CN103450622A - Modified ABS resin and preparation method thereof - Google Patents
Modified ABS resin and preparation method thereof Download PDFInfo
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- CN103450622A CN103450622A CN201210177547XA CN201210177547A CN103450622A CN 103450622 A CN103450622 A CN 103450622A CN 201210177547X A CN201210177547X A CN 201210177547XA CN 201210177547 A CN201210177547 A CN 201210177547A CN 103450622 A CN103450622 A CN 103450622A
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- abs resin
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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
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
Abstract
The invention discloses a modified ABS and a preparation method thereof. The preparation method comprises the following steps: preparing an ABS resin I through a continuous bulk polymerization method; carrying out mixing extrusion on the ABS resin I and a heatproof ABS resin II in a weight ratio of 2:5-3:20 at 180-220 DEG C to obtain the modified ABS. Rubber particles of the ABS resin I have a particle size of 3-8 mum; a continuous phase styrene-acrylonitrile copolymer of the ABS resin I has a molecular weight of 1.5*10<5>-3.5*10<5>; and the rubber particles with particle size within 0.1-2 mum in the ABS resin II account for more than 50% of the bulk volume of the rubber particles. The modified ABS resin provided by the invention has high heat resistance and high impact resistance. The preparation method provided by the invention has simple operations, substantially simplified technology and reduced production cost, is suitable for industrialized production and can satisfy requirements of the application fields such as automobile.
Description
Technical field
The present invention relates to a kind of modified ABS resin 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.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 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 a kind of modified ABS resin and preparation method thereof is provided.This modified ABS resin is without adding any additive, can obtain all very excellent products of heat-resisting and shock resistance, and simple to operate, technique is simplified greatly, has reduced production cost, is suitable for suitability for industrialized production, can meet the needs of the Application Areas such as automobile.
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 modified ABS resin, it comprises the steps: with the standby ABS resin I of continuous bulk polymerization legal system, ABS resin I to be mixed and extrudes in 180 ~ 220 ℃ with the weight part ratio of 2: 5 ~ 3: 20 with heat-resisting ABS resin II, obtains; Wherein, the particle diameter of the rubber particles of described ABS resin I is 3 ~ 8 μ m, and the external phase styrene-acrylonitrile copolymer of described ABS resin I (being called for short SAN) molecular weight is 1.5 * 10
5~ 3.5 * 10
5, in described heat-resisting ABS resin II, the rubber particles of particle diameter in 0.1 ~ 2 μ m accounts for more than 50% of rubber particles cumulative volume.
Wherein, the technology and condition of described continuous bulk polymerization method can adopt the technology and condition of this area routine.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.In the present invention, described continuous bulk polymerization method preferably adopts the technique of continuous bulk polymerization of Chinese Patent Application No. 200410099053.X to be prepared from.
Wherein, the raw material of described ABS resin I preferably comprises the component of following weight parts: 50 ~ 60 parts of mono vinyl arenes monomers, 17 ~ 28 parts of mono-vinyl unsaturated nitrile monomers, 10 ~ 18 parts of graft rubber particles and 1 ~ 5 part of auxiliary agent.
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.
Wherein, described ABS resin I have middle shock strength or high impact strength (those skilled in the art by custom by 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), the general approximately 95 ℃ of left and right of resistance toheat.
Wherein, described heat-resisting ABS resin II can be in this area arbitrary resistance toheat in the ABS resin more than 105 ℃, as long as wherein the rubber particles of particle diameter in 0.1 ~ 2 μ m accounts for more than 50% of rubber particles cumulative volume.
Wherein, the method that the method that described mixing is extruded 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 modified ABS resin 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:
Modified ABS resin 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:
ABS resin I that will be standby by the continuous bulk polymerization legal system and the heat-resisting ABS resin II ratio of 2: 5 by weight, extruding pelletization after being mixed with 50Kg/h in the twin screw extruder that is TE-50 in model, mixing extrusion temperature is 220 ℃, obtains.
Wherein: composition and the weight part thereof of the raw material of ABS resin I are as follows: 60 parts of vinylbenzene, 17 parts of methacrylonitriles, 18 parts of polyisoprene rubbers, 2 parts of organo-peroxide (initiators, Luperox 11M75, ATOFINA company product), 2 parts of alpha-methyl styrene dimer mixtures (chain-transfer agent) and 1 part of mineral oil; In this ABS resin I, the particle diameter of rubber particles is 3 ~ 8 μ m, and external phase SAN weight-average molecular weight is in 1.5 * 10
5~ 2.5 * 10
5in scope.Adopt the ASTMD-256-02 standard to be detected, its shock strength is 14.62KJ/m
2; Adopting ASTMD-1525-00 standard detection vicat softening temperature is 95.3 ℃.
Wherein, heat-resisting ABS resin II is the ABS resin of letex polymerization gained, and 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
2; Adopting ASTMD-1525-00 standard detection vicat softening temperature is 109.6 ℃.
The shock strength that records the modified ABS resin made is 24.76KJ/m
2, the increased value of the relative heat-resisting ABS resin II of its shock strength is 8.78KJ/m
2, the amplification of its shock strength reaches 54.9%.Its shock strength is far above the shock strength of ABS resin I and heat-resisting ABS resin II.It is 105.5 ~ 109.2 ℃ that this product is adopted to ASTMD-256-02 standard detection vicat softening temperature, has higher resistance toheat.
