CN102898734A - Polystyrene resin composition and preparation method thereof - Google Patents
Polystyrene resin composition and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a polystyrene resin composition, which mainly comprises, by weight: 1) 100% of polystyrene; 2) 10-30% of carboxylic styrene butadiene latex modified powder styrene-butadiene rubber; 3) 0.5-1.5% of a peroxide; 4) 0.2-0.5% of a co-cross-linking agent; and 5) 5-10% of a polar monomer grafted polystyrene, wherein the peroxide is a compound comprising an organic peroxide A having a half life of less than 170 DEG C/1 min and an organic peroxide B having a half life of more than 200 DEG C/1 min according to a ratio of 1:5-1:30, and the co-cross-linking agent is one selected from N,N'-p-phenyl dimaleimide (PDM or HVA-2), zinc diacrylate (ZDA), zinc methacrylate, zinc dimethacrylate (ZDMA), trihydroxymethylpropyl trimethylacrylate (TMPTA) or zinc oxide (ZnO). According to the present invention, the composition of the present invention has an excellent comprehensive mechanical property; toughness of the composition is improved by more than 10 times compared with the polystyrene base resin, and strength of the material is maintained or improved maximally so as to expand applications of the polystyrene in automotive, construction, medical equipment, cables, packaging, household electric appliances and other fields. The present invention further discloses a preparation method for the composition.
Description
Technical field
The present invention relates to polystyrene resin composite and preparation method thereof, be specifically related to powder styrene butadiene rubber through polystyrene resin composite of dynamic vulcanization toughening modifying and preparation method thereof.
Background technology
Polystyrene (PS) is that output and consumption are only second to polyethylene, polyvinyl chloride and polyacrylic large resins for universal use, has a wide range of applications in every profession and trade.But the property of PS is crisp, shock strength is low, environmental stress crack resistance and poor heat resistance, so that PS only uses as common plastics.Release anti-impact PS to common people first from DOW company in 1948, the toughening modifying of PS just becomes the important topic of polymer material science research, and people have carried out large quantity research to this.
Toughness reinforcing elastic body toughening and the Rigid Particles Toughened dual mode of adopting of PS.Elastic body toughening refers to mix the method for various thermoplastic elastic bodies in PS, because technique is easy to realize being reported in a large number.Toughening mechanism mainly contains shear zone and crazing Coexistence Theory, cavitation theory etc.Rubber or elastomerics as toughness reinforcing component comprise styrene-butadiene rubber(SBR) (SBR), styrene-butadiene-styrene block copolymer (SBS), cis-1,4-polybutadiene rubber, polybutadiene rubber (PBR), polyisobutene (PIB), and Patents comprises ZL00124687.9, ZL200310121945.0, JP3230754, JP0104111, CN200810226625.4 etc.Although obtaining obvious effect aspect the enhancing touthness of polyphenylethylene by adding with these elastomericss, toughening effect is still limited.
1962, since U.S. A.M.Gessler at first proposed to prepare rubber plastic blend (US3037954) with dynamic vulcanization process, dynamic vulcanization technology was widely used in (as: US4130535, US4594390, ZL200510025249 etc.) in rubber or the elastomeric toughened system.Powdered rubber refers to that particle diameter less than the rubber of 1.0mm, has good dispersiveness, can with the direct blend of resin, have in the resin modified field widely and use.ZL01110736.6 discloses a kind of full sulfuration PS thermoplastic elastomer and preparation method thereof, with the method for common rubber plastic blend particle diameter is not more than the powdered rubber with crosslinking structure and the PS blend of 1 μ m, makes the full sulfuration PS thermoplastic elastomer of satisfactory mechanical property.ZL01110736.7 provides a kind of toughness reinforcing PS that is obtained through melt blending by PS and toughness reinforcing component and preparation method thereof, wherein toughness reinforcing component is to have the powdered rubber that crosslinking structure and median size are not more than 0.5 μ m, or mixed by this kind powdered rubber and at least a unvulcanized thermoplastic elastic body and to form, PS pellet+form of finely divided powder, mehtod butylbenzene+SIS is disclosed among the embodiment, PS pellet+cross-linked powdery butylbenzene+SBS, the composition system of PS pellet+cross-linked powdery butylbenzene.The employing sulphur such as Wang Tong are the twin screw Technology of Dynamic Vulcanized of vulcanizing agent, utilize powder styrene butadiene rubber (PSBR) modification general purpose polystyrene (GPPS) to prepare GPPS/PSBR blend (China Synthetic Rubber Industry, 2 phases of 32 volumes in 2009,148～151 pages).
