CN100386378C - Preparation method of highly impact-resistant and heat-resistant blended ABS resin - Google Patents
Preparation method of highly impact-resistant and heat-resistant blended ABS resin Download PDFInfo
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- CN100386378C CN100386378C CNB2005100266608A CN200510026660A CN100386378C CN 100386378 C CN100386378 C CN 100386378C CN B2005100266608 A CNB2005100266608 A CN B2005100266608A CN 200510026660 A CN200510026660 A CN 200510026660A CN 100386378 C CN100386378 C CN 100386378C
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Abstract
The present invention provides a preparation method of high impact-proof and high heat-proof blending ABS resin. Heat-proof ABS resin obtained by emulsion polymerization and general-purpose ABS resin obtained by main body polymerization are extruded by blending, and the ABS resin with the high impact-proof and the high heat-proof comprehensive properties can be manufactured. The general-purpose ABS resin has low impact strength, medium impact strength or high impact strength, wherein the particle sizes of rubber are 1 to 10 mu m, and rubber particles of which the particle sizes are in the range of 0.1 to 2 mu m occupy more than 50% of the total volume of the rubber particles in the heat-proof ABS resin. Because of the suitable proportion of the two blending resin components and reasonable distribution of the big and small particle sizes of the rubber particles, so a product of the blending ABS resin can simultaneously has the high impact-proof and the high heat-proof properties, the impact strength can reach to 17.8 to 32.6KJ /m<2>, and the Vicat softening temperature can reach to 104 to 110 DEG. The preparation method of the blending ABS resin is simple has low cost, and is suitable for commercial production.
Description
Technical field
The present invention relates to the preparation method of blended ABS resin, relate in particular to a kind of heat-resisting ABS resin that the general ABS resin and the letex polymerization of mass polymerization acquisition are obtained is extruded the blended ABS resin of preparation highly impact-resistant and heat-resistant by blend method.
Background technology
ABS resin has good shock strength, high rigidity and chemical resistant properties, but general resistance toheat is not high.ABS resin such as automobile, motorcycle Application Areas requires material except that having above-mentioned performance, must have excellent heat resisting simultaneously concurrently.In order to satisfy the demand of material Application Areas, people attempt preparing heat-resisting ABS resin by the whole bag of tricks, as preparing ABS resin, synthesize heat-resisting ABS resin by add heat resistance modified monomer in the mass polymerization flow process, pass through to add prepared in reaction heat-resisting ABS resin or the like in the heat-resisting monomer mixing process in the response type forcing machine by adding heat resistance modified monomer in emulsion polymerization process.
US5,212,240 Dow Chemical companies adopt emulsion graft polymerization-mixing method to prepare heat-resisting ABS resin.At first obtain grafted rubber components, produce heat-resisting ABS resin with flumaronitrile-styrene-acrylonitrile terpolymer blending then by letex polymerization.It is 2.8ft.lbs/in that product adopts the socle girder breach shock strength of ASTM256 standard testing product; The heat-drawn wire that adopts ASTM D-648 standard testing product is 245 °F promptly 118.3 ℃; Adopt the inspection of DSC dsc to find that the resin part is miscible, find that simultaneously the interlaminar resin intermiscibility is good more, toughness of products is strong more.But adopt the heat-resisting ABS resin shock strength of aforesaid method production only can reach medium shock strength 14.6KJ/M
2, in use have certain limitation.
As the stable on heating method that improves the ABS thermoplastic resin, known have one by introduce alpha-methyl styrene or other similar monomer methods in copolyreaction.For example, US4,874,829 with alpha-methyl styrene, vinyl cyanide and maleimide monomer continuous polymerization generation multipolymer or trimeric method, in order to break through the low-conversion of alpha-methyl styrene, uses a large amount of highly active vinyl cyanide in the feed composition.Adopt the final easy variable color of resin that generates of aforesaid method and generate gel, this will cause the mechanical property of materials of heat-resisting ABS resin significantly to descend.
