CN114854168A - Heat-resistant flame-retardant ABS composition and preparation method thereof - Google Patents
Heat-resistant flame-retardant ABS composition and preparation method thereof Download PDFInfo
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- CN114854168A CN114854168A CN202210636969.2A CN202210636969A CN114854168A CN 114854168 A CN114854168 A CN 114854168A CN 202210636969 A CN202210636969 A CN 202210636969A CN 114854168 A CN114854168 A CN 114854168A
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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
- C08L2201/02—Flame or fire retardant/resistant
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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
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- 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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
Abstract
The invention relates to the technical field of high polymer materials, in particular to a heat-resistant flame-retardant ABS composition and a preparation method thereof, wherein the heat-resistant flame-retardant ABS composition comprises the following raw materials in parts by weight: 40-60 parts of ABS resin, 1-5 parts of compatilizer, 5-10 parts of flame retardant, 1-5 parts of thermoplastic elastomer, 1-5 parts of heat-resistant modifier, 4-8 parts of toughening modifier, 1-3 parts of lubricant, 1-5 parts of coupling agent and 3-7 parts of graphite whisker. The heat-resistant flame-retardant ABS composition has high flame-retardant effect and stability, the heat distortion temperature can reach more than 100 ℃, the flame-retardant effect and the stability are better on the premise of meeting the mechanical property, all the mechanical properties are kept in optimal balance, the application range is wider, the cost is lower, the process is simple, and therefore, the popularization is convenient.
Description
Technical Field
The invention relates to the technical field of high polymer materials, and particularly relates to a heat-resistant flame-retardant ABS composition and a preparation method thereof.
Background
The ABS resin is a terpolymer consisting of styrene, butadiene and acrylonitrile, integrates the high fluidity of the styrene, the rubber toughness of the butadiene and the chemical resistance of the acrylonitrile, has excellent processability, low temperature resistance, electric insulation performance, chemical corrosion resistance, high gloss and excellent electroplating performance, has the excellent characteristics of good creep resistance, high dimensional stability, small molding shrinkage and the like, and is widely applied to the fields of war industry, automobiles, electronic and electric appliances and the like. On one hand, the oxygen index of the ABS resin is only 18, and the ABS resin belongs to flammable materials; on the other hand, ABS resins themselves are not so heat resistant, and generally have a heat distortion temperature of 82 to 84 ℃ (ASTM D648, 1.82 MPa). Therefore, when the flame retardant is used for electronic and electrical equipment, flame retardant and heat resistant modification is mostly needed to meet the use requirement of safety fire prevention.
ABS resin is one of five synthetic resins, its impact resistance, heat resistance, low temperature resistance, chemical resistance and electrical property are excellent, and it also has the characteristics of easy processing, stable product size and good surface gloss, and can be easily coated and colored, and can also be used for secondary processing of surface spraying metal, electroplating, welding, hot-pressing and bonding, etc., and can be extensively used in the industrial fields of machinery, automobile, electronic and electric appliances, instruments and meters, textile and building, etc., so that it is a thermoplastic engineering plastic with extensive application. However, in some specific cases, the flame retardancy of ABS resins is insufficient.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide the heat-resistant flame-retardant ABS composition which has a high flame-retardant effect and stability, the heat distortion temperature can reach over 100 ℃, the flame-retardant effect and stability are better on the premise of meeting the mechanical property, all the mechanical properties are kept in the best balance, the application range is wider, the cost is lower, the process is simple, and therefore, the heat-resistant flame-retardant ABS composition is convenient to popularize.
The invention aims to provide a preparation method of a heat-resistant flame-retardant ABS composition, which has the advantages of simple preparation method, convenient operation and control, high quality of produced products, low cost, contribution to industrial production and capability of effectively overcoming the defects of the conventional antibacterial coating.
