CN106317753B - A kind of heat-proof ABS resin composition improving chemical resistance - Google Patents
A kind of heat-proof ABS resin composition improving chemical resistance Download PDFInfo
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- CN106317753B CN106317753B CN201610687243.6A CN201610687243A CN106317753B CN 106317753 B CN106317753 B CN 106317753B CN 201610687243 A CN201610687243 A CN 201610687243A CN 106317753 B CN106317753 B CN 106317753B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The present invention relates to a kind of heat-proof ABS resin composition for improving chemical resistance, the ABS resin composition selects 80-93 parts of substance law ABS resins, 3-10 parts of heat-proof modifiers, and 4-10 parts of PA6 resins are prepared for raw material.Its advantage is shown: ABS resin composition of the invention has high heat distortion temperature, high impact strength, good dimensional stability and good chemical resistance, it can be very good to solve the problems, such as auto parts and components high temperature deformation, spray painting lifting and contact chemicals cracking, especially suitable in the automotive upholsteries such as the automobile exterior trimming parts such as heat dissipation grid, rearview mirror, pillar panel and instrument frame, door panel arm rest.
Description
Technical field
The present invention relates to technical field of polymer materials, specifically, being a kind of heat-proof ABS for improving chemical resistance
Resin combination.
Background technique
With the rapid development of the automotive industry, the demand to the ABS resin material of automobile interior exterior portion decoration both at home and abroad
Amount steeply rises.ABS resin has emulsion method ABS resin and two kinds of substance law ABS resin in the market, and the production procedure of the latter is short,
Number of devices is few, and low energy consumption, and environmental pollution is small, and the heat-resisting height of product, distribution performance is good, but its rubber size is larger, acrylonitrile
Content is relatively low, therefore chemical resistance is relatively low.Automobile exterior trimming parts ABS resin material generally requires to do paint baking, bakes
Qi Wendu is 80-95 degree, directly uses the problem of lifting and deformation are easy to appear when substance law ABS baking vanish.Automotive upholstery is used
ABS resin require distribution performance good, heat-resisting height, chemical resistance is good, directly can be very good to meet using substance law ABS
Requirement of the automotive upholstery to distribution performance, but heat resistance is not enough, is easy to appear high/low temperature cyclic test deformation, Er Qieyin
It is bad for its chemical resistance, it is easy to appear the problem of chemicals such as contact cosmetics, alcohol crack.
The country, which has had, at present adds heat-proof modifier directly to improve the heat resistance of substance law ABS resin, this side
Case does not solve the problems, such as that the chemicals-resistant of substance law ABS resin is poor.Also there is patent document by directly adding the knot such as PA6, PBT
Crystalline substance resin material improves ABS resin chemical resistance, but these schemes or additive amount are relatively high, reduce ABS tree
The dimensional stability or additive amount of rouge are relatively low, but without solving the problems, such as compatibility and dispersibility, reduce ABS resin
Impact flexibility.
The present invention addresses the above problem, develops a kind of with the heat-resisting ABS resin group for improving chemical resistance
Object is closed, substance law ABS resin chemical resistance and heat resistance is improved, solves what it was used to be easy to appear in automobile exterior trimming parts
Baking vanish deformation and baking vanish lifting problem solve thermocycling deformation, contactization that it is used to be easy to appear in automotive upholstery
The problem of chemicals such as cosmetic crack, while there are high impact flexibility, good dimensional stability and workability.
Chinese patent literature CN104927334A discloses a kind of PC/ABS of resistance to cosmetics alloy material, the alloy material
Material is made of the component of following parts by weight: 40~80 parts of PC resin, 20~60 parts of ABS resin, and 2~5 parts of POE resin, compatilizer
0.5~1 part, 0.1~1 part of antioxidant, 0.1~1 part of lubricant.But about a kind of improvement chemical resistance of the invention
Heat-proof ABS resin composition yet there are no report.
Summary of the invention
The purpose of the present invention is aiming at the shortcomings in the prior art, provide a kind of heat-proof ABS for improving chemical resistance
Resin combination.
Another purpose of the invention is to provide the preparation of the heat-proof ABS resin composition of the improvement chemical resistance
Method.