CN NO.1126734A discloses and has adopted the maleimide modification to prepare the method for heat-resisting ABS resin.This method comprises mediates a kind of maleimide copolymer, a kind of ABS graft copolymer and optional a kind of AS multipolymer, thereby it is obtain heat-stable master batch resin, and further that a kind of ABS graft copolymer and a kind of AS multipolymer and heat-stable master batch resin is kneaded together.Although but maleimide copolymer has high heat-stable characteristics in the component, compare with common AS resin, low in the molten state current downflow, thereby molding performance is poor.Be injection molded into the mould processing characteristics in order to improve, use this method to have to add softening agent, lubricant etc., must make additive homodisperse in resin in the course of processing, but additive will be penetrated into and cause the outward appearance generation defective that suffers damage on the product surface in links such as injection molding, processing, tends to reduce resistance toheat.
US4,757,109 and the open NO.1983-206657 of Japanese Patent propose a kind of the mixing to improve the stable on heating method of ABS resin with heat stable resin and ABS resin.Above-mentioned heat stable resin is generated with emulsion polymerization by maleimide monomer, vinyl nitrilation thing monomer and aromatic ethylene base, and the maleimide monomer content is high more in the resin, and thermotolerance is good more.Yet because this heat-resisting monomer reaction speed is fast, thermal discharge is big, and content is limited in resin.In order to break through this restriction, it is very complicated that polymerization process becomes; The maleimide monomer content is high more in the polymer resin, and is poor more with the ABS resin intermiscibility, thereby causes the product shock strength to descend.Commercial emulsion method heat-resisting ABS resin is the grafting rubbers copolymerization component that vinylbenzene, vinyl cyanide and rubber generation letex polymerization is obtained high glue content at present, the multipolymer that olefinic monomers such as heat-resisting monomer such as maleimide or maleic anhydride and vinyl cyanide, vinylbenzene are made is by being obtained two kinds of components by the twin screw extruder blending.In order to improve resistance toheat, adding graft copolymer has certain limitation, thereby rubber content can not be too high in the product, therefore generally is difficult to reach have the high-impact performance when product has the high heat resistance energy.
Summary of the invention
The invention provides a kind of preparation method of new highly impact-resistant and heat-resistant blended ABS resin.Specifically, be that the heat-resisting ABS resin of letex polymerization acquisition and the general ABS resin of mass polymerization acquisition are extruded the method that preparation has the blended ABS resin of high-impact and high heat-resisting over-all properties by blend, to overcome the defective that prior art exists.
Find through the deep research inventor, because heat-resisting ABS resin that letex polymerization and mass polymerization obtain respectively and the rubber size in the general ABS resin are in two big zones, average rubber particle size is respectively small particle size and big particle diameter, when the rubber particles of the rubber particles of big particle diameter and small particle size reached the ideal ratio of mixture, blend product was sheared the crazing theory based on ABS resin and is had excellent erosion-resisting characteristics and resistance toheat.Finished the present invention based on above beat all experimental result.
The preparation method of highly impact-resistant and heat-resistant blended ABS resin of the present invention
The heat-resisting ABS resin that obtains by general ABS resin that mass polymerization is obtained and letex polymerization is 1 part of ratio by weight: the blend of 1-25 part is extruded, and promptly makes highly impact-resistant and heat-resistant blended ABS resin.
The bulk polymerization of general ABS resin has had detailed description in many documents, as US NO.5240993, the technology of patent disclosure such as US5569709 and US5414045 is to comprise that mono vinyl arenes monomer, mono-vinyl unsaturated nitrile monomer, rubber are that main material obtains by the continuous bulk polymerization reaction.Owing to adopt the difference on mass polymerization detailed process and the equipment, the resin Composition content that mass polymerization obtains has nothing in common with each other, external phase and disperse phase ratio also exist than big-difference, residing zone of average rubber particle size and rubber size and SAN (styrene-acrylonitrile copolymer) molecular weight change greatly in addition, the general ABS resin that mass polymerization among the present invention obtains is to adopt Chinese patent application 200410099053.X bulk technique to be prepared from, and composition and weight part that general ABS resin comprises are as follows:
50～70 parts of mono vinyl arenes monomers
15～30 parts of mono-vinyl unsaturated nitrile monomers
7～20 parts of rubber
1～4 part of auxiliary agent
Described mono vinyl arenes monomer is selected from vinylbenzene, alpha-methyl styrene; α-ethyl styrene; Halogenated styrenes such as alpha-chloro vinylbenzene, alpha-brominated vinylbenzene etc.; Or alpha-halogen ring-alkylated styrenes such as α-1-chloro-4-methyl-benzene, α-bromo ethyl phenenyl ethene etc.The mono-vinyl unsaturated nitrile monomer is selected from methacrylonitrile, vinyl cyanide, C
1-C
4Alkyl vinyl nitrile or phenyl vinyl nitrile etc.; Rubber is selected from polyisoprene rubber, polybutadiene rubber or styrene-butadiene block copolymer rubber; Auxiliary agent comprises initiator, chain-transfer agent and mineral wet goods.
