CN108794968B - High-strength flame-retardant ABS (acrylonitrile-butadiene-styrene) alloy material and preparation method thereof - Google Patents
High-strength flame-retardant ABS (acrylonitrile-butadiene-styrene) alloy material and preparation method thereof Download PDFInfo
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- 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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- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention relates to the technical field of high polymer materials, and discloses a high-strength flame-retardant ABS alloy material and a preparation method thereof. The ABS alloy material comprises the following raw materials in parts by weight: 20-80 parts of acrylonitrile-butadiene-styrene copolymer, 10-70 parts of polycarbonate, 3-10 parts of compatilizer and 0.1-0.5 part of antioxidant; the ABS alloy material is obtained by mixing, melting and blending, extruding, air-drying and granulating all the components. The alloy material of the invention has higher strength and excellent fire resistance.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a high-strength flame-retardant ABS alloy material and a preparation method thereof.
Background
ABS (acrylonitrile-butadiene-styrene) material has excellent chemical resistance, mechanical properties and excellent processability, and is therefore widely used in the industries of automobiles, home appliances, aviation, ships, and the like. With the continuous demand of products for materials, modified ABS is also increasingly appearing in the market. ABS is one of five synthetic resin materials, its impact resistance, heat resistance, low temperature resistance, chemical resistance and electrical properties are excellent, and it also has the advantages of easy processing, stable product size, good surface gloss, etc., and it is easy to coat and color, and can also be used for secondary processing such as surface spraying metal, electroplating, welding, hot pressing and bonding, and it can be widely used in the fields of machinery, automobile, electronic and electrical appliances, instruments and meters, textile and building industries, and it is a thermoplastic plastic with wide application. However, ABS itself has limited its range of use due to its poor flame retardancy, poor heat stability, poor corrosion resistance, poor electrical insulation, and the like.
Disclosure of Invention
The invention provides an ABS alloy material with excellent flame retardant property, aiming at overcoming the problem of poor flame retardant property of ABS in the prior art.
The invention also provides a preparation method of the ABS alloy material.
In order to achieve the purpose, the invention adopts the following technical scheme: the high-strength flame-retardant ABS alloy material is characterized by comprising the following raw materials in parts by weight: 20-80 parts of acrylonitrile-butadiene-styrene copolymer, 10-70 parts of polycarbonate, 3-10 parts of compatilizer, 0.1-0.5 part of antioxidant and 15-20 parts of flame retardant.
The polycarbonate has good impact resistance, water resistance and dielectric property, good dimensional stability, wear resistance, corrosion resistance and high thermal stability and flame retardance.
Preferably, the compatibilizer is at least one of a maleic anhydride-styrene-acrylonitrile copolymer and a styrene block copolymer.
Preferably, the antioxidant is at least one of antioxidant 1010 and antioxidant 168.
Preferably, the flame retardant comprises a brominated flame retardant, a flame retardant synergist and an anti-sag agent.
Preferably, the brominated flame retardant is decabromodiphenylethane, the flame-retardant synergist is antimony trioxide, and the anti-sagging agent is polytetrafluoroethylene.
According to the invention, decabromodiphenylethane is used as a brominated flame retardant, antimony trioxide is used as a flame-retardant synergist, polytetrafluoroethylene is used as a low-dropout-resistant agent, and after the decabromodiphenylethane, the antimony trioxide and the polytetrafluoroethylene are mixed, the flame-retardant performance of ABS is greatly improved through the synergistic effect of the decabromodiphenylethane, the antimony trioxide and the polytetrafluoroethylene.
Preferably, the formula composition further comprises 20-40 parts of modified polyurethane resin, 5-10 parts of glass fiber and 10-20 parts of modified zeolite.
The polyurethane resin has better mechanical strength, wear resistance and aging resistance, and the strength and aging resistance of the ABS are improved by blending the polyurethane resin and the ABS; the glass fiber can fix the high molecular polymer mutually, improve the strength of ABS and prevent cracking after long-term use.