The purpose of the invention is realized by the following technical scheme: a heat-resistant flame-retardant ABS composition comprises the following raw materials in parts by weight: 40-60 parts of ABS resin, 1-5 parts of compatilizer, 5-10 parts of flame retardant, 1-5 parts of thermoplastic elastomer, 1-5 parts of heat-resistant modifier, 4-8 parts of toughening modifier, 1-3 parts of lubricant, 1-5 parts of coupling agent and 3-7 parts of graphite whisker; the lubricant is pentaerythritol stearate.
The heat-resistant flame-retardant ABS composition has high flame-retardant effect and stability, the heat distortion temperature can reach more than 100 ℃, on the premise of meeting the mechanical property, the flame-retardant effect and the stability are better, all the mechanical properties are kept in optimal balance, the application range is wider, the cost is lower, the process is simple, and therefore, the popularization is convenient. The ABS composition has soft characteristic and excellent stress whitening resistance by adding the thermoplastic elastomer and the toughening modifier; the added graphite whisker has good heat resistance and excellent flame resistance, and can further assist in improving the flame retardant effect of the composition; in addition, the specific types of the added flame retardants can reduce the influence of the flame retardants on the fatigue resistance and the low-temperature bending retention rate of the material, and obviously improve the flame retardant performance.
Preferably, the heat-resistant modifier comprises the following raw materials in parts by weight: 5-10 parts of poly (glycol) diacid, 10-15 parts of polymethyl methacrylate, 4-8 parts of graphite-phase carbon nitride, 5-10 parts of isopropanol, 0.6-1.0 part of acetic acid, 0.2-0.4 part of chitosan, 4-8 parts of polystyrene microspheres and 1-3 parts of polybutadiene.
Preferably, the heat-resistant modifier is prepared by the following method:
s1, adding graphite-phase carbon nitride into isopropanol according to parts by weight, carrying out ultrasonic treatment at 6000-10000Hz for 4-8min, adding acetic acid and chitosan into the isopropanol, carrying out ultrasonic treatment, and taking upper-layer suspension to obtain graphite-phase carbon nitride emulsion for later use;
s2, adding poly (diol diacid) ester and polymethyl methacrylate into the graphite-phase carbon nitride emulsion obtained in the step S1, and stirring at the speed of 200-400r/min for 20-40min to obtain a shell material for later use;
s3, mixing the polystyrene microspheres and polybutadiene, adding the mixture into the shell material obtained in the step S2, centrifuging the mixture at the speed of 7000 and 80000r/min for 8 to 16min, washing the mixture, performing ultrasonic treatment, drying and grinding the mixture to obtain the heat-resistant modifier.
The heat-resistant modifier is prepared from the raw materials and the preparation method, the prepared heat-resistant modifier is of a core-shell structure, the poly (glycol adipate), the polymethyl methacrylate and the graphite-phase carbon nitride emulsion are taken as shell materials, the polystyrene microspheres and the polybutadiene are taken as cores, so that the heat-resistant modifier has the effects of high strength and high heat resistance, is favorable for dispersity in ABS resin, overcomes the defects of poor dispersity, poor effect and the like of a flame-retardant material in the traditional method, improves the flame-retardant property of the ABS composition, and is simple and flexible in operation, good in stability, low in cost, low in operation condition requirement and favorable for large-scale production.
Preferably, the compatilizer is at least one of high rubber powder or maleic anhydride.
The thermoplastic elastomer adopted in the invention has good flexibility, high elasticity and low-temperature performance, and can be used as a toughening agent of ABS resin by adding a certain amount of compatilizer.
Preferably, the flame retardant is at least one of brominated polystyrene, decabromodiphenylethane, decabromodiphenyl ether and triphenyl phosphate. More preferably, the flame retardant is a mixture of brominated polystyrene, decabromodiphenylethane and triphenyl phosphate in a weight ratio of 0.8-1.2:0.6-1.0: 0.3-0.7.
The flame retardant is prepared from the raw materials according to a specific proportion, and can reduce the influence of the flame retardant on the fatigue resistance and the low-temperature bending retention rate of the material by cooperating with respective advantages, so that the dispersion problem of the heat-resistant modifier in the ABS resin is improved, and the sensitivity problem of the flame retardant to the processing temperature is met.
