CN104845026A - Heat-resistant ABS (acrylonitrile-butadiene-styrene) resin composition high in scratch resistance and preparation method of heat-resistant ABS resin composition - Google Patents
Heat-resistant ABS (acrylonitrile-butadiene-styrene) resin composition high in scratch resistance and preparation method of heat-resistant ABS resin composition Download PDFInfo
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- CN104845026A CN104845026A CN201510218335.5A CN201510218335A CN104845026A CN 104845026 A CN104845026 A CN 104845026A CN 201510218335 A CN201510218335 A CN 201510218335A CN 104845026 A CN104845026 A CN 104845026A
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Abstract
The invention relates to a heat-resistant ABS (acrylonitrile-butadiene-styrene) resin composition high in scratch resistance and a preparation method of the heat-resistant ABS resin composition. The heat-resistant ABS resin composition comprises, by weight, 100 parts of acrylonitrile-butadiene-styrene, 5-40 parts of methyl methacrylate-styrene-maleic anhydride terpolymer, 0.2-1.0 part of light stabilizer, 0.5-2.0 parts of other additives. The preparation method includes the steps of stirring and mixing the raw materials in a high-speed mixer fully to obtain a mixture; feeding the mixture into a twin-screw extruder via a metering device; subjecting the mixture to melting and compositing by the aid of conveying, shearing and mixing of screws; subjecting the molten and composited raw materials to re-extrusion, bracing, cooling and granulating to obtain the heat-resistant ABS resin composition high in scratch resistance. The heat-resistant ABS resin composition is not only high in scratch resistance, but also high in mechanical property, weather resistance and heat stability, and thereby being applicable to the field of automotive interior parts.
Description
Technical field
The present invention relates to technical field of polymer materials, relate to a kind of material being applicable to automotive upholstery and preparation method thereof, be specifically related to a kind of to there is heat-proof ABS resin composition of excellent scratch resistance and preparation method thereof.
Background technology
ABS resin has excellent outward appearance, mechanical property, chemical-resistant, dimensional stability and tint permanence.The ABS resin of commercial various different grades, as flame retardant grade, high lighting level, resistance to thermal level, height rush level etc., at automobile, household electrical appliances, electronic apparatus, the different field such as office appliance have a wide range of applications.Wherein heat-proof ABS is the most general in the application of automotive field, especially the inside gadget such as automobile door plate, secondary panel board, sun visor, saucer, glove box, door handle.In addition, heat-proof ABS also can be applicable to the exterior trim fields such as rear vision mirror, grid, license plate, taillight.
For reaching the object of low gloss, automotive upholstery has dermatoglyph structure usually.The scraping effect that in use suffers of inside gadget without spraying is easy to cause the destruction of dermatoglyph, and then causes deteriorated appearance, even loses efficacy.So scratch resistance is a vital performance concerning automotive upholstery application.The pencil hardness of heat-proof ABS, for being generally HB level (500g load), although its scratch resistance is better than PP and PC, but can not meet the requirement of scrape resistant well, and the scratch resistance therefore improving heat-proof ABS is a problem demanding prompt solution.
As a rule, the surface hardness improving resin can improve the scratch resistance of resin, and the surface hardness improving resin then generally can be realized by following two kinds of methods.Wherein the most commonly add the high resin of surface hardness, as PMMA, the resins such as polyether-ether-ketone (PEEK).Because PMMA and ABS has good consistency, add the surface hardness that PMMA resin can increase heat-proof ABS, thus improve its scratch resistance.But the interpolation of PMMA, can cause the deterioration of heat-proof ABS mechanical property, especially obvious on the impact of shock strength.And the thermostability of PMMA is bad, its shaping ceiling temp is mostly below 250 DEG C, and thus when heat-resisting ABS resin about 250 DEG C mold temperatures, PMMA is easy to thermal destruction occurs, and final impact worsens mechanical property and outward appearance.In addition, the filler adding high rigidity also can increase the surface hardness of heat-proof ABS.But as everyone knows, the interpolation of mass filler significantly can reduce the mechanical property of matrix resin.And although the interpolation of filler adds the surface hardness of resin, the resin brittle failure mode that it causes, also easily causes scratch visual, even also likely causes the decline of macroscopic scratch on the contrary.
