CN101735526B - Modified high impact resistant polystyrene composite and method for preparing same - Google Patents

Modified high impact resistant polystyrene composite and method for preparing same Download PDF

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Publication number
CN101735526B
CN101735526B CN2008102266254A CN200810226625A CN101735526B CN 101735526 B CN101735526 B CN 101735526B CN 2008102266254 A CN2008102266254 A CN 2008102266254A CN 200810226625 A CN200810226625 A CN 200810226625A CN 101735526 B CN101735526 B CN 101735526B
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styrene
impact
parts
butylbenzene
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CN101735526A (en
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郭义
巩红光
谢昕
刘永军
段宏义
杨世元
刘义
万伟林
金鼎铭
梁天珍
许惠芳
王卓妮
慕雪梅
邓守军
魏福庆
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China Petroleum and Natural Gas Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/918—Thermal treatment of the stream of extruded material, e.g. cooling characterized by differential heating or cooling
    • B29C48/9185—Thermal treatment of the stream of extruded material, e.g. cooling characterized by differential heating or cooling in the direction of the stream of the material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/04—Particle-shaped
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92895—Barrel or housing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92904—Die; Nozzle zone

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

The invention relates to a modified high impact resistant polystyrene composite and a method for preparing the same. The composite comprises styrene butadiene rubber, inorganic filling materials, impact resistant copolymer of tetraphene and high impact resistant polystyrene, wherein the structural formula of the impact resistant copolymer of tetraphene is St-(St-Bu); based on 100 percent mass of the impact copolymer of tetraphene, the St serving as a homopolymerisation section of styrene accounts for 40 to 60 percent; the St-Bu serving as random copolymerization sections of styrene and butadiene account for 40 to 60 percent, wherein the styrene unit content of the random copolymerization sections of styrene and butadiene is 6 to 28 percent, and the butadiene unit content of the random copolymerization sections of styrene and butadiene is 72 to 94 percent; and the impact copolymer of tetraphene adopts a linear structure or star-shaped structure. Compared with modified high impact polystyrene composites modified by other modifiers in the prior art, the blended modified high impact polystyrene composite has higher toughness, rigidity, low-temperature impact strength and low production cost.

Description

A kind of modified high impact resistant polystyrene composite and preparation method thereof
Technical field
The present invention relates to low temperature resistant highly anti-flush polyphenylacetylene composition of a kind of modification and preparation method thereof.
Background technology
High-impact polystyrene (hereinafter being called HIPS) is actually a kind of modified product of polystyrene, is dispersed in the polystyrene external phase by rubber particle, forms rubber modified polystyrene.The production method of HIPS has grafting copolymerization process and mechanical mixing method.Blending method is because melt viscosity is difficult for overcoming the dispersive problem greatly, and two is alternate only with faint Van der Waals force combination, copolymerization system force of cohesion a little less than, material modified performance is far away from the performance of graft materials, so industrial main employing continuous bulk and two kinds of graft copolymerization technologies of body one suspension.In grafting copolymerization process,, cause after the grafting among the HIPS rubber quality content generally 10% because rubber is limited at styrene solubility.Although HIPS has most of advantages of polystyrene, as rigidity, easy dyeing, easy-formation, and shock strength and stress cracking resistance significantly improve than polystyrene, but rigidity and shock strength the high and low temperature shock strength is poor not enough, limited its further application.