Summary of the invention
The object of the invention provides a kind of polystyrene resin composite.This polystyrene resin composite has excellent shock resistance and comprehensive mechanical property.The present invention further proposes the preparation method of said composition.
Particularly, by weight percentage, resin combination of the present invention mainly comprises: 1) 100% polystyrene; 2) 10%～30% carboxylic styrene butadiene latex modified powder styrene-butadiene rubber(SBR); 3) 0.5%～1.5% superoxide; 4) 0.2%～0.5% additional crosslinker; 5) 5%～10% polar monomer graft polystyrene.
Wherein, the superoxide compound that to be the transformation period form in 1: 5～1: 30 ratio greater than the organo-peroxide B of 200 ℃/1min less than the organo-peroxide A of 170 ℃/1min and transformation period.Particularly, superoxide A was selected from wherein a kind of such as the special butyl ester of the sad tert-butyl ester, t-butyl peroxy-acetate (TBPA), peracetic acid, the peroxidation trimethylacetic acid tert-butyl ester (TBPV), peroxidized t-butyl perbenzoate (TBPB), di-t-butyl peroxy valerate, dibenzoyl peroxide (BPO), preferably adopted peroxidized t-butyl perbenzoate (TBPB); Superoxide B is selected from 1, wherein a kind of such as 1-dimethyl ethyl-hydrogen peroxide (TB), tertbutyl peroxide (TBHP), di-tert-butyl hydrogen peroxide, tertiary amyl hydrogen oxide (TAHP) preferably adopts tertbutyl peroxide (TBHP).Organo-peroxide is the commercially available prod, and its half life temperature is because of manufacturer's difference difference slightly, such as preferred TBPB transformation period T=163～167 ℃/1min; The transformation period T=261 of TBHP～267 ℃/1min.
Additional crosslinker is N, N '-to phenyl-bismaleimide (PDM or HVA-2), dizinc acrylate resin (ZDA), zinc methacrylate, zinc dimethacrylate (ZDMA), trimethyol propane triacrylate (TMPTA), (ZnO) is one kind of for zinc oxide, preferred TMPTA.
Polystyrene described in the composition is the multipolymer of cinnamic homopolymer (GPPS) or vinylbenzene and polybutadiene rubber, can be powdery or granular resin, melt flow rate (MFR) (MFR) 0.5～35g/10min.
Modified powder styrene-butadiene rubber(SBR) described in the composition is the powder styrene butadiene rubber with the carboxylic styrene butadiene latex modification.Rubber size 0.15～the 0.65mm of powder styrene butadiene rubber (PSBR), 100 ℃ of mooney viscosity ML (1+4) are 40～120.
Carboxylic styrene butadiene latex is take divinyl, vinylbenzene as main monomer, and unsaturated carboxylic acid is that function monomer obtains through letex polymerization, and unsaturated carboxylic acid wherein is vinylformic acid, methacrylic acid or 2-ethylacrylic acid, preferred vinylformic acid.The solids content 40～55% of carboxylic styrene butadiene latex, latex particle size 100～170nm.
Grafted polystyrene be under the effect of initiator with the grafts of polar monomer graft to the polystyrene, initiator is selected from a kind of in Potassium Persulphate, dicumyl peroxide, hydrogen phosphide cumene, dibenzoyl peroxide and the ditertiary butyl peroxide, preferred dicumyl peroxide (DCP).Polar monomer is selected from least a in maleic anhydride, vinylformic acid, methacrylic acid, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate or the Tert-butyl Methacrylate, preferable methyl vinylformic acid.The percentage of grafting 0.9～7% of grafted polystyrene.
In the preparation process of composition of the present invention, also need to add the auxiliary agents such as separant, oxidation inhibitor, stablizer, dispersion agent in specific step, the adding of auxiliary agent is only for satisfying the requirement of stable processing, and performance that can the p-poly-phenyl vinyl composition exerts an influence.
