CN103421271A - Highly-impact-resistant and highly-heat-resistant ABS resin and preparation method thereof - Google Patents
Highly-impact-resistant and highly-heat-resistant ABS resin and preparation method thereof Download PDFInfo
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- CN103421271A CN103421271A CN2012101679646A CN201210167964A CN103421271A CN 103421271 A CN103421271 A CN 103421271A CN 2012101679646 A CN2012101679646 A CN 2012101679646A CN 201210167964 A CN201210167964 A CN 201210167964A CN 103421271 A CN103421271 A CN 103421271A
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Abstract
The invention discloses a highly-impact-resistant and highly-heat-resistant ABS resin and a preparation method thereof. The preparation method comprises a step that an ABS resin obtained through bulk polymerization and an ABS resin obtained through emulsion polymerization undergo blending extrusion at 190-220DEG C according to a weight part ratio of 1:2-1:20 to obtain the highly-impact-resistant and highly-heat-resistant ABS resin. The ABS resin obtained through bulk polymerization comprises, by weight, 55-65 parts of a monovinyl aromatic hydrocarbon monomer, 15-30 parts of a monovinyl unsaturated nitrile monomer, 7-20 parts of rubber and 2-5 parts of an assistant. Products having excellent heat and impact resistances can be obtained through using the highly-impact-resistant and highly-heat-resistant ABS resin without adding any additives. The preparation method has the advantages of simple operation, substantially simplified technology and production cost reduction, is suitable for the industrialized production, and can satisfy the needs of the automobile field and the like.
Description
Technical field
The present invention relates to a kind of ABS resin and preparation method thereof, relate in particular to ABS resin of a kind of highly impact-resistant and heat-resistant and preparation method thereof.
Background technology
ABS resin has good shock strength, high rigidity and chemical resistant properties, but general resistance toheat is not high.The ABS resin such as automobile, motorcycle Application Areas requires material except having above-mentioned performance, must have excellent resistance toheat concurrently simultaneously.In order to meet the demand of material Application Areas, people attempt preparing heat-resisting ABS resin by the whole bag of tricks, as by adding heat resistance modified monomer to prepare ABS resin, by add heat resistance modified monomer in the mass polymerization flow process, synthesize heat-resisting ABS resin, by add in the heat-resistant monomer mixing process reaction in the response type forcing machine, prepare heat-resisting ABS resin etc. in emulsion polymerization process.
US 5,212, and 240 Dow Chemical companies adopt emulsion graft polymerization one mixing method to prepare heat-resisting ABS resin.At first obtain grafted rubber components by letex polymerization, then with flumaronitrile-styrene-acrylonitrile terpolymer blending, produce heat-resisting ABS resin.It is 2.8ft.1bs/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 118.3 ℃; Adopt the inspection of DSC dsc to find that the resin part is miscible, find that the interlaminar resin intermiscibility is better simultaneously, toughness of products is stronger.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 there is certain limitation.
As the stable on heating method that improves the ABS thermoplastic resin, known have one by introduce the method for alpha-methyl styrene or other similar monomers in copolyreaction.For example, US 4,874, and 829 generate multipolymer or trimeric method by alpha-methyl styrene, vinyl cyanide and maleimide monomer continuous polymerization, in order to break through the low-conversion of alpha-methyl styrene, use a large amount of highly active vinyl cyanide in feed composition.Adopt the final easy variable color of resin generated of aforesaid method and generate gel, this will cause the mechanical property of materials of heat-resisting ABS resin significantly to descend.
CN1126734A discloses and has adopted the maleimide modification to prepare the method for heat-resisting ABS resin.The method comprises mediates a kind of maleimide copolymer, a kind of ABS graft copolymer and optional a kind of AS multipolymer, thereby obtain heat-resisting master batch resin, and further that a kind of ABS graft copolymer and a kind of AS multipolymer and heat-resisting master batch resin is kneaded together.But although in component, maleimide copolymer has high heat-resisting characteristics, with common AS resin-phase ratio, 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 the method to have to add softening agent, lubricant etc., in the course of processing, must make additive dispersed in resin, but in the links such as injection molding, processing, additive will be penetrated on product surface and cause the outward appearance generation defect that suffers damage, and tends to reduce resistance toheat.