Present stage, many methods that are used to improve HIPS impact property, especially low temperature impact properties came forth out.Use 3-10 part cis-1,4-polybutadiene rubber or styrene-butadiene rubber(SBR) (hereinafter being called SBR) among the CN 1083079A, 3-10 part styrene-butadiene-styrene thermoplastic elastomer (hereinafter being called SBS) carries out toughening modifying HIPS, though, SBS can play good compatibilization effect to cis-1,4-polybutadiene rubber, but the structure of three blocks effect to the SBR increase-volume time is undesirable, mainly be because in the SBR chain structure, divinyl and vinylbenzene are random copolymerization.Moreover this patent without any qualification, is not mentioned the improvement to the low temperature impact strength performance to SBR yet.Use terpolymer EP rubber (hereinafter being called EPDM) and SBS properties-correcting agent among the CN200510010543.2 as the HIPS low temperature impact properties, although this method can be improved the low temperature impact properties of HIPS greatly, but, cause the cost of manufacturing enterprise to increase because the price of EPDM and SBS is very high.In addition, use butylbenzene impact copolymer modification HIPS among the GB1498094, among the embodiment 14, HIPS and butylbenzene impact copolymer ratio are 60:40 (weight ratio) therein, and its Izod normal temperature notched Izod impact strength has reached 22.3KJ/m 2Although this method can improve its impact property to a certain extent, its cost is higher.
Summary of the invention
The purpose of this invention is to provide a kind of cheapness, high inflexible, modified high impact resistant polystyrene composite that low temperature impact properties is good and preparation method thereof.
A kind of modified high impact resistant polystyrene composite, in high-impact polystyrene is 100 mass parts, contain: 100 parts of high-impact polystyrenes, 8～34 parts in low-styrene-content styrene-butadiene rubber(SBR), 5～13 parts of 3～5 parts of activatory mineral fillers and butylbenzene impact copolymers is characterized in that described butylbenzene impact copolymer structural formula is: and St-(St → Bu), be 100% in this butylbenzene impact copolymer massfraction, St is cinnamic homopolymerization section, accounts for 60～40wt%; St → Bu is the random copolymerization section of vinylbenzene and divinyl, account for 40～60wt%, styrene units content accounts for 6～28wt% in the random copolymerization section of vinylbenzene and divinyl, butadiene unit content accounts for 94～72wt%, this butylbenzene impact copolymer both can be a linear structure, also can be hub-and-spoke configuration.
Butylbenzene impact copolymer of the present invention can adopt following method to be prepared: withstand voltage encloses container is clean with high purity nitrogen displacement, in the monomer add-on is 100 mass parts, add 200～500 parts of hexanaphthenes and 40～60 parts of vinylbenzene, add 0.006～0.01 part of butyllithium again as initiator, under 60～90 ℃ of temperature, react; Behind reaction 30～60min, slowly add the mixture of 2.4～16.8 parts of vinylbenzene and 23.2～57.6 parts of divinyl, reinforced time 60～120min, control mix monomer feed rate is less than the speed of response of monomer in the reactor and living polymerization body; Behind reaction 10～20min, termination reaction obtains line style butylbenzene impact copolymer; Perhaps continue to add 0.014～0.05 part of methyltrimethoxy silane as coupling agent, reaction 20～40min obtains star-like butylbenzene impact copolymer.
Wherein the activatory mineral filler adopts ordinary method to be prepared: super mixer is put in the mineral filler that 100 parts of dry water content of crossing are lower than 0.2wt%, when being heated to 100～130 ℃, add 0.5～1.5 part of coupling agent, after mixing 10～15min, discharging, in moisture eliminator, be cooled to room temperature, make the mineral filler of coupling agent activatory, standby.
Activatory mineral filler of the present invention is through one or more the mixture in the talcum powder of coupling agent treatment, lime carbonate, wollastonite powder, mica powder, kaolin, brucite powder, wilkinite, diatomite, the pumice sand.
Wherein coupling agent can be one or more the mixture in silane coupling agent, titanate coupling agent, aluminate coupling agent, rare-earth coupling agent, the aluminium titanium composite coupler.
The effect of coupling agent is to form strong bonding force with chemistry or physical action with inorganic filler surface to combine with the polystyrene resin in the high-impact polystyrene again, forms strong elastica.Like this, help mineral filler and be distributed to equably in the high-impact polystyrene, do the time spent when material is subjected to external force, elastica can play the effect of buffering and dispersive stress, can not cause because the decline of the adding material resistance to impact shock of mineral filler.