To achieve the above object, the technical solution adopted by the present invention is that: it is a kind of improve chemical resistance heat-proof ABS tree
Oil/fat composition, the resin combination are made of the component of following parts by weight:
80-93 parts of substance law ABS resin,
3-10 parts of heat-proof modifier,
4-10 parts of PA6 resin.
The substance law ABS resin be acrylonitrile-butadiene-styrene copolymer, by mass polymerization mode come
Preparation, weight average molecular weight 10,000-15,000, butadiene content 10-15%, acrylonitrile content 20-30%.
The substance law ABS resin is the substance law ABS for being 130,000 containing 24% acrylonitrile, 14% butadiene, molecular weight
Resin.
The heat-proof modifier is the terpolymer or maleic acid of maleic anhydride and methyl methacrylate, styrene
The terpolymer of acid anhydride and acrylonitrile, the terpolymer of styrene or N-phenylmaleimide and maleic anhydride, styrene
Or N-phenylmaleimide and one or more of maleic anhydride, α-methylstyrene, the multiple copolymer of acrylonitrile, institute
The maleic anhydride content for the heat-resistant agent modifying agent stated is 4-10%.
The glass transition temperature of the heat-resistant agent modifying agent is 120-200 DEG C.
The terminal amino group content of the PA6 resin is 48-55%.
The relative viscosity of the PA6 resin is 2.5-2.8.
To realize above-mentioned second purpose, the technical solution adopted by the present invention is that: the preparation method includes following step
It is rapid: substance law ABS resin, heat-proof modifier, PA6 resin and lubricant, antioxidant are put into high-speed mixer and are stirred to get
Mixture is added mixture from the main feed opening of twin-screw, and extruding pelletization obtains product.
The preparation method is the following steps are included: by containing 24% acrylonitrile, 14% butadiene, the sheet that molecular weight is 130,000
Body method ABS resin, the heat-proof modifier that maleic anhydride content is 4%, the PA6 resin that terminal amino group content is 48%, lubricant resist
Oxygen agent is put into stirred 5-20 minutes in high-speed mixer after obtain mixture；Mixture is added from the main feed opening of twin-screw,
Extruding pelletization obtains product, and the barrel temperature of extruder is 180-250 DEG C, screw speed 180-450rpm.
The invention has the advantages that:
1, there is the PA6 resin of specific terminal amino group content to improve the chemicals-resistant of substance law ABS on a small quantity for present invention addition
Performance, adding has the heat-proof modifier of specific maleic anhydride content to improve the heat resistance of substance law ABS, while heat-resisting changing
Property agent in the maleic anhydride of certain content that contains can react with the Amino End Group of certain content in PA6 resin, improve PA6
Dispersion performance of the compatibility performance and a small amount of PA6 resin of resin and substance law ABS in substance law ABS resin, to guarantee most
Finished product has high heat resistance, impact flexibility and good dimensional stability.
2, the PA6 resin that the present invention is used to improve substance law ABS chemical resistance has specific viscosity and specific
Terminal amino group content to guarantee that PA6 resin has good dispersion in substance law ABS, while making PA6 resin have certain crystallization
Degree, to guarantee enough chemical resistances.Reactivity is inadequate if the terminal amino group content of PA6 resin is too low, to product
Compatibility and dispersibility help it is little；If terminal amino group content is excessively high, it can react excessively, PA6 tree is greatly lowered
The crystallinity of rouge, to be unable to reach the purpose for improving chemical resistance.
3, the heat-proof modifier that the present invention is used to improve substance law ABS chemical resistance must have specific maleic acid
Acid anhydride content, if maleic anhydride content is too high, the reaction with PA6 resin excessively can be unable to reach raising chemical resistance
Purpose；It is little to the promotion amplitude of substance law ABS heat resistance if maleic anhydride content is too low, while with PA6 resin
Reaction it is inadequate, be unfavorable for the compatibility and dispersibility of product.
4, the present invention develops a kind of with the heat-proof ABS resin composition for improving chemical resistance, improves substance law
ABS resin chemical resistance and heat resistance solve baking vanish deformation and baking vanish that it is used to be easy to appear in automobile exterior trimming parts
Lifting problem solves the chemicals such as thermocycling deformation, the contact cosmetics that it is used to be easy to appear in automotive upholstery and opens
The problem of splitting, while there are high impact flexibility, good dimensional stability and workability.