The preparation of composition of the present invention can be carried out in Banbury mixer, kneader, twin screw extruder, and the present invention does not do special restriction, 170～200 ℃ of temperature of reaction, reaction times 3～5min.Preferred twin screw extruder, when selecting twin screw extruder to prepare, the preparation technology that can adopt raw material to be pre-mixed, to extrude again.Concrete, the preparation of composition comprises the steps:
(1) preparation of modified powder styrene-butadiene rubber(SBR)
Be that 1: 2～1: 5 water and carboxylic styrene butadiene latex mix with weight ratio; Be warming up to 50～60 ℃ under the whipped state, add 2～5% separants (pressing the weight percent meter of carboxylic styrene butadiene latex) and mix 1～10min; Add powder styrene butadiene rubber again and mix 30～60min, powder styrene butadiene rubber and carboxylic styrene butadiene latex weight ratio are 30: 1～5: 1; Obtain modified powder styrene-butadiene rubber(SBR) by discharging, dehydration, drying;
(2) preparation of grafted polystyrene
The polystyrene weight of using take grafting is as absolutely, and the initiator with 0.1～1.5% mixes with acetone, and the weight ratio of acetone and initiator is 2: 1～7: 1; Mix 3～5min with polystyrene, 3～15% polar monomer again; Mixed material is added twin screw extruder, 170～190 ℃ of temperature of reaction, reaction times 6～12min extrudes, cooling, granulation, obtains the polystyrene graft thing.
(3) preparation of polyphenylacetylene combination
Pressing the weight percent meter of polystyrene, is that 4: 1～2: 1 carboxylic styrene butadiene latex and organo-peroxide mix 5～10min with weight ratio, with additional crosslinker, modified powder styrene-butadiene rubber(SBR) high-speed mixing 5～10min, makes the premix masterbatch again; With premix masterbatch, polystyrene, grafted polystyrene and 0.3～0.9% dispersion agent, 0.14%～0.26% stablizer, 0.1%～0.2% oxidation inhibitor together high-speed mixing 5～10min; Mixed material is added twin screw extruder, 170～200 ℃ of temperature of reaction, reaction times 3～5min extrudes, cooling, granulation, obtains polystyrene resin composite of the present invention.
Wherein, oxidation inhibitor is one or several compounds in phenols, hindered amines, the phosphite ester kind antioxidant.Stablizer is stearates, a kind of as in Zinic stearas or the calcium stearate.Dispersion agent is selected from whiteruss or white oil, preferred white oil.The compound that separant is comprised of fatty acid soaps compounds and stearate compounds and silicon compound.
In the composition of the present invention, at first select active low and active two kinds of high superoxide, can effectively control the powder styrene butadiene rubber vulcanization rate, has good anti-incipient scorch, reach easily best cross-linking density, form stable C-C bond structure, can improve significantly the comprehensive mechanical property such as shock strength, tensile strength, flexural strength of blend system.Avoid using that a kind of superoxide brings is excessive crosslinked or consumption is excessive, be unfavorable for the problems such as safety, environmental protection, reduction cost.Secondly, add modified powder fourth rubber and polarity graftomer, can obviously improve the dispersion state of powder styrene butadiene rubber in the polystyrene matrix.Simultaneously, homodisperse rubber particles is after dynamic vulcanization is crosslinked in the screw mixes extrusion, avoid " reunion " again occurring because bumping, realized that powdered rubber is stable with tiny particle form, be evenly dispersed in the polystyrene substrate, thereby obtain the good polystyrene resin composite of comprehensive mechanical property, composition improves more than 10 times than the basic resin toughness of polystyrene, and the strength of materials is kept to greatest extent or is improved, and has expanded polystyrene at automobile, building, medicine equipment, cable, the application in the fields such as packing and household electrical appliance.
Embodiment
(1) raw material
(2) performance test standard
(3) equipment and instrument
Embodiment and Comparative Examples
Enumerate following examples effect of the present invention is described, but protection scope of the present invention is not limited in these embodiment.
Embodiment 1
(1) preparation of modified powder styrene-butadiene rubber(SBR): 0.01kg water and 0.02kg carboxylic styrene butadiene latex are joined in the cohesion still of 15L, pass into low-pressure steam, slurries are warming up to 55 ℃ mix 3min; Add 1g separant mixing 3min, again 0.2kg powder styrene butadiene rubber 1500a mixing 40min; Discharging, dehydration at 50 ℃ of lower dry 24hr, obtain modified powder styrene-butadiene rubber(SBR).