Embodiment 2:
ABS resin I that will be standby by the continuous bulk polymerization legal system and the heat-resisting ABS resin II ratio of 3: 20 by weight, extruding pelletization after being mixed with 50Kg/h in the twin screw extruder that is TE-50 in model, mixing extrusion temperature is 200 ℃, obtains.
Wherein: composition and the weight part thereof of the raw material of ABS resin I are as follows: 50 parts of α-ethyl styrenes, 28 parts of vinyl cyanide, 18 parts of polybutadiene rubbers, 1.5 parts of organo-peroxide (initiators, Luperox11M75, ATOFINA company product), 1.5 parts of alpha-methyl styrene dimer mixtures (chain-transfer agent) and 1 part of mineral oil; In this ABS resin I, the particle diameter of rubber particles is 3 ~ 8 μ m, and external phase SAN weight-average molecular weight is in 2.0 * 10
5~ 3.5 * 10
5in scope.Adopt the ASTMD-256-02 standard to be detected, its shock strength is 17.14KJ/m
2; Adopting ASTMD-1525-00 standard detection vicat softening temperature is 95.6 ℃.
Wherein, heat-resisting ABS resin II is the ABS resin of letex polymerization gained, and 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
2; Adopting ASTMD-1525-00 standard detection vicat softening temperature is 105.9 ℃.
The shock strength that records the modified ABS resin made is 28.25KJ/m
2, the increased value of the relative heat-resisting ABS resin II of its shock strength is 12.46KJ/m
2, the amplification of its shock strength reaches 78.9%.Its shock strength is far above the shock strength of ABS resin I and heat-resisting ABS resin II.It is 105.7 ~ 108.2 ℃ that this product is adopted to ASTMD-256-02 standard detection vicat softening temperature, has higher resistance toheat.
Embodiment 3:
ABS resin I that will be standby by the continuous bulk polymerization legal system and heat-resisting ABS resin II be the ratio of 3:20 by weight, extruding pelletization after being mixed with 50Kg/h in the twin screw extruder that is TE-50 in model, and mixing extrusion temperature is 180 ℃, obtains.
Wherein: composition and the weight part thereof of the raw material of ABS resin I are as follows: 59 parts of alpha-brominated vinylbenzene, 28 parts of methacrylonitriles, 12 parts of polybutadiene rubbers, 0.4 part of organo-peroxide (initiator, Luperox11M75, ATOFINA company product), 0.4 part of alpha-methyl styrene dimer mixture (chain-transfer agent) and 0.2 part of mineral oil; In this ABS resin I, the particle diameter of rubber particles is 3 ~ 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 12.37KJ/m
2; Adopting ASTMD-1525-00 standard detection vicat softening temperature is 95.1 ℃.
Wherein, heat-resisting ABS resin II is the ABS resin of letex polymerization gained, and 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
2; Adopting ASTMD-1525-00 standard detection vicat softening temperature is 105.9 ℃.
The shock strength that records the modified ABS resin made is 26..58KJ/m
2, the increased value of the relative heat-resisting ABS resin II of its shock strength is 10.79KJ/m
2, the amplification of its shock strength reaches 68.3%.Its shock strength is far above the shock strength of ABS resin I and heat-resisting ABS resin II.It is 105.4 ~ 160.5 ℃ that this product is adopted to ASTMD-256-02 standard detection vicat softening temperature, has higher resistance toheat.
Claims (8)
1. the preparation method of a modified ABS resin, it comprises the steps: with the standby ABS resin I of continuous bulk polymerization legal system, ABS resin I to be mixed and extrudes in 180 ~ 220 ℃ with the weight part ratio of 2: 5 ~ 3: 20 with heat-resisting ABS resin II, obtains; Wherein, the particle diameter of the rubber particles of described ABS resin I is 3 ~ 8 μ m, and the external phase styrene-acrylonitrile copolymer molecular weight of described ABS resin I is 1.5 * 10
5~ 3.5 * 10
5, in described heat-resisting ABS resin II, the rubber particles of particle diameter in 0.1 ~ 2 μ m accounts for more than 50% of rubber particles cumulative volume.
2. preparation method as claimed in claim 1, it is characterized in that, the raw material of described ABS resin I comprises the component of following weight parts: 50 ~ 60 parts of mono vinyl arenes monomers, 17 ~ 28 parts of mono-vinyl unsaturated nitrile monomers, 10 ~ 18 parts of graft rubber particles and 1 ~ 5 part of auxiliary agent.
3. 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.
4. 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.
5. preparation method as claimed in claim 1, is characterized in that, described rubber is polyisoprene rubber, polybutadiene rubber or styrene-butadiene block copolymer rubber.
6. 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.
7. preparation method as claimed in claim 1, is characterized in that, the mixing of stating is extruded as extruding pelletization in the blending extrusion machine.
8. the modified ABS resin that preparation method as described as claim 1 ~ 7 any one makes.
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|---|---|---|---|
| CN201210177547XA CN103450622A (en) | 2012-06-01 | 2012-06-01 | Modified ABS resin and preparation method thereof |
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|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104072934A (en) * | 2014-06-13 | 2014-10-01 | 安徽皖东化工有限公司 | Heat-resistant flame-retardant impact-resistant modified acrylonitrile butadiene styrene (ABS) resin |
-
2012
- 2012-06-01 CN CN201210177547XA patent/CN103450622A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104072934A (en) * | 2014-06-13 | 2014-10-01 | 安徽皖东化工有限公司 | Heat-resistant flame-retardant impact-resistant modified acrylonitrile butadiene styrene (ABS) resin |
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Application publication date: 20131218 |