Preferably, the preparation method of the modified polyurethane resin comprises the following steps: mixing 5-10 parts by weight of hydroxy citric acid, 1-2 parts by weight of methyl trifluoro propyl silicone oil and 2-5 parts by weight of ethylene glycol diglycidyl ether, heating to 60-70 ℃, reacting for 1-3 hours, adding 30-40 parts by weight of toluene diisocyanate and 10-15 parts by weight of polyethylene glycol, stirring, reacting for 3-6 hours, defoaming in vacuum to obtain a polyurethane prepolymer, heating the polyurethane prepolymer to a molten state, adding 0.02-0.05 part by weight of 2-methylpentadiamine chain extender, stirring, reacting for 1-2 hours, and finally carrying out pressure vulcanization and cooling to obtain the modified polyurethane resin.
The method comprises the steps of grafting an epoxy group of ethylene glycol diglycidyl ether onto methyl trifluoropropyl silicone oil by ring opening, then carrying out grafting reaction with hydroxycitric acid, carrying out a polymerization reaction on a low molecular polymer generated by the reaction of the three, monomer toluene diisocyanate and ethylene glycol to generate a polyurethane prepolymer, and adding a 2-methylpentanediamine chain extender to obtain the modified polyurethane resin.
Preferably, the preparation method of the modified zeolite comprises the following steps: adding 1-3 parts by mass of nano silica particles into 30-40 parts by mass of polytetrafluoroethylene emulsion, uniformly stirring, adding 10-15 parts by mass of zeolite, carrying out ultrasonic oscillation for 2-6 hours, standing for 10-20 hours, calcining the filtered zeolite in a muffle furnace at the temperature of 327-350 ℃ for 10-20 hours, and cooling to obtain the modified zeolite.
The invention utilizes the three-dimensional pore structure of zeolite, enables nano-silica and polytetrafluoroethylene emulsion to enter the three-dimensional pore structure of zeolite through ultrasonic oscillation, then leads polytetrafluoroethylene to be melted through high-temperature calcination, then leads the polytetrafluoroethylene to be solidified in the three-dimensional pores of the zeolite through cooling, leads the nano-silica dispersed in the three-dimensional pores to be fixed by the polytetrafluoroethylene, leads the nano-silica not to be easily separated from the zeolite, then takes the zeolite as a carrier to be dispersed in the ABS, greatly improves the mixing uniformity of the nano-silica, in addition, the polytetrafluoroethylene has super-hydrophobic property, can further increase the hydrophobic property of the material, and leads the polytetrafluoroethylene to be solidified in the three-dimensional pores of the zeolite, the abrasion does not cause the reduction of the hydrophobicity of the surface of the material, and the hydrophobic stability is stronger.
A preparation method of a high-strength flame-retardant ABS alloy material comprises the following steps:
1) adding the acrylonitrile-butadiene-styrene copolymer, the polycarbonate and the compatilizer in parts by weight of the formula into a stirrer, stirring for 5-10 minutes, then adding the rest of the formula components, and continuing stirring for 10-20 minutes to obtain a mixed material;
2) and adding the mixed material into a double-screw extruder, and carrying out melt mixing, extrusion, air drying and grain cutting to obtain the ABS alloy material.
Therefore, the invention has the following beneficial effects: (1) polycarbonate and polyurethane are mixed into ABS, so that the strength and the thermal stability of the material are greatly improved; (2) has better flame retardant effect; (3) has stable hydrophobic property.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
In the present invention, unless otherwise specified, all the raw materials and equipment used are commercially available or commonly used in the art, and the methods in the examples are conventional in the art unless otherwise specified.
Example 1
A high-strength flame-retardant ABS alloy material comprises the following raw materials in parts by weight: 20 parts of acrylonitrile-butadiene-styrene copolymer, 10 parts of polycarbonate, 3 parts of maleic anhydride-styrene-acrylonitrile copolymer compatilizer, 0.1 part of 1010 antioxidant and 15 parts of flame retardant. The flame retardant comprises decabromodiphenylethane, antimony trioxide and polytetrafluoroethylene, wherein the mass ratio of the decabromodiphenylethane to the antimony trioxide to the polytetrafluoroethylene is 1:0.1: 0.4.