Specific embodiment
It elaborates below with reference to embodiment to specific embodiment provided by the invention.
The characteristics of in order to preferably embody the heat-proof ABS resin composition for improving chemical resistance, present invention uses
Embodiment 1-7 and comparative example 1-5 has been respectively compared different heat-proof modifier dosages, difference PA6 amount of resin, different maleic anhydrides
Influence of the PA6 resin to material property of the heat-proof modifier of content, different terminal amino group contents.
Embodiment 1-7
By 80Kg containing 24% acrylonitrile, 14% butadiene, the substance law ABS resin that molecular weight is 130,000,10Kg maleic acid
The heat-proof modifier that acid anhydride content is 4%, the PA6 resin that 4Kg terminal amino group content is 48%, 0.5Kg lubricant, 0.3Kg antioxidant
It is put into after being stirred 5-20 minutes in high-speed mixer and obtains mixture.
Mixture is added from the main feed opening of twin-screw, extruding pelletization obtains product, and the barrel temperature of extruder is
180-250 DEG C, screw speed 180-450rpm.
See Table 1 for details for the material prescription of embodiment 1-7.
The material prescription of 1 embodiment 1-7 of table
Comparative example 1-5
See Table 2 for details for the material prescription of comparative example 1-5.
The material prescription of 2 comparative example 1-5 of table
Embodiment 8
The heat-resisting ABS resin for the improvement chemical resistance being prepared above according to embodiment and comparative example is combined
Object prepares test bars according to same injecting condition, and specific physical property detection project is as follows:
Tensile strength: tensile strength is measured according to ASTM D 178；
Bending strength and bending modulus: it is detected according to standard ASTM D790 (3mm/min)；
Beam type notch impact strength: notch impact strength is measured according to ASTM D256 (1/8 " notch, 23 DEG C)；
Melt flow rate (MFR): melt flow rate (MFR) is measured according to ASTM D1238 (240 DEG C, 10Kg)；
Heat distortion temperature (HDT): it under conditions of 1.82MPa, is measured according to ASTM D648 (1/4 ", 120 DEG C/hr)
Heat distortion temperature；
Resistance to suncream, resistance to acetic acid: hand lotion or acetic acid are coated on tensile bars surface, room temperature for 24 hours, observes surface
Cracks.
See Table 3 for details for the test result of embodiment 1-7, and see Table 4 for details for the test result of comparative example 1-5.
The performance data of 3 embodiment 1-7 of table
The performance data of 4 comparative example 1-5 of table
| Test item | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 |
| Tensile strength | 46 | 47 | 40 | 42 | 44 |
| Notch impact strength | 260 | 230 | 190 | 280 | 200 |
| Melt flow rate (MFR) | 15 | 8 | 20 | 10 | 12 |
| Heat distortion temperature | 87 | 92 | 88 | 93 | 90 |
| The cracks of resistance to suncream | Crackle | Crackle | Nothing | Crackle | Nothing |
| The cracks of resistance to acetic acid | Crackle | Crackle | Nothing | Crackle | Nothing |
Compared by the performance of table 3, table 4, it can be seen that only addition PA6 resin can improve the crackle of substance law ABS resin
Situation, but because both PA6 resin and substance law ABS resin are incompatible, the substance law ABS resin after adding PA6 resin
Tensile strength and impact strength all sharp falls；And it only adds heat-proof modifier and is unable to improve splitting for substance law ABS resin
Line situation.Prescribed limit, the heat-proof modifier for providing maleic anhydride content, the PA6 resin for providing terminal amino group content are added, it can be with
Improve the cracks of substance law ABS resin well, while obtaining good physical mechanical property and heat resistance.Work as PA6
Maleic anhydride content of the terminal amino group content of resin lower than 48% or in heat-proof modifier is more than 10%, the impact of products obtained therefrom
Intensity decline is obvious or cracks are without improvement.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
Member, under the premise of not departing from the method for the present invention, can also make several improvement and supplement, such as increase other auxiliary agents (as added
Enter lubricant to improve processing performance), these are improved and supplement also should be regarded as protection scope of the present invention.