In general, N-phenylmaleimide-phenylethylene-maleic anhydride terpolymer (as electrochemical IP series), styrene-maleic anhydride copolymer, alpha-methyl styrene-acrylonitrile copolymer is the heat-proof modifier of the most frequently used heat-proof ABS, but these heat-proof modifiers there is no benefit to the scraping and wiping resistance performance of heat-proof ABS, the lifting of weather resistance.
Summary of the invention
For the technological deficiency of above-mentioned existing heat-proof ABS, the object of the present invention is to provide and a kind of there is heat-proof ABS resin composition of excellent scratch resistance and preparation method thereof, to solve in prior art the problems such as mechanical property worsens, scratch resistance is not good, thermostability is bad existed when preparing heat-resisting ABS resin.The present invention adopts in heat-proof ABS, adds MMA-St-MAH terpolymer, while can improving ABS thermotolerance, can also obviously improve heat-proof ABS scratch resistance, and this heat-proof ABS also has excellent thermostability, mechanical property and weather resistance.Therefore, heat-proof ABS resin composition provided by the invention not only has excellent scraping and wiping resistance performance, and has excellent mechanical property, weather resistance and thermostability.Be applicable to very much being applied to automotive upholstery field.
The object of the invention is to be achieved through the following technical solutions:
The present invention relates to a kind of heat-proof ABS resin composition with excellent scratch resistance, comprise each component of following parts by weight:
As optimal technical scheme, the weight-average molecular weight of described ABS resin is 80000 ~ 150000; In described ABS resin, the mass percentage content of divinyl rubber is 12% ~ 18%.When butadiene rubber content lower than 12% time, the shock strength of heat-proof ABS can significantly reduce.When divinyl rubber content higher than 18% time, rigidity of material and processibility can decline to a great extent.More preferably the weight-average molecular weight of ABS resin is 90000 ~ 130000; In ABS resin, the mass percentage content of divinyl rubber is 14% ~ 18%.
As optimal technical scheme, the mass percentage content of the methyl methacrylate in described Methyl Methacrylate-Styrene-maleic anhydride terpolymer is 35% ~ 70%, cinnamic mass percentage content is 5% ~ 51%, and the mass percentage content of maleic anhydride is 14% ~ 25%.When MMA content lower than 35% time, higher surface hardness can not be provided, and MMA content higher than 70% time, processibility and thermostability will worsen.When MAH content lower than 14% time, the thermotolerance of heat-proof ABS can not effectively promote, and the content of MAH higher than 25% time, the thermostability of MMA-St-MAH will be deteriorated.
As optimal technical scheme, described photostabilizer is one or more mixtures in salicylate, benzophenone, triazines, the UV absorption agent of benzotriazole category and hindered amines free radical scavenger.Described benzophenone UV absorber is as Cyasorb UV-53; Described triazines UV absorption agent is as Cyasorb UV-1164; Described benzotriazole uv absorbers is as Tinuvin 326, Cyasorb UV-5411; Described hindered amines free radical scavenger is as Tinuvin 770, Cyasorb UV-3346.
As optimal technical scheme, other auxiliary agents described are selected from one or more the mixture in silane coupling agent, titanate coupling agent, Hinered phenols antioxidant, phosphite ester kind antioxidant, ethylene bis stearic acid amide, pentaerythritol stearate, Magnesium Stearate, calcium stearate.Specifically comprise antioxygen B900, content is 0.3phr; Lubricate EBS, content is 1.0phr.
The invention still further relates to a kind of preparation method with the heat-proof ABS resin composition of excellent scratch resistance of the present invention, described preparation method comprises the steps:
Step one, to get the raw materials ready by described component and parts by weight;
Step 2, described acrylonitrile-butadiene-styrene resin, Methyl Methacrylate-Styrene-maleic anhydride terpolymer, photostabilizer, other auxiliary agents are stirred in high-speed mixer fully mixing after, send in twin screw extruder through measuring apparatus, the conveying of screw rod, shearing and mixing under, material melting, compound, again through extruding, tie rod, cooling, pelletizing step, obtain the heat-proof ABS resin composition with excellent scratch resistance.
As optimal technical scheme, the screw slenderness ratio of described twin screw extruder is 36 ~ 44, and described twin screw extruder has temperature control unit and vacuum extractor.