(2) preparation of grafted polystyrene: 20g acetone and 4g DCP are put into beaker mix, again the liquid and 1kg polystyrene (666D), the 60g methacrylic acid (MAA) that mix are put into 10L high-speed mixer, high-speed mixing 4min together, the material that mixes is joined in Φ 34 twin screw extruders, the screw zones temperature of reaction (℃) be followed successively by: 170,175,180,185,190,190,185,180,170; After carrying out extrusion reaction 9min, extrude, cooling, granulation, obtain PS-g-MAA grafts a (percentage of grafting is 2.9%).
(3) preparation of highly anti-flush polyphenylacetylene composition: first 0.0005kg TBPB and 0.01kg TBHP are put into beaker and mix, add again 0.03kg carboxylic styrene butadiene latex mixing 5min, then solution and 0.2kg modified powder styrene-butadiene rubber(SBR) 1500a, the 0.004kg TMPTA that mixes put into 10L high-speed mixer high speed mixing 5min together, make the premix masterbatch; With premix masterbatch and polystyrene (666D) 2kg, PS-g-MAA grafts a 0.1kg, the antioxidant 1010 of white oil 32#10g, 3g, the Zinic stearas of 4g, put into together 10L high-speed mixer high speed and mix 5min again; At last the material that mixes is joined in Ф 34 twin screw extruders, the screw zones temperature of reaction (℃) be followed successively by: 170,175,180,185,190,200,195,185,175; After carrying out extrusion reaction 4min, extrude, cooling, granulation, make highly anti-flush polyphenylacetylene composition.The composition pellet of preparation is made standard test specimen with injecting method and is tested, and its performance sees Table 1.
Embodiment 2
(1) preparation of modified powder styrene-butadiene rubber(SBR): 0.01kg water and 0.03kg carboxylic styrene butadiene latex are joined in the cohesion still of 15L, pass into low-pressure steam, slurries are warming up to 55 ℃ mix 3min; Add 1.5g separant mixing 3min, again 0.25kg powder styrene butadiene rubber 1500a mixing 40min; Discharging, dehydration at 50 ℃ of lower dry 24hr, obtain modified powder styrene-butadiene rubber(SBR).
(2) preparation of grafted polystyrene: with embodiment 1
(3) preparation of highly anti-flush polyphenylacetylene composition: first 0.0007kg TBPB and 0.018kg TBHP are put into beaker and mix, add again 0.03kg carboxylic styrene butadiene latex mixing 5min, then solution and 0.25kg modified powder styrene-butadiene rubber(SBR) 1500a, the 0.005kg TMPTA that mixes put into high-speed mixer high speed mixing 5min together, make the premix masterbatch; With premix masterbatch and polystyrene (666D) 2kg, PS-g-MAA grafts a 0.12kg, the antioxidant 1010 of white oil 32#10g, 3g, the Zinic stearas of 4g, put into together 10L high-speed mixer high speed and mix 5min again; At last the material that mixes is joined in Ф 34 twin screw extruders, the screw zones temperature of reaction (℃) be followed successively by: 170,175,180,185,190,200,195,185,175; After carrying out extrusion reaction 4min, extrude, cooling, granulation, make highly anti-flush polyphenylacetylene composition.The composition pellet of preparation is made standard test specimen with injecting method and is tested, and its performance sees Table 1.
Embodiment 3
(1) preparation of modified powder styrene-butadiene rubber(SBR): 0.01kg water and 0.04kg carboxylic styrene butadiene latex are joined in the cohesion still of 15L, pass into low-pressure steam, slurries are warming up to 55 ℃ mix 3min; Add 1.8g separant mixing 3min, again 0.3kg powder styrene butadiene rubber 1500a mixing 40min; Discharging, dehydration at 50 ℃ of lower dry 24hr, obtain modified powder styrene-butadiene rubber(SBR).