Preferably, the thermoplastic elastomer is at least one of a polyurethane thermoplastic elastomer and a polyether ester thermoplastic elastomer.
Preferably, the toughening modifier is at least one of nitrile rubber and styrene butadiene rubber. More preferably, the toughening modifier is a mixture of nitrile rubber and styrene butadiene rubber according to the weight ratio of 0.8-1.2: 0.6-1.0.
The toughening modifier is adopted in the invention, so that the flexibility of the ABS composition can be increased, and the comprehensive performance of the ABS composition can be improved.
Preferably, the coupling agent is at least one of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent and a zirconate coupling agent.
The invention also provides a preparation method of the heat-resistant flame-retardant ABS composition, which comprises the following steps:
according to the weight parts, ABS resin, a compatilizer, a flame retardant, a thermoplastic elastomer, a heat-resistant modifier, a toughening modifier, a lubricant and a coupling agent are mixed and then added into a main feeding port of an extruder, the temperature of a first zone is 160-plus-180 ℃, the temperature of a second zone is 175-plus-185 ℃, the temperature of a third zone is 175-plus-185 ℃, the temperature of a fourth zone is 165-plus-175 ℃ and the temperature of a fifth zone is 155-plus-165 ℃ for extrusion, and graphite whiskers are added into a first exhaust hole or a side feeding port of the extruder at the same time for melting and granulation to obtain the heat-resistant flame-retardant ABS composition.
The heat-resistant flame-retardant ABS composition is prepared by the method, has high flame-retardant effect and stability, has the heat distortion temperature of over 100 ℃, has better flame-retardant effect and stability on the premise of meeting the mechanical property, keeps the best balance of all mechanical properties, has wider application range, lower cost and simple process, is convenient to popularize, has simple preparation method, convenient operation and control, high quality of produced products and low cost, is beneficial to industrial production, and can effectively overcome the defects of the conventional antibacterial coating.
The invention has the beneficial effects that: the heat-resistant flame-retardant ABS composition has high flame-retardant effect and stability, the heat distortion temperature can reach more than 100 ℃, the flame-retardant effect and the stability are better on the premise of meeting the mechanical property, all the mechanical properties are kept in optimal balance, the application range is wider, the cost is lower, the process is simple, and therefore, the popularization is convenient.
The preparation method of the heat-resistant flame-retardant ABS composition is simple, convenient to operate and control, high in quality of produced products, low in cost, beneficial to industrial production and capable of effectively overcoming the defects of the conventional antibacterial coating.
Detailed Description
The present invention will be further described with reference to the following examples for facilitating understanding of those skilled in the art, and the description of the embodiments is not intended to limit the present invention.
Example 1
A heat-resistant flame-retardant ABS composition comprises the following raw materials in parts by weight: 40 parts of ABS resin, 1 part of compatilizer, 5 parts of flame retardant, 1 part of thermoplastic elastomer, 1 part of heat-resistant modifier, 4 parts of toughening modifier, 1 part of lubricant, 1 part of coupling agent and 3 parts of graphite whisker; the lubricant is pentaerythritol stearate.
The heat-resistant modifier comprises the following raw materials in parts by weight: 5 parts of poly (glycol) diacid, 10 parts of polymethyl methacrylate, 4 parts of graphite-phase carbon nitride, 5 parts of isopropanol, 0.6 part of acetic acid, 0.2 part of chitosan, 4 parts of polystyrene microspheres and 1 part of polybutadiene; the graphite-phase carbon nitride is produced by Koxing carbon industry Co., Ltd, Haiman city; the polystyrene microsphere is prepared from polystyrene microsphere (PSt) produced by Suzhou New Material science and technology (Suzhou) Co.