US 4,757,109 and Japanese Patent Publication No.1983-206657 propose a kind ofly by heat stable resin and ABS resin, to mix to improve the stable on heating method of ABS resin.Above-mentioned heat stable resin is generated with emulsion polymerization by maleimide monomer, vinyl nitrile compound monomer and aromatic ethylene base, and in resin, the maleimide monomer content is higher, and thermotolerance is better.Yet, because this heat-resistant monomer speed of reaction is fast, thermal discharge is large, and content is limited in resin.In order to break through this restriction, it is very complicated that polymerization process becomes; In polymer resin, the maleimide monomer content is higher, poorer with the ABS resin intermiscibility, thereby causes the product shock strength to descend.Commercial emulsion method heat-resisting ABS resin is vinylbenzene, vinyl cyanide and rubber generation letex polymerization to be obtained to the grafting rubbers copolymerization component of high glue content at present, the multipolymer that the olefinic monomers such as the heat-resistant monomers such as maleimide or maleic anhydride and vinyl cyanide, vinylbenzene are made, by being obtained two kinds of components by the twin screw extruder blending.In order to improve resistance toheat, add graft copolymer that certain limitation is arranged, thereby in product, rubber content can not be too high, therefore generally be difficult to reach product have high heat resistance can the time there is the high-impact performance.
Summary of the invention
Technical problem to be solved by this invention is to overcome the defect that the impact-resistance of ABS resin in prior art, anti-thermotolerance and over-all properties are difficult to take into account, and blended ABS resin of a kind of highly impact-resistant and heat-resistant and preparation method thereof is provided.
The present invention solves the problems of the technologies described above by the following technical programs.
The invention provides a kind of preparation method of ABS resin of highly impact-resistant and heat-resistant, it comprises the steps: that the blending extrusion temperature is 190 ~ 220 ℃ and get final product by the ABS resin of the ABS resin of mass polymerization gained and the letex polymerization gained ratio blending extrusion of 1:2 ~ 1:20 by weight;
Wherein, the ABS resin of described mass polymerization gained comprises composition and weight part are as follows:
Wherein, described mono vinyl arenes monomer can be the conventional mono vinyl arenes monomer used in this area, is preferably vinylbenzene, alpha-methyl styrene, α-ethyl styrene, halogenated styrenes or alpha-halogen ring-alkylated styrenes.Described halogenated styrenes is preferably alpha-chloro vinylbenzene and/or alpha-brominated vinylbenzene etc.Described alpha-halogen ring-alkylated styrenes is α-1-chloro-4-methyl-benzene and/or α-ethyl styrene etc. preferably.
Wherein, described mono-vinyl unsaturated nitrile monomer can be the conventional mono-vinyl unsaturated nitrile monomer used in this area, is preferably methacrylonitrile, vinyl cyanide, C
1-C
4One or more in alkyl vinyl nitrile and phenyl vinyl nitrile.
Wherein, described rubber is the conventional rubber used in this area, is preferably polyisoprene rubber, polybutadiene rubber or styrene-butadiene block copolymer rubber.
Wherein, described auxiliary agent is the conventional auxiliary agent used in this area, preferably comprises one or more in initiator, chain-transfer agent and mineral oil.
The bulk polymerization of ABS resin is described later in detail in many documents, as disclosed technology of patent such as US5240993, US5569709 and US5414045, be to comprise that mono vinyl arenes monomer, mono-vinyl unsaturated nitrile monomer, rubber are that main material reacts acquisition by continuous bulk polymerization.Drink difference owing to adopting on mass polymerization detailed process and equipment, the resin Composition content that mass polymerization obtains is different, also there are larger difference in external phase and disperse phase ratio, the residing zone of average rubber particle size and rubber size and SAN(styrene-acrylonitrile copolymer in addition) the change of molecular weight is larger, and the ABS resin of the described mass polymerization gained in the present invention is to adopt Chinese Patent Application No. 200410099053.X bulk technique to be prepared from.
Wherein, in the ABS resin of described mass polymerization gained, the particle diameter of rubber particles is 1 ~ 10 μ m, 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
5.The ABS resin of this mass polymerization gained has low shock strength, middle shock strength or high impact strength, and (in the same industry, the technician is by being accustomed to 10KJ/m
2Hereinafter referred to as low shock strength, 10 ~ be less than 17KJ/m
2For middle shock strength, 17KJ/m
2Be more than high impact strength), resistance toheat is general, approximately 95 ℃ of left and right.
Wherein, in the ABS resin of described letex polymerization gained, the rubber particles of particle diameter in 0.1 ~ 2 μ m scope accounts for more than 50% of rubber particles cumulative volume, and the ABS resin of this letex polymerization gained has middle shock strength and good resistance toheat, approximately 105 ℃ of left and right.