(2) preparation of grafted polystyrene: with embodiment 1
(3) preparation of highly anti-flush polyphenylacetylene composition: first 0.0009kg TBPB and 0.016kg TBHP are put into beaker and mix, add again 0.03kg carboxylic styrene butadiene latex mixing 5min, then solution and 0.3kg modified powder styrene-butadiene rubber(SBR) 1500a, the 0.006kg TMPTA that mixes put into high-speed mixer high speed mixing 5min together, make the premix masterbatch; With premix masterbatch and polystyrene (666D) 2kg, PS-g-MAA grafts a 0.13kg, the antioxidant 1010 of white oil 32#10g, 4g, the Zinic stearas of 5g, put into together 10L high-speed mixer high speed and mix 5min again; At last the material that mixes is joined in Ф 34 twin screw extruders, the screw zones temperature of reaction (℃) be followed successively by: 170,175,180,185,190,200,195,185,175; After carrying out extrusion reaction 4min, extrude, cooling, granulation, make highly anti-flush polyphenylacetylene composition.The composition pellet of preparation is made standard test specimen with injecting method and is tested, and its performance sees Table 1.
Embodiment 4
(1) preparation of modified powder styrene-butadiene rubber(SBR): 0.01kg water and 0.05kg carboxylic styrene butadiene latex are joined in the cohesion still of 15L, pass into low-pressure steam, slurries are warming up to 55 ℃ mix 3min; Add 1.1g separant mixing 3min, again 0.32kg powder styrene butadiene rubber 1712a mixing 40min; Discharging, dehydration at 50 ℃ of lower dry 24hr, obtain modified powder styrene-butadiene rubber(SBR).
(2) preparation of grafted polystyrene: with embodiment 1
(4) preparation of highly anti-flush polyphenylacetylene composition: first 0.001kg TBPB and 0.009kg TBHP are put into beaker and mix, add again 0.03kg carboxylic styrene butadiene latex mixing 5min, then solution and 0.32kg modified powder styrene-butadiene rubber(SBR) 1712a, the 0.004kg TMPTA that mixes put into 10L high-speed mixer high speed mixing 5min together, make the premix masterbatch; With premix masterbatch and polystyrene (666D) 2kg, PS-g-MAA grafts a 0.14kg, the antioxidant 1010 of white oil 32#10g, 3g, the Zinic stearas of 4g, put into together 10L high-speed mixer high speed and mix 5min again; At last the material that mixes is joined in Ф 34 twin screw extruders, the screw zones temperature of reaction (℃) be followed successively by: 170,175,180,185,190,200,195,185,175; After carrying out extrusion reaction 4min, extrude, cooling, granulation, make highly anti-flush polyphenylacetylene composition.The composition pellet of preparation is made standard test specimen with injecting method and is tested, and its performance sees Table 1.
Embodiment 5
(1) preparation of modified powder styrene-butadiene rubber(SBR): 0.01kg water and 0.05kg carboxylic styrene butadiene latex are joined in the cohesion still of 15L, pass into low-pressure steam, slurries are warming up to 55 ℃ mix 3min; Add 1.3g separant mixing 3min, again 0.35kg powder styrene butadiene rubber 1712a mixing 40min; Discharging, dehydration at 50 ℃ of lower dry 24hr, obtain modified powder styrene-butadiene rubber(SBR).
(2) preparation of grafted polystyrene: with embodiment 1
(3) preparation of highly anti-flush polyphenylacetylene composition: first 0.002kg TBPA and 0.014kgTBHP are put into beaker and mix, add again 0.04kg carboxylic styrene butadiene latex mixing 5min, then solution and 0.35kg modified powder styrene-butadiene rubber(SBR) 1712a, the 0.006kg ZDA that mixes put into high-speed mixer high speed mixing 5min together, make the premix masterbatch; With premix masterbatch and polystyrene (666D) 2kg, PS-g-MAA grafts a 0.15kg, the antioxidant 1010 of white oil 32#12g, 4g, the Zinic stearas of 5g, put into together 10L high-speed mixer high speed and mix 5min again; At last the material that mixes is joined in Ф 34 twin screw extruders, the screw zones temperature of reaction (℃) be followed successively by: 170,175,180,185,190,200,195,185,175; After carrying out extrusion reaction 4min, extrude, cooling, granulation, make highly anti-flush polyphenylacetylene composition.The composition pellet of preparation is made standard test specimen with injecting method and is tested, and its performance sees Table 1.