The heat-resistant modifier is prepared by the following method:
s1, adding the graphite-phase carbon nitride into isopropanol according to parts by weight, carrying out ultrasonic treatment for 4min at 6000Hz, adding acetic acid and chitosan into the isopropanol, carrying out ultrasonic treatment, and taking an upper-layer suspension to obtain a graphite-phase carbon nitride emulsion for later use;
s2, adding polyglycol ester diacid and polymethyl methacrylate into the graphite-phase carbon nitride emulsion obtained in the step S1, and stirring at the speed of 200r/min for 20min to obtain a shell material for later use;
s3, mixing the polystyrene microspheres and the polybutadiene, adding the mixture into the shell material obtained in the step S2, centrifuging the mixture at the speed of 7000r/min for 8min, washing the mixture, performing ultrasonic treatment, drying the mixture, and grinding the mixture to obtain the heat-resistant modifier.
The compatilizer is high rubber powder; the thermoplastic elastomer is a polyurethane thermoplastic elastomer produced by Dongguan city Chong plastic Co.
The flame retardant is a mixture of brominated polystyrene, decabromodiphenylethane and triphenyl phosphate according to the weight ratio of 0.8:0.6: 0.3.
The toughening modifier is a mixture of nitrile rubber and styrene butadiene rubber in a weight ratio of 0.8: 0.6.
The coupling agent is a silane coupling agent, and the silane coupling agent is a silane coupling agent KH-570.
The preparation method of the heat-resistant flame-retardant ABS composition comprises the following steps:
according to the weight parts, ABS resin, a compatilizer, a flame retardant, a thermoplastic elastomer, a heat-resistant modifier, a toughening modifier, a lubricant and a coupling agent are mixed and then added into a main feeding port of an extruder, the temperature of a first zone is 160 ℃, the temperature of a second zone is 175 ℃, the temperature of a third zone is 175 ℃, the temperature of a fourth zone is 165 ℃ and the temperature of a fifth zone is 155 ℃, the mixture is extruded, and meanwhile, graphite whiskers are added into a first exhaust hole or a side feeding port of the extruder, and the mixture is subjected to melting granulation to obtain the heat-resistant flame-retardant ABS composition.
Example 2
A heat-resistant flame-retardant ABS composition comprises the following raw materials in parts by weight: 45 parts of ABS resin, 2 parts of compatilizer, 7 parts of flame retardant, 2 parts of thermoplastic elastomer, 2 parts of heat-resistant modifier, 5 parts of toughening modifier, 1.5 parts of lubricant, 2 parts of coupling agent and 4 parts of graphite whisker; the lubricant is pentaerythritol stearate.
The heat-resistant modifier comprises the following raw materials in parts by weight: 6 parts of poly (glycol ester) diacid, 11 parts of polymethyl methacrylate, 5 parts of graphite-phase carbon nitride, 6 parts of isopropanol, 0.7 part of acetic acid, 0.25 part of chitosan, 5 parts of polystyrene microspheres and 1.5 parts of polybutadiene; the graphite-phase carbon nitride is produced by Koxing carbon industry Co., Ltd, Haiman city; the polystyrene microsphere is prepared from polystyrene microsphere (PSt) produced by Suzhou New Material science and technology (Suzhou) Co.
The heat-resistant modifier is prepared by the following method:
s1, adding graphite-phase carbon nitride into isopropanol according to parts by weight, carrying out ultrasonic treatment for 5min at 7000Hz, adding acetic acid and chitosan into the isopropanol, carrying out ultrasonic treatment, and taking an upper suspension to obtain a graphite-phase carbon nitride emulsion for later use;
s2, adding polyglycol ester diacid and polymethyl methacrylate into the graphite-phase carbon nitride emulsion obtained in the step S1, and stirring at the speed of 250r/min for 25min to obtain a shell material for later use;
s3, mixing the polystyrene microspheres and the polybutadiene, adding the mixture into the shell material obtained in the step S2, centrifuging the mixture for 10min at the speed of 7200r/min, washing the mixture, performing ultrasonic treatment, drying the mixture, and grinding the mixture to obtain the heat-resistant modifier.
The compatilizer is maleic anhydride.
The flame retardant is a mixture of brominated polystyrene, decabromodiphenylethane and triphenyl phosphate according to the weight ratio of 0.9:0.7: 0.4.
The thermoplastic elastomer is a polyurethane thermoplastic elastomer, and the polyurethane thermoplastic elastomer is produced by Chong plastic Co.