In the present invention, after the ABS resin of the ABS resin of described mass polymerization gained and described letex polymerization gained is dispersed by described blending extrusion, rubber phase wherein is by new spatiality redistribution.After blend reaches a certain proper ratio, in above-mentioned two kinds of components, the external phase SAN of rubber phase and different molecular weight reaches optimum regime.Thereby the graft rubber upper layer at utmost reduces aggregation extent and effectively prevents the contact between the rubber phase region in this case.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 the mechanical property that has improved heat-resisting ABS resin is as erosion-resisting characteristics.When components do match, blend components can not cause because of a certain component that wherein erosion-resisting characteristics is lower the product erosion-resisting characteristics to descend, and can keep on the contrary the high-performance of high-impact component, even can make the erosion-resisting characteristics of blend product higher than arbitrary component.
Wherein, the method that the method for described blending extrusion and condition are this area routine and condition, generally adopt extruding pelletization in the blending extrusion machine to get final product.
The present invention also provides a kind of ABS resin of the highly impact-resistant and heat-resistant made by above-mentioned preparation method.
On the basis that meets this area general knowledge, above-mentioned each optimum condition, but arbitrary combination obtains the preferred embodiments of the invention.
Agents useful for same of the present invention and raw material be commercially available obtaining all.
Positive progressive effect of the present invention is:
The ABS resin of highly impact-resistant and heat-resistant of the present invention is without adding any additive, can obtain all very excellent products of heat-resisting and shock resistance, simple to operate, technique is simplified greatly, reduce production cost, be suitable for suitability for industrialized production, can meet the needs of the Application Areass such as automobile.
Embodiment
Mode below by embodiment further illustrates the present invention, but does not therefore limit the present invention among described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example, according to ordinary method and condition, or select according to catalogue.
Embodiment 1:
By the ABS resin of the ABS resin of mass polymerization gained (component A1) and letex polymerization gained (B component 1) ratio of 1:2 by weight, carry out extruding pelletization after blend with 50Kg/h in the twin screw extruder that is TE-50 in model, the blending extrusion temperature is 220 ℃, obtains.
Wherein: the composition and the weight part thereof that in component A1, comprise are as follows:
In component A1, the particle diameter of rubber particles is 4 ~ 10 μ m, and external phase SAN weight-average molecular weight is in 7.5 * 10
4~ 3.0 * 10
5In scope.Adopt the ASTMD-256-02 standard to be detected, its shock strength is 12.48KJ/m
2Adopting ASTMD-1525-00 standard detection vicat softening temperature is 94.2 ℃.
B component 1: be the ABS resin of letex polymerization gained, trade names are that Lustran HH1827(Bayer A.G produces), the rubber particles that wherein particle diameter is 0.1 ~ 2 μ m accounts for more than 50% of rubber particles cumulative volume.Adopt the ASTMD-256-02 standard to be detected, its shock strength is 15.98KJ/m
2Adopting ASTMD-1525-00 standard detection vicat softening temperature is 109.6 ℃.
The shock strength that records product is 28.15KJ/m
2, the increased value of the relative B component 1 of its shock strength is 12.17KJ/m
2, the amplification of its shock strength reaches 76.2%.Its shock strength is far above the shock strength of component A1 and B component 1.It is 106 ~ 109.6 ℃ that this product is adopted to ASTMD-256-02 standard detection vicat softening temperature, has higher resistance toheat.
Embodiment 2:
By the ABS resin of the ABS resin of mass polymerization gained (component A2) and letex polymerization gained (B component 2) ratio of 1:20 by weight, carry out extruding pelletization after blend with 50Kg/h in the twin screw extruder that is TE-50 in model, the blending extrusion temperature is 190 ℃, obtains.
Wherein: the composition and the weight part thereof that in component A2, comprise are as follows:
In component A2, the particle diameter of rubber particles is 1 ~ 10 μ m, and external phase SAN weight-average molecular weight is in 5 * 10
4~ 2.0 * 10
5In scope.Adopt the ASTMD-256-02 standard to be detected, its shock strength is 11.26KJ/m
2Adopting ASTMD-1525-00 standard detection vicat softening temperature is 92.1 ℃.