Embodiment 6
(1) preparation of modified powder styrene-butadiene rubber(SBR): 0.01kg water and 0.06kg carboxylic styrene butadiene latex are joined in the cohesion still of 15L, pass into low-pressure steam, slurries are warming up to 55 ℃ mix 3min; Add 1.5g separant mixing 3min, again 0.4kg powder styrene butadiene rubber 1500a mixing 40min; Discharging, dehydration at 50 ℃ of lower dry 24hr, obtain modified powder styrene-butadiene rubber(SBR).
(2) preparation of grafted polystyrene: 35g acetone and 7g DCP are put into beaker mix, again the liquid and 1kg polystyrene (492J), the 90g methacrylic acid (MAA) that mix are put into 10L high-speed mixer, high-speed mixing 4min together, the material that mixes is joined in Ф 34 twin screw extruders, the screw zones temperature of reaction (℃) be followed successively by: 170,175,180,185,190,190,185,180,170; After carrying out extrusion reaction 9min, extrude, cooling, granulation, obtain PS-g-MAA grafts b (percentage of grafting is 4.2%).
(3) preparation of highly anti-flush polyphenylacetylene composition: first 0.003kg TBPB and 0.024kg TBHP are put into beaker and mix, add again 0.04kg carboxylic styrene butadiene latex mixing 5min, then solution and 0.4kg modified powder styrene-butadiene rubber(SBR) 1500a, the 0.006kg TMPTA that mixes put into high-speed mixer high speed mixing 5min together, make the premix masterbatch; With premix masterbatch and polystyrene (492J) 2kg, PS-g-MAA grafts b 0.15kg, the antioxidant 1010 of white oil 32#12g, 4g, the Zinic stearas of 5g, put into together 10L high-speed mixer high speed and mix 5min again; At last the material that mixes is joined in Ф 34 twin screw extruders, the screw zones temperature of reaction (℃) be followed successively by: 170,175,180,185,190,200,195,185,175; After carrying out extrusion reaction 4min, extrude, cooling, granulation, make highly anti-flush polyphenylacetylene composition.The composition pellet of preparation is made standard test specimen with injecting method and is tested, and its performance sees Table 1.
Embodiment 7
(1) preparation of modified powder styrene-butadiene rubber(SBR): 0.02kg water and 0.07kg carboxylic styrene butadiene latex are joined in the cohesion still of 15L, pass into low-pressure steam, slurries are warming up to 55 ℃ mix 3min; Add 1.5g separant mixing 3min, again 0.55kg powder styrene butadiene rubber 1712a mixing 40min; Discharging, dehydration at 50 ℃ of lower dry 24hr, obtain modified powder styrene-butadiene rubber(SBR).
(2) preparation of grafted polystyrene: with embodiment 6
(3) preparation of highly anti-flush polyphenylacetylene composition: first 0.004kg TBPB and 0.022kg TBHP are put into beaker and mix, add again 0.05kg carboxylic styrene butadiene latex mixing 5min, then solution and 0.55kg modified powder styrene-butadiene rubber(SBR) 1712a, the 0.008kg TMPTA that mixes put into high-speed mixer high speed mixing 5min together, make the premix masterbatch; With premix masterbatch and polystyrene (492J) 2kg, PS-g-MAA grafts b 0.17kg, the antioxidant 1010 of white oil 32#12g, 4g, the Zinic stearas of 5g, put into together 10L high-speed mixer high speed and mix 5min again; At last the material that mixes is joined in Ф 34 twin screw extruders, the screw zones temperature of reaction (℃) be followed successively by: 170,175,180,185,190,200,195,185,175; After carrying out extrusion reaction 4min, extrude, cooling, granulation, make highly anti-flush polyphenylacetylene composition.The composition pellet of preparation is made standard test specimen with injecting method and is tested, and its performance sees Table 1.
Embodiment 8
(1) preparation of modified powder styrene-butadiene rubber(SBR): with embodiment 7
(2) preparation of grafted polystyrene: with embodiment 6
(3) preparation of highly anti-flush polyphenylacetylene composition: first 0.005kg TBPB and 0.025kg TBHP are put into beaker and mix, add again 0.06kg carboxylic styrene butadiene latex mixing 5min, then solution and 0.58kg modified powder styrene-butadiene rubber(SBR) 1712a, the 0.009kg TMPTA that mixes put into high-speed mixer high speed mixing 5min together, make the premix masterbatch; With premix masterbatch and polystyrene (492J) 2kg, PS-g-MAA grafts b 0.17kg, the antioxidant 1010 of white oil 32#12g, 5g, the Zinic stearas of 5g, put into together 10L high-speed mixer high speed and mix 5min again; At last the material that mixes is joined in Ф 34 twin screw extruders, the screw zones temperature of reaction (℃) be followed successively by: 170,175,180,185,190,200,195,185,175; After carrying out extrusion reaction 4min, extrude, cooling, granulation, make highly anti-flush polyphenylacetylene composition.The composition pellet of preparation is made standard test specimen with injecting method and is tested, and its performance sees Table 1.