Because the resistance to low temperature of indication of the present invention is meant that use temperature is not less than the environment under-40 ℃, therefore require styrene-butadiene rubber(SBR) under this environment, still to keep its snappiness, that is to say that the second-order transition temperature of used styrene-butadiene rubber(SBR) can not be lower than-40 ℃.
Because the second-order transition temperature of styrene-butadiene rubber(SBR) is relevant with the styrene content in the styrene-butadiene rubber(SBR), the second-order transition temperature of the high more styrene-butadiene rubber(SBR) of styrene content is high more, therefore it is necessary selecting the styrene-butadiene rubber(SBR) of suitable styrene content, generally selects the styrene-butadiene rubber(SBR) of styrene content 10～24wt%.
In addition, molecular weight is bigger, and it is high more to add the man-hour melt viscosity, causes styrene-butadiene rubber(SBR) to be difficult for spreading out in melt, and form bad (the ideal form should be a spheric), so the weight-average molecular weight of styrene-butadiene rubber(SBR) should be at 100000～220000g/mol.
The consistency of styrene-butadiene rubber(SBR) and high-impact polystyrene is relatively poor, and rubber particles is dispersed in the polystyrene matrix, not only can not play toughness reinforcing effect, can become the interfacial stress centrostigma on the contrary, causes material damage, makes material property reduce greatly.The butylbenzene impact copolymer is the two good compatilizer, and the vinylbenzene segment can reach well blend with the high-impact polystyrene matrix, and butadiene-styrene random copolymerization segment can reach well blend with styrene-butadiene rubber(SBR).Therefore, butylbenzene impact copolymer of the present invention makes that not only styrene-butadiene rubber(SBR) is distributed in the high-impact polystyrene well, and can make that the styrene-butadiene rubber(SBR) form improves, particle diminishes, and material property is greatly improved.In order to bring into play the due compatible role of butylbenzene impact copolymer, require butylbenzene impact copolymer random copolymerization segment part styrene content should be as far as possible with styrene-butadiene rubber(SBR) in styrene content consistent as far as possible.
Can also add 0.1～0.5 part of auxiliary agent in the modified high impact resistant polystyrene blend composition of the present invention, as oxidation inhibitor, UV light stabilizing agent etc.
The preparation technology of modified high impact resistant polystyrene blend composition of the present invention divides two steps.First step: with load weighted styrene-butadiene rubber(SBR), activatory mineral filler, auxiliary agent blend 10～15min in mixing roll, granulation, the temperature of mixing roll is 20～50 ℃; Second step: middle product and butylbenzene impact copolymer, high-impact polystyrene that first step is obtained melt extrude in forcing machine, and barrel temperature is: 160～190 ℃ of leading portions, 180～230 ℃ in stage casing, 200～230 ℃ of back segments; 200～230 ℃ of die head temperatures, cooling, granulation can make the product of oyster white cylindrical pellet.
The modified high impact resistant polystyrene blend composition that the present invention produces is in toughness, rigidity, particularly low temperature impact properties all near or be better than adopting other properties-correcting agent to carry out the prior art of modification, and production cost is low.
Embodiment
Raw material sources
Styrene-butadiene rubber(SBR) 1500 (styrene content 23.5%) CNPC Lanzhou Petrochemical Company synthetic rubber plant
Styrene-butadiene rubber(SBR) 1810 (styrene content 10%) U.S. Goodyear Tire ﹠ Rubber Co
High-impact polystyrene PH-888G very beautifies worker company limited in Zhenjiang
K-resin KR-03 U.S. Karen Phillips company
The self-control of butylbenzene impact copolymer
Silane coupling agent KH-151 Nanjing can Dehua worker company limited
Titanate coupling agent KH-102 Nanjing can Dehua worker company limited
Tianzhang City's green chemical industry auxiliary reagent factory, aluminate coupling agent LS-60 Anhui Province
Breeze factory in the light calcium carbonate Ningyang County of Shandong Province capital
Breeze factory in the talcum powder Ningyang County of Shandong Province capital
Kaolin J01 Xuzhou Jia He kaolin factory
The dependence test reference to standard
Modulus in flexure GB9341-88
Tensile strength GB/1040
Simple beam impact strength GB/T1043-93
Embodiment and Comparative Examples test-results are listed in the table 1.