A preparation method of a high-strength flame-retardant ABS alloy material comprises the following steps:
1) adding the acrylonitrile-butadiene-styrene copolymer, the polycarbonate and the compatilizer in parts by weight of the formula into a stirrer, stirring for 5 minutes, then adding the rest components of the formula, and continuing stirring for 10 minutes to obtain a mixed material;
2) and adding the mixed material into a double-screw extruder, and carrying out melt mixing, extrusion, air drying and grain cutting to obtain the ABS alloy material.
Example 2
A high-strength flame-retardant ABS alloy material comprises the following raw materials in parts by weight: 20 parts of acrylonitrile-butadiene-styrene copolymer, 10 parts of polycarbonate, 3 parts of maleic anhydride-styrene-acrylonitrile copolymer compatilizer, 0.1 part of 1010 antioxidant, 15 parts of flame retardant, 20 parts of modified polyurethane resin, 5 parts of glass fiber and 10 parts of modified zeolite. The flame retardant comprises decabromodiphenylethane, antimony trioxide and polytetrafluoroethylene, wherein the mass ratio of the decabromodiphenylethane to the antimony trioxide to the polytetrafluoroethylene is 1:0.1: 0.4.
The preparation method of the modified polyurethane resin comprises the following steps:
mixing 5 parts by weight of hydroxycitric acid, 1 part by weight of methyl trifluoropropyl silicone oil and 2 parts by weight of ethylene glycol diglycidyl ether, heating to 60 ℃, reacting for 1 hour, adding 30 parts by weight of toluene diisocyanate and 10 parts by weight of polyethylene glycol, stirring for reacting for 3 hours, defoaming in vacuum to obtain a polyurethane prepolymer, heating the polyurethane prepolymer to a molten state, adding 0.02 part by weight of 2-methylpentanediamine chain extender, stirring for reacting for 1 hour, and finally, carrying out pressure vulcanization and cooling to obtain the modified polyurethane resin.
The preparation method of the modified zeolite comprises the following steps:
firstly, adding 1 part by mass of nano silica particles into 30 parts by mass of polytetrafluoroethylene emulsion, uniformly stirring, then adding 10 parts by mass of zeolite, carrying out ultrasonic oscillation for 2 hours, standing for 10 hours, putting the filtered zeolite into a muffle furnace, calcining for 10 hours at the temperature of 327 ℃, and cooling to obtain the modified zeolite.
A preparation method of a high-strength flame-retardant ABS alloy material comprises the following steps:
1) adding the acrylonitrile-butadiene-styrene copolymer, the polycarbonate and the compatilizer in parts by weight of the formula into a stirrer, stirring for 5 minutes, then adding the rest components of the formula, and continuing stirring for 10 minutes to obtain a mixed material;
2) and adding the mixed material into a double-screw extruder, and carrying out melt mixing, extrusion, air drying and grain cutting to obtain the ABS alloy material.
Example 3
A high-strength flame-retardant ABS alloy material comprises the following raw materials in parts by weight: 30 parts of acrylonitrile-butadiene-styrene copolymer, 30 parts of polycarbonate, 4 parts of styrene block copolymer compatilizer, 0.2 part of 168 antioxidant, 16 parts of flame retardant, 25 parts of modified polyurethane resin, 6 parts of glass fiber and 12 parts of modified zeolite. The flame retardant comprises decabromodiphenylethane, antimony trioxide and polytetrafluoroethylene, wherein the mass ratio of the decabromodiphenylethane to the antimony trioxide to the polytetrafluoroethylene is 1:0.1: 0.4.