The toughening modifier is a mixture of nitrile rubber and styrene butadiene rubber in a weight ratio of 0.9: 0.7.
The coupling agent is a titanate coupling agent, and the titanate coupling agent is a titanate coupling agent 201.
The preparation method of the heat-resistant flame-retardant ABS composition comprises the following steps:
according to the weight parts, ABS resin, a compatilizer, a flame retardant, a thermoplastic elastomer, a heat-resistant modifier, a toughening modifier, a lubricant and a coupling agent are mixed and then added into a main feeding port of an extruder, the temperature of a first zone is 165 ℃, the temperature of a second zone is 178 ℃, the temperature of a third zone is 178 ℃, the temperature of a fourth zone is 168 ℃, the temperature of a fifth zone is 158 ℃, the mixture is extruded, meanwhile, graphite whiskers are added into a first exhaust hole or a side feeding port of the extruder, and the heat-resistant flame-retardant ABS composition is obtained through melting granulation.
Example 3
A heat-resistant flame-retardant ABS composition comprises the following raw materials in parts by weight: 50 parts of ABS resin, 3 parts of compatilizer, 8 parts of flame retardant, 3 parts of thermoplastic elastomer, 3 parts of heat-resistant modifier, 6 parts of toughening modifier, 2 parts of lubricant, 3 parts of coupling agent and 5 parts of graphite whisker; the lubricant is pentaerythritol stearate.
The heat-resistant modifier comprises the following raw materials in parts by weight: 7 parts of poly (glycol) diacid, 12 parts of polymethyl methacrylate, 6 parts of graphite-phase carbon nitride, 8 parts of isopropanol, 0.8 part of acetic acid, 0.3 part of chitosan, 6 parts of polystyrene microspheres and 2 parts of polybutadiene; the graphite-phase carbon nitride is produced by Koxing carbon industry Co., Ltd, Haiman city; the polystyrene microsphere is prepared from polystyrene microsphere (PSt) produced by Suzhou New Material science and technology (Suzhou) Co.
The heat-resistant modifier is prepared by the following method:
s1, adding graphite-phase carbon nitride into isopropanol according to parts by weight, carrying out ultrasonic treatment for 6min at 8000Hz, adding acetic acid and chitosan into the isopropanol, carrying out ultrasonic treatment, and taking an upper suspension to obtain a graphite-phase carbon nitride emulsion for later use;
s2, adding polyglycol ester diacid and polymethyl methacrylate into the graphite-phase carbon nitride emulsion obtained in the step S1, and stirring at the speed of 300r/min for 30min to obtain a shell material for later use;
s3, mixing the polystyrene microspheres and the polybutadiene, adding the mixture into the shell material obtained in the step S2, centrifuging the mixture for 12min at the speed of 7500r/min, washing the mixture, performing ultrasonic treatment, drying the mixture, and grinding the mixture to obtain the heat-resistant modifier.
The compatilizer is high rubber powder.
The flame retardant is a mixture of brominated polystyrene, decabromodiphenylethane and triphenyl phosphate according to the weight ratio of 1.0:0.8: 0.5.
The thermoplastic elastomer is a polyurethane thermoplastic elastomer, and the polyurethane thermoplastic elastomer is produced by Chong plastic Co.
The toughening modifier is a mixture of nitrile rubber and styrene butadiene rubber according to a weight ratio of 1.0: 0.8.
The coupling agent is an aluminate coupling agent, and the aluminate coupling agent is an aluminate coupling agent dl 411.
The preparation method of the heat-resistant flame-retardant ABS composition comprises the following steps:
according to the weight parts, ABS resin, a compatilizer, a flame retardant, a thermoplastic elastomer, a heat-resistant modifier, a toughening modifier, a lubricant and a coupling agent are mixed and then added into a main feeding port of an extruder, the temperature of a first zone is 170 ℃, the temperature of a second zone is 180 ℃, the temperature of a third zone is 180 ℃, the temperature of a fourth zone is 170 ℃ and the temperature of a fifth zone is 160 ℃, the mixture is extruded, meanwhile, graphite whiskers are added into a first exhaust hole or a side feeding port of the extruder, and the heat-resistant flame-retardant ABS composition is obtained through melting granulation.