As optimal technical scheme, the extrusion temperature of described twin screw extruder is 200 ~ 250 DEG C, and screw speed is 200 ~ 500 revs/min.
Compared with prior art, the present invention has following beneficial effect:
The present composition adopts Methyl Methacrylate-Styrene-maleic anhydride terpolymer as the heat-proof modifier of heat-proof ABS, while making to improve heat-proof ABS scraping and wiping resistance performance, can also have excellent mechanical property, thermostability and weather resistance, this is that prior art can not realize simultaneously simultaneously.This will increase the range of application of heat-proof ABS in automotive trim field greatly.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.Following examples will contribute to those skilled in the art and understand the present invention further, but not limit the present invention in any form.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, some distortion and improvement can also be made.These all belong to protection scope of the present invention.
Component is related to and characteristic is as follows in following embodiment and comparative example:
ABS-1 resin, weight-average molecular weight 90,000, butadiene content 18%;
ABS-2 resin, weight-average molecular weight 110,000, butadiene content 16%;
ABS-3 resin, weight-average molecular weight 130,000, butadiene content 14%;
MMA-St-MAH-A resin, MMA content 35%, MAH content 14%;
MMA-St-MAH-B resin, MMA content 45%, MAH content 18%;
MMA-St-MAH-C resin, MMA content 60%, MAH content 20%;
MMA-St-MAH-D resin, MMA content 70%, MAH content 18%;
MMA-St-MAH-E resin, MMA content 50%, MAH content 25%;
MMA-St-MAH-F resin, MMA content 50%, MAH content 28%;
N-phenylmaleimide-styrene-maleic anhydride copolymer (N-PMI-St-MAH) is electrochemical MSNH;
PMMA resin is the V040 of French Arkema.
embodiment 1 ~ 7
Embodiment 1 ~ 7 relates to and a kind ofly has heat-proof ABS resin composition of excellent scratch resistance and preparation method thereof; The feed composition that described resin combination adopts is as shown in table 1, is prepared as follows:
Step one, get the raw materials ready by the component shown in table 1 and parts by weight, for better evaluating and testing weather resistance, each embodiment adds 1 weight part Masterbatch all in addition;
Step 2, by ABS resin, MMA-St-MAH terpolymer, photostabilizer, other auxiliary agents, look is female in high-speed mixer, stir fully mixing after, send in twin screw extruder through measuring apparatus, the conveying of screw rod, shearing and mixing under, material melting, compound, again through extruding, tie rod, cooling, pelletizing step, obtain the heat-proof ABS resin composition with excellent scratch resistance.
Wherein the screw slenderness ratio of twin screw extruder is 40, and the extrusion temperature leading portion of twin screw extruder is 200 ~ 230 DEG C, and stage casing temperature is 240 ~ 260 DEG C, and head temperature is 250 DEG C.Screw speed is 300 revs/min.
In the present invention, photostabilizer is not limited to enumerating in table 1, can be one or more mixtures in salicylate, benzophenone, triazines, the UV absorption agent of benzotriazole category and hindered amines free radical scavenger, and consumption can be 0.2 ~ 1.0 part.Other auxiliary agents can be selected from one or more the mixture in silane coupling agent, titanate coupling agent, Hinered phenols antioxidant, phosphite ester kind antioxidant, ethylene bis stearic acid amide, pentaerythritol stearate, Magnesium Stearate, calcium stearate; Consumption is 0.5 ~ 2.0 part.
comparative example 1 ~ 3
Comparative example 1 ~ 3 relates to a kind of ABS resin composition and method of making the same; The feed composition that described resin combination adopts is as shown in table 1, is prepared as follows:
Step one, get the raw materials ready by the component shown in table 1 and parts by weight, for better evaluating and testing weather resistance, each comparative example adds 1 weight part Masterbatch all in addition;
Step 2, each component stirred in high-speed mixer fully mixing after, send in twin screw extruder through measuring apparatus, the conveying of screw rod, shearing and mixing under, material melting, compound, again through extruding, tie rod, cooling, pelletizing step, obtain the heat-proof ABS resin composition with excellent scratch resistance.