Embodiment 1:
100 parts of dry water content of crossing are lower than 0.2% light calcium carbonate and put into super mixer, when being heated to 110 ℃, add 1 part of silane coupling agent, mix after 10 minutes, discharging is cooled to room temperature in moisture eliminator, standby.
Withstand voltage encloses container is clean with high purity nitrogen displacement, be 100 mass parts in the monomer add-on, add 400 parts of hexanaphthenes and 60 parts of vinylbenzene, add 0.007 part of butyllithium again as initiator, under 80 ℃ of temperature, react; Behind the reaction 30min, slowly add the mixture of 9.4 parts of vinylbenzene and 30.6 parts of divinyl, reinforced time 70min; Behind the reaction 10min, termination reaction obtains line style butylbenzene impact copolymer;
With 3 parts of silane coupling agent activatory light calcium carbonates, 0.2 part of oxidation inhibitor, 0.1 part of UV light stabilizing agent, 15 parts of 10min mixing on double roll mill of styrene-butadiene rubber(SBR) (combined styrene 23.5%), granulation, the temperature of double roll mill is 30 ℃; With 100 parts of high-impact polystyrenes; 7 parts of butylbenzene impact copolymers (random section styrene content is 25%; mass ratio of vinylbenzene section and butadiene-styrene random copolymerization section is 60:40); on high-speed mixer, mix 5min; again through the twin screw extruder extruding pelletization; barrel temperature is: 160 ℃, 180 ℃ of leading portions, 200 ℃, 220 ℃ in stage casing, 220 ℃, 210 ℃ of back segments; 220 ℃ of die head temperatures, cooling, granulation can obtain the SBR modified high-impact polystyrene.
Embodiment 2:
100 parts of dry water content of crossing are lower than 0.2% talcum powder and put into super mixer, when being heated to 100 ℃, adds 0.5 part of titanate coupling agent, behind the mixing 15min, discharging is cooled to room temperature in moisture eliminator, standby.
Withstand voltage encloses container is clean with high purity nitrogen displacement, be 100 mass parts in the monomer add-on, add 300 parts of hexanaphthenes and 40 parts of vinylbenzene, add 0.008 part of butyllithium again as initiator, under 70 ℃ of temperature, react; Behind the reaction 45min, slowly add the mixture of 15 parts of vinylbenzene and 45 parts of divinyl, reinforced time 100min; Behind the reaction 15min, termination reaction obtains line style butylbenzene impact copolymer;
With 5 parts of titanate coupling agent activated talc powders, 0.1 part of oxidation inhibitor, 0.2 part of UV light stabilizing agent, 34 parts of 15min mixing on mixing roll of styrene-butadiene rubber(SBR) (combined styrene 23.5%), granulation, the temperature of double roll mill is 20 ℃; With 100 parts of high-impact polystyrenes; 13 parts of butylbenzene impact copolymers (random section styrene content is 25%; mass ratio of vinylbenzene section and butadiene-styrene random copolymerization section is 40:60); on high-speed mixer, mix 5min; again through the twin screw extruder extruding pelletization; 160 ℃, 180 ℃, 190 ℃, 200 ℃, 220 ℃, 230 ℃ in stage casing, 230 ℃, 220 ℃, 210 ℃ of back segments; 230 ℃ of die head temperatures obtain the SBR modified high-impact polystyrene.
Embodiment 3:
100 parts of dry water content of crossing are lower than 0.2% kaolin and put into super mixer, when being heated to 120 ℃, adds 0.8 part of aluminate coupling agent, behind the mixing 12min, discharging is cooled to room temperature in moisture eliminator, standby.
