unit of 15 ~ 27wt% and 25 ~ 32wt%, and the dipolymer be wherein made up of styrene monomer, α-methylstyrenemonomer or acrylic monomer and trimeric content are less than 8500ppm;
0 ~ 5wt% styrene-acrylonitrile based copolymer, the acrylic monomeric unit of the styrenic monomer unit containing 65 ~ 76wt% and 24 ~ 35wt%, wherein styrene-α-methylstyrene-acrylic copolymer and styrene-acrylonitrile based copolymer form continuous matrix phase; And
The rubber particles of 20 ~ 25wt%, wherein rubber particles is disperse phase, and be dispersed in continuous matrix mutually in.
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 μm.
10. rubber modified styrene series resin as claimed in claim 7, wherein acrylic monomeric unit is vinyl cyanide or Alpha-Methyl vinyl cyanide.
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GB1247322A (en) * 1969-02-05 1971-09-22 Hoechst Ag Copolymers and a process for their preparation
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