Example 4
A heat-resistant flame-retardant ABS composition comprises the following raw materials in parts by weight: 50 parts of ABS resin, 4 parts of compatilizer, 9 parts of flame retardant, 4 parts of thermoplastic elastomer, 4 parts of heat-resistant modifier, 7 parts of toughening modifier, 2.5 parts of lubricant, 4 parts of coupling agent and 6 parts of graphite whisker; the lubricant is pentaerythritol stearate.
The heat-resistant modifier comprises the following raw materials in parts by weight: 8 parts of poly (glycol ester) diacid, 14 parts of polymethyl methacrylate, 7 parts of graphite-phase carbon nitride, 9 parts of isopropanol, 0.9 part of acetic acid, 0.35 part of chitosan, 7 parts of polystyrene microspheres and 2.5 parts of polybutadiene; the graphite-phase carbon nitride is produced by Koxing carbon industry Co., Ltd, Haiman city; the polystyrene microsphere is prepared from polystyrene microsphere (PSt) produced by Suzhou New Material science and technology (Suzhou) Co.
The heat-resistant modifier is prepared by the following method:
s1, adding graphite phase carbon nitride into isopropanol according to parts by weight, carrying out ultrasonic treatment for 7min at 9000Hz, adding acetic acid and chitosan into the isopropanol, carrying out ultrasonic treatment, and taking an upper layer suspension to obtain a graphite phase carbon nitride emulsion for later use;
s2, adding polyglycol ester diacid and polymethyl methacrylate into the graphite-phase carbon nitride emulsion obtained in the step S1, and stirring at the speed of 350r/min for 35min to obtain a shell material for later use;
s3, mixing the polystyrene microspheres and the polybutadiene, adding the mixture into the shell material obtained in the step S2, centrifuging the mixture for 14min at the speed of 7800r/min, washing the mixture, performing ultrasonic treatment, drying the mixture, and grinding the mixture to obtain the heat-resistant modifier.
The compatilizer is high rubber powder.
The flame retardant is a mixture of brominated polystyrene, decabromodiphenylethane and triphenyl phosphate according to the weight ratio of 1.1:0.9: 0.6.
The thermoplastic elastomer is a polyurethane thermoplastic elastomer, and the polyurethane thermoplastic elastomer is produced by Chong plastic Co.
The toughening modifier is a mixture of nitrile rubber and styrene butadiene rubber in a weight ratio of 1.1: 0.9.
The coupling agent is a silane coupling agent, and the silane coupling agent is a silane coupling agent KH-570.
The preparation method of the heat-resistant flame-retardant ABS composition comprises the following steps:
according to the weight parts, ABS resin, a compatilizer, a flame retardant, a thermoplastic elastomer, a heat-resistant modifier, a toughening modifier, a lubricant and a coupling agent are mixed and then added into a main feeding port of an extruder, the temperature of a first zone is 175 ℃, the temperature of a second zone is 183 ℃, the temperature of a third zone is 183 ℃, the temperature of a fourth zone is 173 ℃, the temperature of a fifth zone is 163 ℃, the mixture is extruded, and meanwhile, graphite whiskers are added into a first exhaust hole or a side feeding port of the extruder, and the heat-resistant flame-retardant ABS composition is obtained through melting granulation.
Example 5
A heat-resistant flame-retardant ABS composition comprises the following raw materials in parts by weight: 60 parts of ABS resin, 5 parts of compatilizer, 10 parts of flame retardant, 5 parts of thermoplastic elastomer, 5 parts of heat-resistant modifier, 8 parts of toughening modifier, 3 parts of lubricant, 5 parts of coupling agent and 7 parts of graphite whisker; the lubricant is pentaerythritol stearate.