Withstand voltage encloses container is clean with high purity nitrogen displacement, be 100 mass parts in the monomer add-on, add 400 parts of hexanaphthenes and 40 parts of vinylbenzene, add 0.007 part of butyllithium again as initiator, under 65 ℃ of temperature, react; Behind the reaction 60min, slowly add the mixture of 16.2 parts of vinylbenzene and 43.8 parts of divinyl, reinforced time 120min; Behind the reaction 20min, termination reaction obtains line style butylbenzene impact copolymer.
With 4 parts of aluminate coupling agent activatory wollastonite powder, 0.1 part of oxidation inhibitor, 0.2 part of UV light stabilizing agent, 34 parts of 12min mixing on double roll mill of styrene-butadiene rubber(SBR) (combined styrene 23.5%), granulation, the temperature of double roll mill is 40 ℃; With 100 parts of high-impact polystyrenes; 5 parts of butylbenzene impact copolymers (random block part styrene content is 27%; the mass ratio 40:60 of vinylbenzene section and butadiene-styrene random copolymerization section); mix 5min on high-speed mixer; again through the twin screw extruder extruding pelletization; barrel temperature is identical with embodiment 2,230 ℃ of die head temperatures obtain the SBR modified high-impact polystyrene.
Embodiment 4:
The water content that drying is crossed is lower than 50 parts of light calcium carbonates and 50 parts of talcum powder of 0.2% and puts into super mixer, when being heated to 130 ℃, adds 1.5 parts of silane coupling agents, mix 15min after, discharging is cooled to room temperature in moisture eliminator, standby.
Withstand voltage encloses container is clean with high purity nitrogen displacement, be 100 mass parts in the monomer add-on, add 500 parts of hexanaphthenes and 60 parts of vinylbenzene, add 0.01 part of butyllithium again as initiator, under 85 ℃ of temperature, react; Behind the reaction 30min, slowly add the mixture of 9.6 parts of vinylbenzene and 30.4 parts of divinyl, reinforced time 60min; Behind the reaction 10min, add 0.03 part of methyltrimethoxy silane as coupling agent, reaction 30min obtains star-like butylbenzene impact copolymer.
With silane coupling agent activatory light calcium carbonate and 4 parts, 0.3 part oxidation inhibitor of talcum powder, 0.1 part of UV light stabilizing agent, 8 parts of 12min mixing on double roll mill of styrene-butadiene rubber(SBR) (combined styrene content 23.5%), granulation, the temperature of double roll mill are 30 ℃; With 7 parts of 100 parts of high-impact polystyrenes and butylbenzene impact copolymers (random block part combined styrene content is 24%, the mass ratio 60:40 of vinylbenzene section and butadiene-styrene random copolymerization section), on super mixer, mix 5min; With the charging simultaneously in the different charging opening of twin screw extruder of above-mentioned mixed product, barrel temperature is identical with embodiment 1, and extruding pelletization obtains the SBR modified high-impact polystyrene.
Embodiment 5:
100 parts of dry water content of crossing are lower than 0.2% light calcium carbonate and put into super mixer, when being heated to 110 ℃, adds the titanate coupling agent of 0.6 part of silane coupling agent and 0.8 part, behind the mixing 13min, discharging is cooled to room temperature in moisture eliminator, standby.
Withstand voltage encloses container is clean with high purity nitrogen displacement, be 100 mass parts in the monomer add-on, add 300 parts of hexanaphthenes and 40 parts of vinylbenzene, add 0.006 part of butyllithium again as initiator, under 60 ℃ of temperature, react; Behind the reaction 60min, slowly add the mixture of 6.6 parts of vinylbenzene and 53.4 parts of divinyl, reinforced time 120min; Behind the reaction 12min, termination reaction obtains line style butylbenzene impact copolymer.