The particle diameter of rubber particles is 1～10 μ m in the general ABS resin that described mass polymerization obtains, and the median size of rubber particles is 2～6 μ m, and external phase SAN weight-average molecular weight is 5 * 10
4-3.5 * 10
5This resin has low shock strength, middle shock strength or high impact strength, and (technician is by being accustomed to 10KJ/m in the same industry
2Hereinafter referred to as low shock strength, 10-is less than 17KJ/m
2Be middle shock strength, 17KJ/m
2More than be high impact strength), resistance toheat is general, about about 95 ℃.
The rubber particles that particle diameter is in 0.1～2 mu m range in the heat-resisting ABS resin that described letex polymerization obtains accounts for more than 50% of rubber particles cumulative volume, and this resin has middle shock strength and good heat-resistant, about about 105 ℃.
After the above-mentioned two kinds resins with different rubber particles particle diameters are extruded homodisperse by blend, rubber phase is by new spatiality redistribution in the general ABS resin that heat-resisting ABS resin that letex polymerization obtains and mass polymerization obtain, after blend reached a certain proper ratio, the external phase SAN of rubber phase and different molecular weight reached optimum regime in above-mentioned two kinds of components.Thereby the graft rubber upper layer at utmost reduces aggregation extent and effectively prevents contact between the rubber phase region in this case.Here the particle diameter of rubber particles can reflect the difference of rubber phase grafting upper layer.By the heat-resisting ABS resin that letex polymerization obtains, as one of blend components, its rubber size is in less relatively zone, and overall size of particles is less, and the particle diameter that accounts for the rubber particles of percent by volume more than 50% is in 0.1～2 mu m range; This less rubber particles helps shear yielding.Another blend components is the general ABS resin that obtains by mass polymerization, and its rubber particles size is totally bigger, is in 1～10 μ m, and this bigger rubber particles/particle agglomeration can effectively cause crazing.Two kinds of toughness reinforcing forms of crazing and shear yielding common existence of competition mutually in blend product, after the component mixing reaches best proportion, two kinds of mechanism of action make the ABS resin toughening effect reach maximization, thereby have improved the mechanical property such as the erosion-resisting characteristics of heat-resisting ABS resin.When components do match, blend components can not cause the product erosion-resisting characteristics to descend because of a certain component that wherein erosion-resisting characteristics is lower, can keep the high-performance of high-impact component on the contrary, even can make the erosion-resisting characteristics of blend product be higher than arbitrary component.
The preparation technology of blended ABS resin of the present invention is very easy, can adopt ordinary method well known in the art, and extruding pelletization gets final product in the blend forcing machine.
The inventor confirms by experiment, and the general ABS resin that mass polymerization obtains is understood the shock resistance that directly influence the blended ABS resin product with the proportioning of the heat-resisting ABS resin that letex polymerization obtains, so the present invention controls the two suitable ratio, that is:
1 part of the general ABS resin that mass polymerization obtains
1～25 part of the heat-resisting ABS resin that letex polymerization obtains
And two kinds of ABS resin are owing to have the rubber size that varies in size, so blended ABS resin product of the present invention can possess excellent heat resisting and high impact resistance simultaneously.Test data by following embodiment shows, adopts the ASTMD-256-02 standard to detect, and its shock resistance can reach 17.8～32.6KJ/M
2, adopt ASTMD-1525-00 standard detection vicat softening temperature can reach 104～110 ℃.