The heat-resistant modifier comprises the following raw materials in parts by weight: 10 parts of poly (glycol) diacid, 15 parts of polymethyl methacrylate, 8 parts of graphite-phase carbon nitride, 10 parts of isopropanol, 1.0 part of acetic acid, 0.4 part of chitosan, 8 parts of polystyrene microspheres and 3 parts of polybutadiene; the graphite-phase carbon nitride is produced by Koxing carbon industry Co., Ltd, Haiman city; the polystyrene microsphere is prepared from polystyrene microsphere (PSt) produced by Suzhou New Material science and technology (Suzhou) Co.
The heat-resistant modifier is prepared by the following method:
s1, adding graphite-phase carbon nitride into isopropanol according to parts by weight, performing ultrasonic treatment for 8min at 10000Hz, adding acetic acid and chitosan into the isopropanol, performing ultrasonic treatment, and taking an upper layer suspension to obtain a graphite-phase carbon nitride emulsion for later use;
s2, adding polyglycol ester diacid and polymethyl methacrylate into the graphite-phase carbon nitride emulsion obtained in the step S1, and stirring at the speed of 400r/min for 40min to obtain a shell material for later use;
s3, mixing the polystyrene microspheres and the polybutadiene, adding the mixture into the shell material obtained in the step S2, centrifuging the mixture for 16min at the speed of 80000r/min, washing the mixture, performing ultrasonic treatment, drying the mixture, and grinding the mixture to obtain the heat-resistant modifier.
The compatilizer is high rubber powder.
The flame retardant is a mixture of brominated polystyrene, decabromodiphenylethane and triphenyl phosphate according to the weight ratio of 1.2:1.0: 0.7.
The thermoplastic elastomer is a polyurethane thermoplastic elastomer, and the polyurethane thermoplastic elastomer is produced by Chong plastic Co.
The toughening modifier is a mixture of nitrile rubber and styrene butadiene rubber according to a weight ratio of 1.2: 1.0.
The coupling agent is a titanate coupling agent, and the titanate coupling agent is a titanate coupling agent 201.
The preparation method of the heat-resistant flame-retardant ABS composition comprises the following steps:
according to the weight parts, ABS resin, a compatilizer, a flame retardant, a thermoplastic elastomer, a heat-resistant modifier, a toughening modifier, a lubricant and a coupling agent are mixed and then added into a main feeding port of an extruder, the temperature of a first zone is 180 ℃, the temperature of a second zone is 185 ℃, the temperature of a third zone is 185 ℃, the temperature of a fourth zone is 175 ℃, the temperature of a fifth zone is 165 ℃, the mixture is extruded, and meanwhile, graphite whiskers are added into a first exhaust hole or a side feeding port of the extruder, and the heat-resistant flame-retardant ABS composition is obtained through melt granulation.
Comparative example 1
This comparative example differs from example 1 above in that: the raw materials of the heat-resistant flame-retardant ABS composition in the comparative example are not added with lubricant and graphite whiskers, and the rest of the comparative example is the same as that in example 1, and is not repeated.
Comparative example 2
This comparative example differs from example 3 above in that: the raw materials for preparing the heat-resistant flame-retardant ABS composition in the comparative example are not added with the heat-resistant modifier, and the rest of the comparative example is the same as the example 3 and is not repeated.
Comparative example 3
This comparative example differs from example 5 above in that: in the comparative example, graphite phase carbon nitride, isopropanol, acetic acid and chitosan are not added in the raw materials for preparing the heat-resistant flame-retardant ABS composition, and the rest of the comparative example is the same as that in example 5, and is not repeated.
The heat-resistant flame-retardant ABS compositions prepared in examples 1, 3, 5 and comparative examples 1-3 were subjected to performance tests, the results of which are shown in Table 1 below:
the tensile strength is tested by adopting the GB1040 standard; the elongation at break is tested by the GB1040 standard; the bending strength is tested by adopting the GB9341 standard; oxidation index (GB/T2406-2009); the flame retardant rating was tested by GT/T17591-2006.