Wherein the screw slenderness ratio of twin screw extruder is 40, and the extrusion temperature leading portion of twin screw extruder is 200 ~ 230 DEG C, and stage casing temperature is 240 ~ 260 DEG C, and head temperature is 250 DEG C.Screw speed is 300 revs/min.
Carry out performance test to embodiment 1 ~ 7 and comparative example 1 ~ 3, testing method is described below:
The test of tensile strength is carried out according to ASTM D638 standard, and test speed is 50mm/min.
The test of notched Izod impact strength is carried out according to ASTM D256 standard.
Melting index test is carried out according to ASTM D1238 standard, load 10kg, probe temperature 220 DEG C.
Vicat softening point temperature carries out according to ASTM D1525 standard, load 5kg, heat-up rate 50 DEG C/h.
Weathering resistance test is carried out according to SAE J2412 automotive upholstery standard, and irradiance 0.55W/m2@340nm, irradiation total energy is 601KJ/m2.For testing aberration better, by resin-made for grey.
Surface hardness test is carried out according to GB/T6739 standard.
Heat stability testing uses thermogravimetic analysis (TGA) (TGA) method, 10 DEG C/min temperature rise rate, and temperature time weightless using 2% is as criterion.
Test result is as shown in table 1.
Table 1
Can learn from each embodiment of table 1 and comparative example, the present invention adopts MMA-St-MAH as heat-proof modifier, can significantly improve pencil hardness and the thermotolerance of heat-proof ABS, thus improve its scratch resistance.In addition, the more important thing is, while improving scratch resistance, can also not obvious affect thermostability and mechanical property while, significantly promote its weather resistance.The over-all properties of the heat-proof ABS especially prepared by embodiment 3,4,5,6,7 is very excellent.Otherwise the heat-proof ABS of tradition preparation, as comparative example 1, then has obviously poor scratch resistance, processing characteristics and weathering resistance.And adopt PMMA to go to improve hardness and weathering resistance, then as shown in comparative example 2, shock strength, processing characteristics and thermostability can be had a strong impact on.If adopt the MMA-St-MAH (comparative example 3) that MAH content is higher, it is also very significant to the deterioration degree of thermostability.Visible the present invention can provide a kind of heat-proof ABS with excellent scratch resistance, weathering resistance, thermostability, mechanical property.
Above specific embodiments of the invention are described.It is to be appreciated that the present invention is not limited to above-mentioned particular implementation, those skilled in the art can make various distortion or amendment within the scope of the claims, and this does not affect flesh and blood of the present invention.
Claims (8)
1. there is a heat-proof ABS resin composition for excellent scratch resistance, it is characterized in that, comprise each component of following parts by weight:
2. the heat-proof ABS resin composition with excellent scratch resistance according to claim 1, is characterized in that, the weight-average molecular weight of described ABS resin is 80000 ~ 150000; In described ABS resin, the mass percentage content of divinyl rubber is 12% ~ 18%.
3. the heat-proof ABS resin composition with excellent scratch resistance according to claim 1, it is characterized in that, the mass percentage content of the methyl methacrylate in described Methyl Methacrylate-Styrene-maleic anhydride terpolymer is 35% ~ 70%, cinnamic mass percentage content is 5% ~ 51%, and the mass percentage content of maleic anhydride is 14% ~ 25%.
4. the heat-proof ABS resin composition with excellent scratch resistance according to claim 1, it is characterized in that, described photostabilizer is one or more in salicylate, benzophenone, triazines, the UV absorption agent of benzotriazole category and hindered amines free radical scavenger.
5. the heat-proof ABS resin composition with excellent scratch resistance according to claim 1, it is characterized in that, other auxiliary agents described are selected from one or more the mixture in silane coupling agent, titanate coupling agent, Hinered phenols antioxidant, phosphite ester kind antioxidant, ethylene bis stearic acid amide, pentaerythritol stearate, Magnesium Stearate, calcium stearate.
6. the preparation method with the heat-proof ABS resin composition of excellent scratch resistance according to any one of Claims 1 to 5, is characterized in that, described preparation method comprises the steps:
Step one, to get the raw materials ready by described component and parts by weight;
Step 2, described acrylonitrile-butadiene-styrene resin, Methyl Methacrylate-Styrene-maleic anhydride terpolymer, photostabilizer, other auxiliary agents are stirred in high-speed mixer fully mixing after, send in twin screw extruder through measuring apparatus, the conveying of screw rod, shearing and mixing under, material melting, compound, again through extruding, tie rod, cooling, pelletizing step, obtain the heat-proof ABS resin composition with excellent scratch resistance.