Comparative Examples 1
(1) preparation of modified powder styrene-butadiene rubber(SBR): with embodiment 1
(2) preparation of grafted polystyrene: with embodiment 1
(3) preparation of highly anti-flush polyphenylacetylene composition: other condition is identical with embodiment 1, and difference is not add in the composition preparation process TBPB, and the add-on of TBHP is 0.0105kg.
Comparative Examples 2
(1) preparation of modified powder styrene-butadiene rubber(SBR): with embodiment 2
(2) preparation of grafted polystyrene: with embodiment 1
(3) preparation of highly anti-flush polyphenylacetylene composition: other condition is identical with embodiment 2, and difference is not add in the composition preparation process TBHP, and the add-on of TBPB is 0.0187kg.
Comparative Examples 3
(1) preparation of modified powder styrene-butadiene rubber(SBR): with embodiment 3
(2) preparation of grafted polystyrene: with embodiment 1
(3) preparation of highly anti-flush polyphenylacetylene composition: other condition is identical with embodiment 3, and difference is not add in the composition preparation process TBPB and TBHP.
Comparative Examples 4
(1) preparation of modified powder styrene-butadiene rubber(SBR): with embodiment 4
(2) preparation of grafted polystyrene: with embodiment 1
(3) preparation of highly anti-flush polyphenylacetylene composition: other condition is identical with embodiment 4, and difference is not add in the composition preparation process TMPTA.
Comparative Examples 5
(1) preparation of grafted polystyrene: with embodiment 1
(2) preparation of highly anti-flush polyphenylacetylene composition: except the powder styrene butadiene rubber 1712a that adds unmodified processing, other component additions are identical with embodiment 5 with the preparation method.
Comparative Examples 6
(1) preparation of modified powder styrene-butadiene rubber(SBR): with embodiment 6
(2) preparation of highly anti-flush polyphenylacetylene composition: except do not add PS-g-MAA grafts b (percentage of grafting is 4.2%) in the preparation process of composition, other component additions are identical with embodiment 6 with the preparation method.
Comparative Examples 7
(1) preparation of modified powder styrene-butadiene rubber(SBR): with embodiment 7
(2) preparation of grafted polystyrene: with embodiment 6
(3) preparation of highly anti-flush polyphenylacetylene composition: difference is that the add-on of TBPB in the composition preparation process is that the add-on of 0.02, TBHP is 0.05kg, and other component additions are identical with embodiment 7 with the preparation method.
Comparative Examples 8
(1) preparation of modified powder styrene-butadiene rubber(SBR): with embodiment 7
(2) preparation of grafted polystyrene: with embodiment 6
(3) preparation of highly anti-flush polyphenylacetylene composition: difference is not add in the composition preparation process TBPB and TBHP, but adds sulphur (S), and the add-on of sulphur is 0.03kg, and other component additions are identical with embodiment 8 with the preparation method.
The physical and mechanical properties of table 1 polyphenylacetylene combination
Reference sample 1
*: commercially available Sinopec Yanshan Petrochemical company produce polystyrene (666D) from measured value.
Reference sample 2
*: commercially available Sinopec Yanshan Petrochemical company produces testing oneself of polystyrene (492J).
Claims (9)
1. polystyrene resin composite is characterized in that by weight percentage, composition mainly comprises: 1) 100% polystyrene; 2) 10%～30% carboxylic styrene butadiene latex modified powder styrene-butadiene rubber(SBR); 3) 0.5%～1.5% superoxide; 4) 0.2%～0.5% additional crosslinker; 5) 5%～10% polar monomer graft polystyrene;
Wherein, the superoxide compound that to be the transformation period form in 1: 5～1: 30 ratio greater than the organo-peroxide B of 200 ℃/1min less than the organo-peroxide A of 170 ℃/1min and transformation period;
Additional crosslinker is N, N '-one kind of to phenyl-bismaleimide, dizinc acrylate resin, zinc methacrylate, zinc dimethacrylate, trimethyol propane triacrylate or zinc oxide.