With 4 parts of silane coupling agent and titanate coupling agent activatory light calcium carbonates, 0.2 30 parts in part oxidation inhibitor, 0.2 part of UV light stabilizing agent, styrene-butadiene rubber(SBR) (combined styrene content 10%), mixing 10min on the double roll mill, granulation, the temperature of double roll mill is 25 ℃; With 7 parts of 100 parts of high-impact polystyrenes and butylbenzene impact copolymers (random block part combined styrene content is 11%, the mass ratio 40:60 of vinylbenzene section and butadiene-styrene random copolymerization section), on super mixer, mix 5min; With the charging simultaneously in the different charging opening of twin screw extruder of above-mentioned mixed product, extruding pelletization, barrel temperature is identical with embodiment 2, obtains the SBR modified high-impact polystyrene.
Comparative Examples 1:
Other processing condition and raw material add-on are identical with embodiment 1, and difference is not add the butylbenzene impact copolymer, obtain the SBR modified high-impact polystyrene.
Comparative Examples 2:
Other processing condition and raw material add-on are identical with embodiment 2, and difference is not add the butylbenzene impact copolymer, obtain the SBR modified high-impact polystyrene.
Comparative Examples 3:
Other processing condition and raw material add-on are identical with embodiment 2, and difference is not add the butylbenzene impact copolymer, but add 13 parts of SBS, obtain the SBR modified high-impact polystyrene.
Comparative Examples 4:
Other processing condition and raw material add-on are identical with embodiment 4, and difference is not add the butylbenzene impact copolymer, but add 7 parts of SBS, obtain the SBR modified high-impact polystyrene.
Comparative Examples 5:
Other processing condition and raw material add-on are identical with embodiment 2, and difference is not add the butylbenzene impact copolymer, but add 13 parts of K-resin KR-03, obtain the SBR modified high-impact polystyrene.
Comparative Examples 6:
Other processing condition and raw material add-on are identical with embodiment 5, and difference is not add the butylbenzene impact copolymer, but add 7 parts of K-resin KR-03, obtain the SBR modified high-impact polystyrene.
Table 1 embodiment and Comparative Examples test-results
Embodiment and Comparative Examples Tensile strength (MPa) Simply supported beam breach normal temperature (25 ℃) shock strength (KJ/m 2) Simply supported beam breach low temperature (40 ℃) shock strength (KJ/m 2) Modulus in flexure (MPa)
Embodiment 1 29 22 14 1680
Embodiment 2 23 28 18 1590
Embodiment 3 21 17 12 1580
Embodiment 4 33 18 13 1650
Embodiment 5 20 35 25 1420
Comparative Examples 1 24 11 9 1560
Comparative Examples 2 22 14 9 1450
Comparative Examples 3 20 19 13 1470
Comparative Examples 4 28 12 11 1590
Comparative Examples 5 23 17 11 1500
Comparative Examples 6 18 19 12 1400
From embodiment 1～5 as can be known, along with the increase and the component butylbenzene impact copolymer content of component styrene-butadiene rubber(SBR) content are suitable, SBR modified highly anti-flush polyphenylacetylene composition shock strength increases, but modulus in flexure reduces; Under the approaching situation of styrene-butadiene rubber(SBR) content, styrene content increases in the styrene-butadiene rubber(SBR), and shock strength increases.
From Comparative Examples 1～2 as can be known, do not having under the compatilizer butylbenzene impact copolymer situation, the impact property of product and rigidity are all very poor; From Comparative Examples 3～6 as can be known, exist under the situation at SBS and K-resin, under the butylbenzene impact copolymer existence of the present invention than corresponding proportion, impact property and firm poor performance.