Test by following embodiment 1, embodiment 2 and embodiment 3 as seen, when two kinds of component blend ratios are suitable, in the ABS resin that mass polymerization obtains in the heat-resisting ABS resin of bigger rubber particles and letex polymerization acquisition less rubber particles reach perfect condition at blend product spatial distribution state.The middle anti-impact heat-resisting ABS resin that letex polymerization obtains is after the general ABS blend that mass polymerization obtains, shear yielding when being subjected to extraneous stress, the rubber particles of small particle size takes place, the big particle diameter of rubber that comprises the rigidity san copolymer simultaneously becomes the firm anchor point of rubber fento when suitable volumes per-cent, the crazing that disperse phase is produced effectively disperses and stops, and has absorbed lot of energy; Good toughening effect is played in the generation acting in conjunction of shear yielding and multiple crazing.
Therefore the general ABS resin of mass polymerization acquisition has obvious toughening effect to the heat-resisting ABS resin that letex polymerization obtains, and the amplification maximum can reach 100%.Blend is extruded the blended ABS resin of the present invention that obtains and is not only had excellent erosion-resisting characteristics, and has good heat-resistant simultaneously.
As seen from the above technical solution, blended ABS resin of the present invention need not to add any additives, can obtain heat-resisting and all very excellent product of shock resistance, simple to operate, technology is simplified greatly, reduce production cost, be suitable for suitability for industrialized production, can satisfy the needs of Application Areass such as automobile.
Embodiment
Embodiment 1
The general ABS resin (B component 1) that mass polymerization is obtained and the heat-resisting ABS resin (component A1) of letex polymerization acquisition are in Different Weight part ratio listed in the table 1, extruding pelletization after model is to carry out blend with 50Kg/h in the twin screw extruder of TE-50, the blend extrusion temperature is 180～220 ℃.
Wherein: the composition and the weight part thereof that comprise in the B component 1 are as follows:
63 parts of vinylbenzene
21.2 parts of vinyl cyanide
12.2 parts of polybutadiene rubbers
1.3 parts of organo-peroxides (initiator, Luperox 11M75, ATOFINA company product)
1.3 parts in alpha-methyl styrene dimer mixture (chain-transfer agent)
1 part in mineral oil
The particle diameter of rubber particles is 1～10 μ m in the B component 1, and external phase SAN weight-average molecular weight is in 5 * 10
4-2.5 * 10
5In the scope.Adopt the ASTMD-256-02 standard to detect, its shock strength is 11.31KJ/M
2Adopting ASTMD-1525-00 standard detection vicat softening temperature is 92.5 ℃.
Component A1: be the heat-resisting ABS resin that letex polymerization obtains, trade names are STAREXSR0320 (production of Korea S SAMSUNG company), and wherein particle diameter is that the rubber particles of 0.1～2 μ m accounts for more than 50% of rubber particles cumulative volume.Adopt the ASTMD-256-02 standard to detect, its shock strength is 15.79KJ/M
2Adopting ASTMD-1525-00 standard detection vicat softening temperature is 105.9 ℃.
The shock strength of the blend product that table 1 component A1 and B component 1 make after the blend in varing proportions
| Blend weight part ratio | Izod | The Izod increased value | Izod amplification | Vicat |
| A1∶B1 | KJ/M2 | KJ/M2 | ％ | ℃ |
| 20∶1 | 23.78 | 7.99 | 50.6 | 105.8 |
| 15∶1 | 31.72 | 15.93 | 100.9 | 105.5 |
| 10∶1 | 30.54 | 14.75 | 93.4 | 104.0 |
| 5∶1 | 28.87 | 13.08 | 82.8 | |
| 2∶1 | 27.38 | 11.59 | 73.4 | 108.0 |
Remarks: Izod increased value in the table 1: the difference of blend product and B component 1 shock strength.
Izod amplification: the ratio of above-mentioned Izod increased value and B component 1 shock strength.