Claims (7)
1. it is a kind of improve chemical resistance heat-proof ABS resin composition, which is characterized in that the resin combination by with
The component of lower parts by weight is made:
80-93 parts of substance law ABS resin,
3-10 parts of heat-proof modifier,
4-10 parts of PA6 resin；
The heat-proof modifier be maleic anhydride and methyl methacrylate, the terpolymer of styrene or maleic anhydride with
The terpolymer or N- of acrylonitrile, the terpolymer of styrene or N-phenylmaleimide and maleic anhydride, styrene
Phenyl maleimide and one or more of maleic anhydride, α-methylstyrene, the multiple copolymer of acrylonitrile, it is described
The maleic anhydride content of heat-resistant agent modifying agent is 4-10%；
The terminal amino group content of the PA6 resin is 48-55%.
2. the heat-proof ABS resin composition according to claim 1 for improving chemical resistance, which is characterized in that described
Substance law ABS resin be acrylonitrile-butadiene-styrene copolymer, prepared by mass polymerization mode, it is heavy divide equally
Son amount is 10,000-15,000, butadiene content 10-15%, acrylonitrile content 20-30%.
3. the heat-proof ABS resin composition according to claim 1 for improving chemical resistance, which is characterized in that described
Substance law ABS resin be 130,000 containing 24% acrylonitrile, 14% butadiene, molecular weight substance law ABS resin.
4. the heat-proof ABS resin composition according to claim 1 for improving chemical resistance, which is characterized in that described
Heat-resistant agent modifying agent glass transition temperature be 120-200 DEG C.
5. the heat-proof ABS resin composition according to claim 1 for improving chemical resistance, which is characterized in that described
PA6 resin relative viscosity be 2.5-2.8.
6. the preparation method of the heat-proof ABS resin composition according to claim 1 for improving chemical resistance, feature
It is, the preparation method is the following steps are included: be put into high-speed stirring for substance law ABS resin, heat-proof modifier, PA6 resin
It mixes and stirs to get mixture in machine, mixture is added from the main feed opening of twin-screw, extruding pelletization obtains product.
7. the preparation method of the heat-proof ABS resin composition according to claim 6 for improving chemical resistance, feature
It is, the preparation method is the following steps are included: by containing 24% acrylonitrile, 14% butadiene, the ontology that molecular weight is 130,000
Method ABS resin, the heat-proof modifier that maleic anhydride content is 4%, the PA6 resin that terminal amino group content is 48% are put into high-speed stirred
Mixture is obtained after stirring 5-20 minutes in machine；Mixture is added from the main feed opening of twin-screw, extruding pelletization obtains product,
The barrel temperature of extruder is 180-250 DEG C, screw speed 180-450rpm.
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| CN201610687243.6A CN106317753B (en) | 2016-08-18 | 2016-08-18 | A kind of heat-proof ABS resin composition improving chemical resistance |
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| CN111087748B (en) * | 2019-12-27 | 2022-02-15 | 上海普利特复合材料股份有限公司 | Antistatic ABS resin composition with improved chemical resistance and preparation method thereof |
| CN114230964A (en) * | 2021-12-24 | 2022-03-25 | 上海日之升科技有限公司 | High-heat-resistance antistatic ABS material and preparation method thereof |
| CN115975333A (en) * | 2022-09-20 | 2023-04-18 | 广东拓亿信息科技有限公司 | Corrosion-resistant environment-friendly plastic shell and preparation method thereof |
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| KR100442922B1 (en) * | 2001-10-29 | 2004-08-02 | 주식회사 엘지화학 | Acrylonitril butadiene styrene resin having superior chemical-proof and transmittancy and method for preparing thereof |
| CN101210098A (en) * | 2007-11-29 | 2008-07-02 | 上海锦湖日丽塑料有限公司 | Acetic acid resisting ABS material |
| CN101870797B (en) * | 2010-03-29 | 2013-07-03 | 金发科技股份有限公司 | Polyacrylonitrile-butadiene-styrene modified compound and preparation method thereof |
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