The preparation method of the modified polyurethane resin comprises the following steps:
mixing 6 parts by weight of hydroxycitric acid, 1 part by weight of methyl trifluoropropyl silicone oil and 3 parts by weight of ethylene glycol diglycidyl ether, heating to 65 ℃, reacting for 1.5h, adding 33 parts by weight of toluene diisocyanate and 12 parts by weight of polyethylene glycol, stirring for reacting for 4h, defoaming in vacuum to obtain a polyurethane prepolymer, heating the polyurethane prepolymer to a molten state, adding 0.03 part by weight of 2-methylpentanediamine chain extender, stirring for reacting for 1h, and finally, carrying out pressure vulcanization and cooling to obtain the modified polyurethane resin.
The preparation method of the modified zeolite comprises the following steps:
adding 1 part by mass of nano silica particles into 32 parts by mass of polytetrafluoroethylene emulsion, uniformly stirring, adding 12 parts by mass of zeolite, carrying out ultrasonic oscillation for 3 hours, standing for 13 hours, putting the filtered zeolite into a muffle furnace, calcining for 13 hours at the temperature of 330 ℃, and cooling to obtain the modified zeolite.
A preparation method of a high-strength flame-retardant ABS alloy material comprises the following steps:
1) adding the acrylonitrile-butadiene-styrene copolymer, the polycarbonate and the compatilizer in parts by weight of the formula into a stirrer, stirring for 6 minutes, then adding the rest components of the formula, and continuing stirring for 12 minutes to obtain a mixed material;
2) and adding the mixed material into a double-screw extruder, and carrying out melt mixing, extrusion, air drying and grain cutting to obtain the ABS alloy material.
Example 4
A high-strength flame-retardant ABS alloy material comprises the following raw materials in parts by weight: 50 parts of acrylonitrile-butadiene-styrene copolymer, 40 parts of polycarbonate, 6 parts of maleic anhydride-styrene-acrylonitrile copolymer compatilizer, 0.3 part of 1010 antioxidant, 17 parts of flame retardant, 30 parts of modified polyurethane resin, 7 parts of glass fiber and 16 parts of modified zeolite. The flame retardant comprises decabromodiphenylethane, antimony trioxide and polytetrafluoroethylene, wherein the mass ratio of the decabromodiphenylethane to the antimony trioxide to the polytetrafluoroethylene is 1:0.2: 0.5.
The preparation method of the modified polyurethane resin comprises the following steps:
mixing 7 parts by weight of hydroxycitric acid, 1.5 parts by weight of methyl trifluoropropyl silicone oil and 3.5 parts by weight of ethylene glycol diglycidyl ether, heating to 66 ℃, reacting for 2 hours, adding 36 parts by weight of toluene diisocyanate and 13 parts by weight of polyethylene glycol, stirring for reacting for 4.5 hours, defoaming in vacuum to obtain a polyurethane prepolymer, heating the polyurethane prepolymer to a molten state, adding 0.03 part by weight of 2-methylpentadiamine chain extender, stirring for reacting for 1.5 hours, and finally, carrying out pressure vulcanization and cooling to obtain the modified polyurethane resin.
The preparation method of the modified zeolite comprises the following steps:
adding 2 parts by mass of nano silica particles into 35 parts by mass of polytetrafluoroethylene emulsion, uniformly stirring, adding 13 parts by mass of zeolite, carrying out ultrasonic oscillation for 4 hours, standing for 16 hours, putting the filtered zeolite into a muffle furnace, calcining for 15 hours at the temperature of 335 ℃, and cooling to obtain the modified zeolite.
A preparation method of a high-strength flame-retardant ABS alloy material comprises the following steps:
1) adding the acrylonitrile-butadiene-styrene copolymer, the polycarbonate and the compatilizer in parts by weight of the formula into a stirrer, stirring for 7 minutes, then adding the rest components of the formula, and continuing stirring for 15 minutes to obtain a mixed material;
2) and adding the mixed material into a double-screw extruder, and carrying out melt mixing, extrusion, air drying and grain cutting to obtain the ABS alloy material.