Vicat: vicat softening temperature
Table 1 shows, when component A1 and B component 1 blend ratio are 10: 1～15: 1, adopts the shock strength of ASTMD-256-02 standard detection blend product ABS resin can surpass 30KJ/M
2, far above the shock strength of component A1 and B component 1.It is 104.0～108.0 ℃ that the blend product ABS resin adopts ASTMD-1525-00 standard detection vicat softening temperature, has higher heat resistance.
Rubber size and distribution in table 2 component A1 and the blended ABS resin product
Remarks: ABS resin is dissolved in the acetone solvent, adopts the JL9200 laser particle size analyzer to analyze rubber size and distribution.
Table 2 as seen, trade names are the rubber particles generation noticeable change behind the general ABS resin blending and modifying that mass polymerization obtains of STAREX SR0320 heat-resisting ABS resin, become by original unimodal distribution and to have two significantly two kinds of size distribution zones of size, be in small particle size rubber particles in 0.1 μ m～1 mu m range and account for rubber particles total volume percent 34.42% and drop to 5.86%, the middle particle diameter rubber particles that is in 1 μ m～4 mu m ranges slightly descends.22.71% before by the blend of the above big particle diameter rubber particles of 4 μ m increases to 53.76%.The above results shows component A1 behind blending and modifying, wherein rubber size and the significant variation of the generation that distributes.
Embodiment 2
The general ABS resin (B component 2) that mass polymerization is obtained and the heat-resisting ABS resin (component A1) of letex polymerization acquisition are in Different Weight part ratio listed in the table 3, extruding pelletization after model is to carry out blend with 50Kg/h in the twin screw extruder of TE-50, the blend extrusion temperature is 180～220 ℃.
Wherein: the composition and the weight part thereof that comprise in the B component 2 are as follows:
63 parts of vinylbenzene
21 parts of vinyl cyanide
13 parts of polybutadiene rubbers
Organo-peroxide (initiator, Luperox 11M75,
ATOFINA company product) 1.3 part
1.3 parts in alpha-methyl styrene dimer mixture (chain-transfer agent)
0.4 part in mineral oil
The particle diameter of rubber particles is 1～10 μ m in the B component 2, and external phase SAN weight-average molecular weight is in 1 * 10
5-3.5 * 10
5In the scope.Adopt the ASTMD-256-02 standard to detect, its shock strength is 20.23KJ/M
2Adopting ASTMD-1525-00 standard detection vicat softening temperature is 96.3 ℃.
Component A1: be the heat-resisting ABS resin that letex polymerization obtains, trade names are STAREXSR0320 (production of Korea S SAMSUNG company), wherein particle diameter is that the rubber particles of 0.1～2 μ m accounts for more than 50% of rubber particles cumulative volume, adopt the ASTMD-256-02 standard to detect, its shock strength is 15.79KJ/M
2Adopting ASTMD-1525-00 standard detection vicat softening temperature is 105.9 ℃.
The shock strength of the blend product that table 3 component A1 and B component 2 make after the blend in varing proportions
| The blend ratio | Izod | The Izod increased value | Izod amplification | Vicat |
| A1∶B2 | KJ/M 2 | KJ/M 2 | ％ | ℃ |
| 20∶1 | 27.79 | 12 | 76.0 | 105.5 |
| 15∶1 | 29.87 | 14.08 | 89.2 | 105 |
| 10∶1 | 31.34 | 15.55 | 98.5 | 104.5 |
| 5∶1 | 31.81 | 16.02 | 101.5 | |
| 2∶1 | 32.6 | 16.81 | 106.5 | 108.0 |
Remarks: Izod increased value in the table 3: the difference of blend product and B component 2 shock strengths.
Izod amplification: the ratio of above-mentioned Izod increased value and B component 2 shock strengths.
Vicat: vicat softening temperature
Rubber size and distribution in table 4 component A1 and the blended ABS resin product
Remarks: ABS resin is dissolved in the acetone solvent, adopts the JL9200 laser particle size analyzer to analyze rubber size and distribution.