7. the preparation method with the heat-proof ABS resin composition of excellent scratch resistance according to claim 6, is characterized in that, the screw slenderness ratio of described twin screw extruder is 36 ~ 44, and described twin screw extruder has temperature control unit and vacuum extractor.
8. the preparation method with the heat-proof ABS resin composition of excellent scratch resistance according to claim 6, is characterized in that, the extrusion temperature of described twin screw extruder is 200 ~ 250 DEG C, and screw speed is 200 ~ 500 revs/min.
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| CN201510218335.5A CN104845026A (en) | 2015-04-30 | 2015-04-30 | Heat-resistant ABS (acrylonitrile-butadiene-styrene) resin composition high in scratch resistance and preparation method of heat-resistant ABS resin composition |
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| CN201510218335.5A CN104845026A (en) | 2015-04-30 | 2015-04-30 | Heat-resistant ABS (acrylonitrile-butadiene-styrene) resin composition high in scratch resistance and preparation method of heat-resistant ABS resin composition |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107501850A (en) * | 2017-09-11 | 2017-12-22 | 广西鑫深科技有限公司 | Automobile rear spoiler proprietary material and preparation method thereof is prepared using discarded ABS resin |
| CN112574525A (en) * | 2020-12-10 | 2021-03-30 | 上海金发科技发展有限公司 | Heat-resistant composition for thin-wall friction welding and preparation method thereof |
| CN113621214A (en) * | 2021-09-03 | 2021-11-09 | 万敬新材料(上海)有限公司 | Polycarbonate/styrene-butadiene-acrylonitrile PC/ABS alloy |
| CN114736483A (en) * | 2022-03-29 | 2022-07-12 | 江苏金发科技新材料有限公司 | High-fluidity, high-heat-resistance and good-appearance ABS (acrylonitrile-butadiene-styrene) composition as well as preparation method and application thereof |
| US11814513B2 (en) | 2018-10-31 | 2023-11-14 | Lotte Chemical Corporation | Thermoplastic resin composition and molded product using same |
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| CN102471559A (en) * | 2009-08-07 | 2012-05-23 | Lg化学株式会社 | Thermoplastic resin composition |
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| CN102471559A (en) * | 2009-08-07 | 2012-05-23 | Lg化学株式会社 | Thermoplastic resin composition |
| CN101817967A (en) * | 2009-12-25 | 2010-09-01 | 上海锦湖日丽塑料有限公司 | Electroplating ABS composite and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107501850A (en) * | 2017-09-11 | 2017-12-22 | 广西鑫深科技有限公司 | Automobile rear spoiler proprietary material and preparation method thereof is prepared using discarded ABS resin |
| US11814513B2 (en) | 2018-10-31 | 2023-11-14 | Lotte Chemical Corporation | Thermoplastic resin composition and molded product using same |
| CN112574525A (en) * | 2020-12-10 | 2021-03-30 | 上海金发科技发展有限公司 | Heat-resistant composition for thin-wall friction welding and preparation method thereof |
| CN112574525B (en) * | 2020-12-10 | 2023-04-18 | 上海金发科技发展有限公司 | Heat-resistant composition for thin-wall friction welding and preparation method thereof |
| CN113621214A (en) * | 2021-09-03 | 2021-11-09 | 万敬新材料(上海)有限公司 | Polycarbonate/styrene-butadiene-acrylonitrile PC/ABS alloy |
| CN114736483A (en) * | 2022-03-29 | 2022-07-12 | 江苏金发科技新材料有限公司 | High-fluidity, high-heat-resistance and good-appearance ABS (acrylonitrile-butadiene-styrene) composition as well as preparation method and application thereof |
| CN114736483B (en) * | 2022-03-29 | 2023-10-17 | 江苏金发科技新材料有限公司 | High-fluidity high-heat-resistance ABS composition with good appearance, and preparation method and application thereof |
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Application publication date: 20150819 |