Example 5
A high-strength flame-retardant ABS alloy material comprises the following raw materials in parts by weight: 70 parts of acrylonitrile-butadiene-styrene copolymer, 60 parts of polycarbonate, 8 parts of styrene block copolymer compatilizer, 0.4 part of 168 antioxidant, 18 parts of flame retardant, 35 parts of modified polyurethane resin, 8 parts of glass fiber and 18 parts of modified zeolite. The flame retardant comprises decabromodiphenylethane, antimony trioxide and polytetrafluoroethylene, wherein the mass ratio of the decabromodiphenylethane to the antimony trioxide to the polytetrafluoroethylene is 1:0.3: 0.6.
The preparation method of the modified polyurethane resin comprises the following steps:
mixing 8 parts by weight of hydroxycitric acid, 2 parts by weight of methyl trifluoropropyl silicone oil and 4 parts by weight of ethylene glycol diglycidyl ether, heating to 68 ℃, reacting for 2.5 hours, adding 38 parts by weight of toluene diisocyanate and 14 parts by weight of polyethylene glycol, stirring for reacting for 5 hours, defoaming in vacuum to obtain a polyurethane prepolymer, heating the polyurethane prepolymer to a molten state, adding 0.04 part by weight of 2-methylpentanediamine chain extender, stirring for reacting for 2 hours, and finally, carrying out pressure vulcanization and cooling to obtain the modified polyurethane resin.
The preparation method of the modified zeolite comprises the following steps:
adding 3 parts by mass of nano silicon dioxide particles into 38 parts by mass of polytetrafluoroethylene emulsion, uniformly stirring, adding 14 parts by mass of zeolite, carrying out ultrasonic oscillation for 5 hours, standing for 18 hours, putting the filtered zeolite into a muffle furnace, calcining for 18 hours at the temperature of 340 ℃, and cooling to obtain the modified zeolite.
A preparation method of a high-strength flame-retardant ABS alloy material comprises the following steps:
1) adding the acrylonitrile-butadiene-styrene copolymer, the polycarbonate and the compatilizer in parts by weight of the formula into a stirrer, stirring for 8 minutes, then adding the rest components of the formula, and continuing stirring for 18 minutes to obtain a mixed material;
2) and adding the mixed material into a double-screw extruder, and carrying out melt mixing, extrusion, air drying and grain cutting to obtain the ABS alloy material.
Example 6
A high-strength flame-retardant ABS alloy material comprises the following raw materials in parts by weight: 80 parts of acrylonitrile-butadiene-styrene copolymer, 70 parts of polycarbonate, 10 parts of maleic anhydride-styrene-acrylonitrile copolymer compatilizer, 0.5 part of 1010 antioxidant, 20 parts of flame retardant, 40 parts of modified polyurethane resin, 10 parts of glass fiber and 20 parts of modified zeolite. The flame retardant comprises decabromodiphenylethane, antimony trioxide and polytetrafluoroethylene, wherein the mass ratio of the decabromodiphenylethane to the antimony trioxide to the polytetrafluoroethylene is 1:0.3: 0.6.
The preparation method of the modified polyurethane resin comprises the following steps:
mixing 10 parts by weight of hydroxycitric acid, 2 parts by weight of methyl trifluoropropyl silicone oil and 5 parts by weight of ethylene glycol diglycidyl ether, heating to 70 ℃, reacting for 3 hours, adding 40 parts by weight of toluene diisocyanate and 15 parts by weight of polyethylene glycol, stirring for reacting for 6 hours, defoaming in vacuum to obtain a polyurethane prepolymer, heating the polyurethane prepolymer to a molten state, adding 0.05 part by weight of 2-methylpentanediamine chain extender, stirring for reacting for 2 hours, and finally, carrying out pressure vulcanization and cooling to obtain the modified polyurethane resin.
The preparation method of the modified zeolite comprises the following steps:
adding 3 parts by mass of nano silica particles into 40 parts by mass of polytetrafluoroethylene emulsion, uniformly stirring, adding 15 parts by mass of zeolite, carrying out ultrasonic oscillation for 6 hours, standing for 20 hours, putting the filtered zeolite into a muffle furnace, calcining for 20 hours at the temperature of 350 ℃, and cooling to obtain the modified zeolite.