B component 2: be the ABS resin of letex polymerization gained, trade names are that Lustran HH1827(Bayer A.G produces), the rubber particles that wherein particle diameter is 0.1 ~ 2 μ m accounts for more than 50% of rubber particles cumulative volume.Adopt the ASTMD-256-02 standard to be detected, its shock strength is 15.98KJ/m
2Adopting ASTMD-1525-00 standard detection vicat softening temperature is 109.6 ℃.
The shock strength that records product is 25.73KJ/m
2, the increased value of the relative B component 2 of its shock strength is 9.75KJ/m
2, the amplification of its shock strength reaches 61.1%.Its shock strength is far above the shock strength of component A2 and B component 2.It is 103 ~ 108 ℃ that this product is adopted to ASTMD-256-02 standard detection vicat softening temperature, has higher resistance toheat.
Embodiment 3:
By the ABS resin of the ABS resin of mass polymerization gained (component A3) and letex polymerization gained (B component 3) ratio of 1:10 by weight, carry out extruding pelletization after blend with 50Kg/h in the twin screw extruder that is TE-50 in model, the blending extrusion temperature is 200 ℃, obtains.
Wherein: the composition and the weight part thereof that in component A3, comprise are as follows:
In component A3, the particle diameter of rubber particles is 1 ~ 8 μ m, and external phase SAN weight-average molecular weight is in 1.5 * 10
5~ 3.5 * 10
5In scope.Adopt the ASTMD-256-02 standard to be detected, its shock strength is 15.63KJ/m
2Adopting ASTMD-1525-00 standard detection vicat softening temperature is 96.4 ℃.
B component 3: be the ABS resin of letex polymerization gained, trade names are that STAREX SR0320(Korea S SAMSUNG company produces), the rubber particles that wherein particle diameter is 0.1 ~ 2 μ m accounts for more than 50% of rubber particles cumulative volume.Adopt the ASTMD-256-02 standard to be detected, its shock strength is 15.79KJ/m
2Adopting ASTMD-1525-00 standard detection vicat softening temperature is 105.9 ℃.
The shock strength that records product is 32.55KJ/m
2, the increased value of the relative B component 3 of its shock strength is 16.76KJ/m
2, the amplification of its shock strength reaches 106.1%.Its shock strength is far above the shock strength of component A3 and B component 3.It is 104.5 ~ 107 ℃ that this product is adopted to ASTMD-256-02 standard detection vicat softening temperature, has higher resistance toheat.
Claims (9)
1. the preparation method of the ABS resin of a highly impact-resistant and heat-resistant, its comprise the steps: by the ABS resin of the ABS resin of mass polymerization gained and letex polymerization gained by weight the ratio of 1:2 ~ 1:20 in 190 ~ 220 ℃ of lower blending extrusions, obtain;
Wherein, the ABS resin of described mass polymerization gained comprises composition and weight part are as follows:
2. preparation method as claimed in claim 1, is characterized in that, described mono vinyl arenes monomer is vinylbenzene, alpha-methyl styrene, α-ethyl styrene, halogenated styrenes or alpha-halogen ring-alkylated styrenes; Described halogenated styrenes is alpha-chloro vinylbenzene and/or alpha-brominated vinylbenzene; Described alpha-halogen ring-alkylated styrenes is α-1-chloro-4-methyl-benzene and/or α-ethyl styrene.
3. preparation method as claimed in claim 1, is characterized in that, described mono-vinyl unsaturated nitrile monomer is methacrylonitrile, vinyl cyanide, C
1-C
4One or more in alkyl vinyl nitrile and phenyl vinyl nitrile.
4. preparation method as claimed in claim 1, is characterized in that, described rubber is polyisoprene rubber, polybutadiene rubber or styrene-butadiene block copolymer rubber.
5. preparation method as claimed in claim 1, is characterized in that, described auxiliary agent comprises one or more in initiator, chain-transfer agent and mineral oil.
6. preparation method as claimed in claim 1, is characterized in that, in the ABS resin of described mass polymerization gained, the particle diameter of rubber particles is 1 ~ 10 μ m, 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
5.
7. preparation method as claimed in claim 1, is characterized in that, in the ABS resin of described letex polymerization gained, the rubber particles of particle diameter in 0.1 ~ 2m scope accounts for more than 50% of rubber particles cumulative volume.
8. preparation method as claimed in claim 1, is characterized in that, described blending extrusion is extruding pelletization in the blending extrusion machine.
9. the ABS resin of the highly impact-resistant and heat-resistant that a preparation method as described as claim 1 ~ 8 any one makes.
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Application publication date: 20131204 |