(A1: B2) increase, the shock strength of blend product is on a declining curve with the blend ratio in table 3 explanation.When the blend ratio is 2: 1～5: 1, adopt the shock strength of ASTMD-256-02 standard detection blend product ABS resin to surpass 30KJ/M
2, far above the shock strength of component A1 and B component 2.It is 104.5-108.0 ℃ that the blend product ABS resin adopts ASTMD-1525-00 standard detection vicat softening temperature, has higher heat resistance.
By table 4 as seen, trade names are the rubber particles generation noticeable change behind the general ABS resin blending and modifying that mass polymerization obtains of STAREX SR0320 heat-resisting ABS resin, being in small particle size rubber particles in 0.1 μ m～1 mu m range accounts for the rubber particles total volume percent and drops to 4.04% by original 34.42%, its particle diameter of rubber particles of middle particle diameter mainly is in 1 μ m～4 μ m volume percent and slightly descends, and the above big particle diameter rubber particles volume percent of 4 μ m then rises to 57.27% by 22.71%.The above results shows when the variation of rubber size and distribution thereof makes ABS resin be subjected to extraneous stress, and deformation of small particle size rubber particles generation shear yielding and big particle diameter rubber particles multiple crazing take place act on simultaneously and absorbed big energy and shown good shock resistance.Remarkable toughness reinforcing basic reason behind the middle anti-impact heat-resisting ABS resin blending and modifying that big small particle size distribution rationally is the letex polymerization acquisition.
Embodiment 3
The general ABS resin (B component 2) that mass polymerization is obtained and the heat-resisting ABS resin (component A2) of letex polymerization acquisition are in Different Weight part ratio listed in the table 5, extruding pelletization after model is to carry out blend with 50Kg/h in the twin screw extruder of TE-50, the blend extrusion temperature is 180～220 ℃.
Wherein: the composition and the weight part thereof that comprise in the B component 2 are as follows:
63 parts of vinylbenzene
21 parts of vinyl cyanide
13 parts of polybutadiene rubbers
1.3 parts of organo-peroxides (initiator, Luperox 11M75, ATOFINA company product)
1.3 parts in alpha-methyl styrene dimer mixture (chain-transfer agent)
0.4 part in mineral oil
The particle diameter of rubber particles is 1～10 μ m in the B component 2, and external phase SAN weight-average molecular weight is in 5 * 10
4-2.5 * 10
5In the scope.Adopt the ASTMD-256-02 standard to detect, its shock strength is 20.23KJ/M
2, adopting ASTMD-1525-00 standard detection vicat softening temperature is 96.3 ℃.
Component A2 is that heat-resisting ABS resin trade names that letex polymerization obtains are that Lustran HH1827 (Bayer A.G's production) particle diameter wherein is that the rubber particles of 0.1～2 μ m accounts for more than 50% of rubber particles cumulative volume, adopt the ASTMD-256-02 standard to detect, its shock strength is 15.98KJ/M
2, adopting ASTMD-1525-00 standard detection vicat softening temperature is 109.6 ℃.
The shock strength of the blend product that table 5 component A2 and B component 2 make after the blend in varing proportions
| The blend ratio | Izod | The Izod increased value | Izod amplification |
| A2∶B2 | KJ/M 2 | KJ/M 2 | ％ |
| 20∶1 | 17.82 | 1.84 | 11.5 |
| 15∶1 | 17.87 | 1.89 | 11.8 |
| 10∶1 | 18.29 | 2.31 | 14.5 |
| 5∶1 | 19.05 | 3.07 | 19.2 |
| 2∶1 | 22.58 | 6.6 | 41.3 |
Remarks: Izod increased value in the table 1: the difference of blend product and B component 2 shock strengths.
Izod amplification: the ratio of above-mentioned Izod increased value and B component 2 shock strengths.
Table 5 shows the blend product shock strength, and (A2: B2) increase is on a declining curve with the blend ratio.When the blend ratio is 2: 1, adopt the shock strength of ASTMD-256-02 standard detection blend product ABS resin to surpass 22KJ/M
2, far above the shock strength of component A2 and B component 2.It is 105.5～110 ℃ that the blend product ABS resin adopts ASTMD-256-02 standard detection vicat softening temperature, has higher heat resistance.