A preparation method of a high-strength flame-retardant ABS alloy material comprises the following steps:
1) adding the acrylonitrile-butadiene-styrene copolymer, the polycarbonate and the compatilizer in parts by weight of the formula into a stirrer, stirring for 10 minutes, then adding the rest components of the formula, and continuing stirring for 20 minutes to obtain a mixed material;
2) and adding the mixed material into a double-screw extruder, and carrying out melt mixing, extrusion, air drying and grain cutting to obtain the ABS alloy material.
Examples sample performance testing:
although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (7)
1. The high-strength flame-retardant ABS alloy material is characterized by comprising the following raw materials in parts by weight:
20-80 parts of acrylonitrile-butadiene-styrene copolymer, 10-70 parts of polycarbonate, 3-10 parts of compatilizer, 0.1-0.5 part of antioxidant and 15-20 parts of flame retardant;
the modified polyurethane resin comprises 20-40 parts of modified polyurethane resin, 5-10 parts of glass fiber and 10-20 parts of modified zeolite;
the preparation method of the modified polyurethane resin comprises the following steps: mixing 5-10 parts by weight of hydroxy citric acid, 1-2 parts by weight of methyl trifluoro propyl silicone oil and 2-5 parts by weight of ethylene glycol diglycidyl ether, heating to 60-70 ℃, reacting for 1-3 hours, adding 30-40 parts by weight of toluene diisocyanate and 10-15 parts by weight of polyethylene glycol, stirring, reacting for 3-6 hours, defoaming in vacuum to obtain a polyurethane prepolymer, heating the polyurethane prepolymer to a molten state, adding 0.02-0.05 part by weight of 2-methylpentadiamine chain extender, stirring, reacting for 1-2 hours, and finally carrying out pressure vulcanization and cooling to obtain the modified polyurethane resin.
2. The ABS alloy material of claim 1, wherein the compatibilizer is at least one of a maleic anhydride-styrene-acrylonitrile copolymer and a styrene block copolymer.
3. The ABS alloy material of claim 1, wherein the antioxidant is at least one of antioxidant 1010 and antioxidant 168.
4. The ABS alloy material of claim 1, wherein the flame retardant comprises a brominated flame retardant, a flame retardant synergist and an anti-dripping agent.
5. The ABS alloy material of claim 4, wherein the brominated flame retardant is decabromodiphenylethane, the flame retardant synergist is antimony trioxide, and the anti-dripping agent is polytetrafluoroethylene.
6. The high-strength flame-retardant ABS alloy material of claim 1, wherein the preparation method of the modified zeolite comprises: adding 1-3 parts by mass of nano silica particles into 30-40 parts by mass of polytetrafluoroethylene emulsion, uniformly stirring, adding 10-15 parts by mass of zeolite, carrying out ultrasonic oscillation for 2-6 hours, standing for 10-20 hours, calcining the filtered zeolite in a muffle furnace at the temperature of 327-350 ℃ for 10-20 hours, and cooling to obtain the modified zeolite.
7. The preparation method of the high-strength flame-retardant ABS alloy material as claimed in any of claims 1-6, characterized by comprising the following steps:
1) adding the acrylonitrile-butadiene-styrene copolymer, the polycarbonate and the compatilizer in parts by weight of the formula into a stirrer, stirring for 5-10 minutes, then adding the rest of the formula components, and continuing stirring for 10-20 minutes to obtain a mixed material;
2) and adding the mixed material into a double-screw extruder, and carrying out melt mixing, extrusion, air drying and grain cutting to obtain the ABS alloy material.
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| CN102070894A (en) * | 2011-01-19 | 2011-05-25 | 烟台万华聚氨酯股份有限公司 | High-fluidity high-impact-resistance scraping-resistance polycarbonate composition and preparation method thereof |
| 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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