Claims (5)

1. modified high impact resistant polystyrene composite, in high-impact polystyrene is 100 mass parts, contain: 100 parts of high-impact polystyrenes, 8～34 parts in low-styrene-content styrene-butadiene rubber(SBR), 3～5 parts of activatory mineral fillers, 5～13 parts and 0.1～0.5 part auxiliary agent of butylbenzene impact copolymer, it is characterized in that described butylbenzene impact copolymer structural formula is: St-(St → Bu), in this butylbenzene impact copolymer massfraction is 100%, and St is cinnamic homopolymerization section, accounts for 60～40wt%; St → Bu is the random copolymerization section of vinylbenzene and divinyl, account for 40～60wt%, styrene units content accounts for 6～28wt% in the random copolymerization section of vinylbenzene and divinyl, butadiene unit content accounts for 94～72wt%, styrene content is 10～24wt% in the described styrene-butadiene rubber(SBR), this butylbenzene impact copolymer is linear structure or hub-and-spoke configuration, and described activatory mineral filler is through one or more the mixture in the talcum powder of coupling agent treatment, lime carbonate, wollastonite powder, mica powder, kaolin, brucite powder, wilkinite, diatomite, the pumice sand.
2. modified high impact resistant polystyrene composite as claimed in claim 1, it is characterized in that the butylbenzene impact copolymer adopts following method to be prepared: withstand voltage encloses container is clean with high purity nitrogen displacement, in the total monomer add-on is 100 mass parts, add 200～500 parts of hexanaphthenes and 40～60 parts of vinylbenzene, add 0.006～0.01 part of butyllithium again as initiator, under 60～90 ℃ of temperature, react; Behind reaction 30～60min, slowly add the mixture of 2.4～16.8 parts of vinylbenzene and 23.2～57.6 parts of divinyl, reinforced time 60～120min, control mix monomer feed rate is less than the speed of response of monomer in the reactor and living polymerization body; Behind reaction 10～20min, termination reaction obtains line style butylbenzene impact copolymer; Continue to add 0.014～0.05 part of methyltrimethoxy silane as coupling agent, reaction 20～40min obtains star-like butylbenzene impact copolymer.
3. modified high impact resistant polystyrene composite as claimed in claim 1, the weight-average molecular weight that it is characterized in that described styrene-butadiene rubber(SBR) is 100000～220000g/mol.
4. modified high impact resistant polystyrene composite as claimed in claim 1 is characterized in that described coupling agent is one or more the mixture in silane coupling agent, titanate coupling agent, aluminate coupling agent, rare-earth coupling agent, the aluminium titanium composite coupler.
5. the preparation method of a modified high impact resistant polystyrene composite as claimed in claim 1, it is characterized in that the first step: with load weighted styrene-butadiene rubber(SBR), activatory mineral filler, auxiliary agent blend 10～15min in mixing roll, granulation, the temperature of mixing roll are 20～50 ℃; Second step: middle product and butylbenzene impact copolymer, high-impact polystyrene that the first step is obtained melt extrude in forcing machine, and barrel temperature is: 160～190 ℃ of leading portions, 180～230 ℃ in stage casing, 200～230 ℃ of back segments; 200～230 ℃ of die head temperatures, cooling, granulation can make the product of oyster white cylindrical pellet.
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CN102408639B (en) * 2010-09-21 2014-08-06 中国石油天然气股份有限公司 Impact-resistant polystyrene resin composition and preparation method thereof
CN102558915A (en) * 2010-12-30 2012-07-11 上海宝利纳材料科技有限公司 Modified talcum powder and preparation method and application thereof
CN102115509B (en) * 2010-12-31 2012-07-04 大连理工大学 Starlike branched polybutadiene of rare earth catalyst system and preparation method thereof
CN102898734B (en) * 2011-07-25 2015-05-13 中国石油天然气股份有限公司 Polystyrene resin composition and preparation method thereof
CN102775715A (en) * 2012-08-21 2012-11-14 四川塑金科技有限公司 Modified regeneration high impact polystyrene for tubes and pipe fittings and preparation method of high impact polystyrene
CN103804810A (en) * 2014-01-20 2014-05-21 苏州新区华士达工程塑胶有限公司 Polystyrene brittle modified plastic
US10577487B2 (en) * 2016-05-06 2020-03-03 Canon Kabushiki Kaisha Thermoplastic resin composition, molded article, and manufacturing method of molded article
CN110405966B (en) * 2019-07-19 2021-11-16 株洲时代新材料科技股份有限公司 Preparation method of in-situ grafted modified rubber

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