Claims (6)
1. the preparation method of a highly impact-resistant and heat-resistant blended ABS resin, it is characterized in that: the heat-resisting ABS resin that obtains by general ABS resin that mass polymerization is obtained and letex polymerization is 1 part of ratio by weight: the blend of 1-25 part is extruded, promptly make highly impact-resistant and heat-resistant blended ABS resin, the general ABS resin that described mass polymerization obtains has low shock strength, middle shock strength or high impact strength, wherein the particle diameter of rubber particles is 1-10 μ m, and external phase SAN molecular weight is 5 * 10
4-3.5 * 10
5The heat-resisting ABS resin of described letex polymerization has middle shock strength, and wherein the rubber particles that is in 0.1～2 mu m range of particle diameter accounts for more than 50% of rubber particles cumulative volume.
2. preparation method as claimed in claim 1 is characterized in that composition and weight part thereof that general ABS resin that described mass polymerization obtains comprises are as follows:
50～70 parts of mono vinyl arenes monomers
15～30 parts of mono-vinyl unsaturated nitrile monomers
7～20 parts of rubber
Auxiliary agent 1-4 part.
3. preparation method as claimed in claim 2 is characterized in that described mono vinyl arenes monomer is selected from vinylbenzene, alpha-methyl styrene, α-ethyl styrene, alpha-chloro vinylbenzene, alpha-brominated vinylbenzene, α-1-chloro-4-methyl-benzene or α-bromo ethyl phenenyl ethene.
4. as preparation method according to claim 2, it is characterized in that described mono-vinyl unsaturated nitrile monomer is selected from vinyl cyanide, methacrylonitrile, C1-C4 alkyl mono-vinyl nitrile or phenyl vinyl nitrile.
5. preparation method according to claim 2 is characterized in that described rubber is selected from styrene-butadiene block copolymer rubber, polybutadiene rubber or polyisoprene rubber.
6. preparation method as claimed in claim 2 is characterized in that described auxiliary agent comprises initiator, chain-transfer agent and mineral oil.
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| CN101885893B (en) * | 2009-05-13 | 2013-03-06 | 中国石油化工股份有限公司 | ABS (Acrylonitrile Butadiene Styrene) resin and preparation method thereof |
| KR101576726B1 (en) * | 2013-07-02 | 2015-12-10 | 주식회사 엘지화학 | Heat-resistant san resin, method for preparing the resin and heat-resistant abs resin composition containing the same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5491194A (en) * | 1991-05-24 | 1996-02-13 | The Dow Chemical Company | Thermally processable blends of high modulus polyurethanes and mass polymerized ABS resins |
| CN1188119A (en) * | 1996-11-28 | 1998-07-22 | 拜尔公司 | Improved thermoplastic moulding compositions of the ABS type |
| US5795936A (en) * | 1996-06-27 | 1998-08-18 | Chi Mei Corporation | Styrenic resin composition |
| CN1345355A (en) * | 1999-03-25 | 2002-04-17 | 美国拜尔公司 | Compsotiion containing polycarbonate and grafted rubber having improved low-temperature toughness |
| US6492467B1 (en) * | 2001-05-09 | 2002-12-10 | Bayer Corporation | Process for making ABS polymeric blends |
-
2005
- 2005-06-10 CN CNB2005100266608A patent/CN100386378C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5491194A (en) * | 1991-05-24 | 1996-02-13 | The Dow Chemical Company | Thermally processable blends of high modulus polyurethanes and mass polymerized ABS resins |
| US5795936A (en) * | 1996-06-27 | 1998-08-18 | Chi Mei Corporation | Styrenic resin composition |
| CN1188119A (en) * | 1996-11-28 | 1998-07-22 | 拜尔公司 | Improved thermoplastic moulding compositions of the ABS type |
| CN1345355A (en) * | 1999-03-25 | 2002-04-17 | 美国拜尔公司 | Compsotiion containing polycarbonate and grafted rubber having improved low-temperature toughness |
| US6492467B1 (en) * | 2001-05-09 | 2002-12-10 | Bayer Corporation | Process for making ABS polymeric blends |
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