TABLE 1
As can be seen from the comparison among examples 1, 3 and 5 and comparative examples 1 to 3, the heat-resistant flame-retardant ABS composition added with the lubricant, the heat-resistant modifier and the graphite whisker has good mechanical properties, flame-retardant effect and stability, and has wide market prospect and application value.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.
Claims (10)
1. A heat-resistant flame-retardant ABS composition is characterized in that: the feed comprises the following raw materials in parts by weight: 40-60 parts of ABS resin, 1-5 parts of compatilizer, 5-10 parts of flame retardant, 1-5 parts of thermoplastic elastomer, 1-5 parts of heat-resistant modifier, 4-8 parts of toughening modifier, 1-3 parts of lubricant, 1-5 parts of coupling agent and 3-7 parts of graphite whisker.
2. The heat-resistant flame-retardant ABS composition according to claim 1, characterized in that: the heat-resistant modifier comprises the following raw materials in parts by weight: 5-10 parts of poly (glycol) diacid, 10-15 parts of polymethyl methacrylate, 4-8 parts of graphite-phase carbon nitride, 5-10 parts of isopropanol, 0.6-1.0 part of acetic acid, 0.2-0.4 part of chitosan, 4-8 parts of polystyrene microspheres and 1-3 parts of polybutadiene.
3. The heat-resistant flame-retardant ABS composition according to claim 2, characterized in that: the heat-resistant modifier is prepared by the following method:
s1, adding graphite-phase carbon nitride into isopropanol according to parts by weight, carrying out ultrasonic treatment at 6000-10000Hz for 4-8min, adding acetic acid and chitosan into the isopropanol, carrying out ultrasonic treatment, and taking upper-layer suspension to obtain graphite-phase carbon nitride emulsion for later use;
s2, adding poly (diol diacid) ester and polymethyl methacrylate into the graphite-phase carbon nitride emulsion obtained in the step S1, and stirring at the speed of 200-400r/min for 20-40min to obtain a shell material for later use;
s3, mixing the polystyrene microspheres and polybutadiene, adding the mixture into the shell material obtained in the step S2, centrifuging the mixture at the speed of 7000 and 80000r/min for 8 to 16min, washing the mixture, performing ultrasonic treatment, drying and grinding the mixture to obtain the heat-resistant modifier.
4. The heat-resistant flame-retardant ABS composition according to claim 1, characterized in that: the compatilizer is at least one of high rubber powder or maleic anhydride.
5. The heat-resistant flame-retardant ABS composition according to claim 1, characterized in that: the flame retardant is at least one of brominated polystyrene, decabromodiphenylethane, decabromodiphenyl ether and triphenyl phosphate.
6. The heat and flame resistant ABS composition according to claim 1, wherein: the thermoplastic elastomer is at least one of polyurethane thermoplastic elastomer and polyether ester thermoplastic elastomer.
7. The heat-resistant flame-retardant ABS composition according to claim 1, characterized in that: the toughening modifier is at least one of nitrile rubber and styrene butadiene rubber.
8. The heat-resistant flame-retardant ABS composition according to claim 1, characterized in that: the lubricant is pentaerythritol stearate.
9. The heat-resistant flame-retardant ABS composition according to claim 1, characterized in that: the coupling agent is at least one of silane coupling agent, titanate coupling agent, aluminate coupling agent and zirconate coupling agent.
10. A method for preparing a heat and flame resistant ABS composition according to any of claims 1-9, characterized in that: is prepared by the following steps:
according to the weight parts, ABS resin, a compatilizer, a flame retardant, a thermoplastic elastomer, a heat-resistant modifier, a toughening modifier, a lubricant and a coupling agent are mixed and then added into a main feeding port of an extruder, the temperature of a first zone is 160-plus-180 ℃, the temperature of a second zone is 175-plus-185 ℃, the temperature of a third zone is 175-plus-185 ℃, the temperature of a fourth zone is 165-plus-175 ℃ and the temperature of a fifth zone is 155-plus-165 ℃ for extrusion, and graphite whiskers are added into a first exhaust hole or a side feeding port of the extruder at the same time for melting and granulation to obtain the heat-resistant flame-retardant ABS composition.
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