2. composition according to claim 1 is characterized in that polystyrene is cinnamic homopolymer, or the multipolymer of vinylbenzene and polybutadiene rubber, melt flow rate (MFR) 0.5～35g/10min.
3. composition according to claim 1 is characterized in that the rubber size 0.15～0.65mm of powder styrene butadiene rubber, and 100 ℃ of mooney viscosity ML (1+4) are 40～120.
4. composition according to claim 1, it is characterized in that carboxylic styrene butadiene latex is as main monomer take divinyl, vinylbenzene, unsaturated carboxylic acid is that function monomer obtains through letex polymerization, unsaturated carboxylic acid wherein is vinylformic acid, methacrylic acid or 2-ethylacrylic acid, the solids content 40～55% of carboxylic styrene butadiene latex, latex particle size 100～170nm.
5. composition according to claim 1, it is characterized in that the polar monomer graft polystyrene be under the effect of initiator with the grafts of polar monomer graft to the polystyrene, its percentage of grafting 0.9～7%.
6. composition according to claim 5 is characterized in that initiator is dicumyl peroxide, and polar monomer is methacrylic acid.
7. method for preparing one of the described composition of claim 1-6 is characterized in that the composition preparation carries out 170～200 ℃ of temperature of reaction, reaction times 3～5min in Banbury mixer, kneader or twin screw extruder.
8. the preparation method of described composition according to claim 7 is characterized in that comprising the steps:
(1) preparation of modified powder styrene-butadiene rubber(SBR)
Be that 1: 2～1: 5 water and carboxylic styrene butadiene latex mix with weight ratio; Be warming up to 50～60 ℃ under the whipped state, add 2～5% separants (pressing the weight percent meter of carboxylic styrene butadiene latex) and mix 1～10min; Add powder styrene butadiene rubber again and mix 30～60min, powder styrene butadiene rubber and carboxylic styrene butadiene latex weight ratio are 30: 1～5: 1; Obtain modified powder styrene-butadiene rubber(SBR) by discharging, dehydration, drying;
(2) preparation of grafted polystyrene
The polystyrene weight of using take grafting is as absolutely, and the initiator with 0.1～1.5% mixes with acetone, and the weight ratio of acetone and initiator is 2: 1～7: 1; Mix 3～5min with polystyrene, 3～15% polar monomer again; Mixed material is added twin screw extruder, 170～190 ℃ of temperature of reaction, reaction times 6～12min extrudes, cooling, granulation, obtains the polystyrene graft thing;
(3) preparation of polyphenylacetylene combination
Pressing the weight percent meter of polystyrene, is that 4: 1～2: 1 carboxylic styrene butadiene latex and organo-peroxide mix 5～10min with weight ratio, with additional crosslinker, modified powder styrene-butadiene rubber(SBR) high-speed mixing 5～10min, makes the premix masterbatch again; With premix masterbatch, polystyrene, grafted polystyrene and 0.3～0.9% dispersion agent, 0.14%～0.26% stablizer, 0.1%～0.2% oxidation inhibitor together high-speed mixing 5～10min; Mixed material is added twin screw extruder, 170～200 ℃ of temperature of reaction, reaction times 3～5min extrudes, cooling, granulation, obtains polystyrene resin composite of the present invention.
9. the preparation method of described composition according to claim 8 is characterized in that oxidation inhibitor is one or several compounds in phenols, hindered amines, the phosphite ester kind antioxidant; Stablizer is a kind of in Zinic stearas or the calcium stearate; Dispersion agent is whiteruss or white oil; The compound that separant is comprised of fatty acid soaps compounds, stearate compounds and silicon compound.
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| CN105294943A (en) * | 2015-12-08 | 2016-02-03 | 重庆可益荧新材料有限公司 | Regenerating method of polystyrene wastes |
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| CN111073353A (en) * | 2018-10-18 | 2020-04-28 | 中国石油天然气股份有限公司 | Preparation method of ultra-dispersed nano white carbon black used as rubber filler |
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