CN114656747B - ABS flame-retardant composite material with high impact resistance and low volume resistance and preparation method thereof - Google Patents
ABS flame-retardant composite material with high impact resistance and low volume resistance and preparation method thereof Download PDFInfo
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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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K2201/017—Additives being an antistatic agent
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- 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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- C08L2201/04—Antistatic
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Abstract
The invention discloses a high-impact low-volume resistance ABS flame-retardant composite material, which is prepared from the following raw materials, by mass, 100 parts of ABS resin, 20-30 parts of styrene-butadiene copolymer, 3-10 parts of flame retardant, 1-4 parts of antistatic agent, 0.5-2 parts of structural strength enhancer and 1-5 parts of adaptation modifier. According to the ABS flame-retardant composite material with high impact resistance and low volume resistance, the antistatic property of an antistatic agent in the composite material is improved by adding the styrene-butadiene copolymer, and meanwhile, the toughness of a composite material system is improved; the structural strength reinforcing agent is added to improve the mechanical properties of the composite material such as impact resistance, stretching resistance and the like; the antistatic agent and the flame retardant are not interfered with each other, and the obtained ABS flame-retardant composite material has excellent impact strength, good/stable antistatic performance and excellent flame retardant performance.
Description
Technical Field
The invention relates to the technical field of composite materials and preparation thereof, in particular to an ABS flame-retardant composite material with high impact resistance and low volume resistance and a preparation method thereof.
Background
The acrylonitrile-butadiene-styrene copolymer (ABS) is a terpolymer of acrylonitrile, 1, 3-butadiene and styrene, is a thermoplastic high-molecular material with higher strength, good toughness and easy processing and forming, the processed product has smooth surface, is easy to dye and electroplate, the product can be normally used in a wider temperature range of-25 ℃ to 60 ℃, and meanwhile, the ABS can be mixed with various resins to form a blend, and the ABS is mainly used for alloys, plastics, ABS brands and the like in the prior art.
Although ABS resin has good mechanical property and use property, it can be widely used in various fields, but ABS resin itselfHigh insulating electrical properties (surface resistivity of 4X 10) 15 Omega) and lower oxygen index (20%) are used for easily accumulating static electricity and being inflammable, particularly, combustion phenomenon caused by static electricity accumulation is easy to occur, and the application of the ABS material in the fields of mines, petrochemical industry and the like is greatly limited. In order to increase antistatic and flame-retardant properties of the ABS material, the ABS resin is processed into an antistatic ABS flame-retardant composite material by adding an antistatic agent and a flame retardant in the prior art, but the addition of the antistatic agent and the flame retardant inevitably leads to the reduction of mechanical properties such as impact strength and the like of the composite material, and mutual interference is easy to occur between the antistatic agent and the flame retardant, so that the antistatic property is difficult to maintain permanently and stably.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an ABS flame-retardant composite material with high impact resistance and low volume resistance and a preparation method thereof.
The technical scheme adopted for solving the technical problems is as follows:
the ABS flame-retardant composite material with high impact resistance and low volume resistance comprises, by mass, 100 parts of ABS resin, 20-30 parts of styrene-butadiene copolymer, 3-10 parts of flame retardant, 1-4 parts of antistatic agent, 0.5-2 parts of structural strength reinforcing agent and 1-5 parts of adaptation modifier.
Further, the butadiene content of the styrene-butadiene copolymer is more than 60%, and the ABS rubber powder can effectively improve the impact strength of the composite material. The styrene-butadiene copolymer can reduce the glass transition temperature of a composite material system to a certain extent, and can improve the antistatic property of the composite material added with the antistatic agent on the basis, because the movement of chain segments of the styrene-butadiene copolymer becomes easier at the use temperature along with the reduction of the glass transition temperature of the composite material, thereby promoting the migration of antistatic agent molecules in the system to the surface of the composite material and reducing the surface resistivity of the composite material system; however, the addition of the styrene-butadiene copolymer can reduce the impact resistance and the tensile strength of the composite material, and on the basis, the impact caused by the addition of the structural strength reinforcing agent can be well reduced.
Further, the structural strength enhancer is hydrophobically modified powder of the optical rod waste material.
Further, the preparation method of the hydrophobically modified powder of the light bar waste comprises the following steps: drying, crushing and sieving the optical fiber preform waste to obtain 50-60 mesh granules, roasting the obtained granules at 500-600 ℃ for 1.5-2.5h, taking out and naturally cooling in a dryer to obtain nano powder, then placing the obtained nano powder in a dry heat environment for activation treatment, reacting the activated nano powder with a silane coupling agent in a xylene solution, centrifuging, taking out a solid, washing and drying to obtain the optical fiber preform.
Further, the activation condition is that the activation is carried out for 12-18 hours at 150-160 ℃ in a drying oven; the reaction conditions with the silane coupling agent are as follows: the weight ratio of the activated nano powder to the silane coupling agent is 1:1-2, namely, 1 mass part of the nano powder to 1-2 mass parts of the silane coupling agent are mixed, 2-3 mass parts of the mixture of the activated nano powder and the silane coupling agent is placed in 10-20 weight parts of dimethylbenzene, and the mixture reacts for 6-8 hours at the temperature of 110-120 ℃; the washing is carried out by using sewage ethanol for washing for at least two times, centrifugal solid removal is carried out after each washing is completed, and finally, the hydrophobically modified powder of the optical rod waste material is obtained after full drying. The light bar waste hydrophobically modified powder is nano fine particles, the particle size is small, the surface is porous, polar hydroxyl existing on the surface is modified after being treated by a silane coupling agent, the light bar waste hydrophobically modified powder can be uniformly dispersed in a polymer ABS material with low polarity to form a compound, and ABS and styrene-butadiene copolymer molecular chains can well pass through pores on the light bar waste hydrophobically modified powder particles to be crosslinked and compounded with the particles, so that the light bar waste hydrophobically modified powder can better resist impact and stretching, and meanwhile, the influence of the addition of the styrene-butadiene copolymer and the adaptation modifier on the mechanical property of the composite material is reduced.
Further, the flame retardant is a composite of tetrabromobisphenol A and antimony pentoxide, wherein the weight ratio of the tetrabromobisphenol A to the antimony pentoxide is 2-3:1, namely 2-3 parts by mass of tetrabromobisphenol A and 1 part by mass of antimony pentoxide are compounded to obtain the flame retardant. The addition of the flame retardant can influence the mechanical property of the composite material system, so the influence on the mechanical property of the composite material system caused by the addition of the flame retardant is reduced by adding a larger proportion of the styrene-butadiene copolymer to be matched with the structural strength reinforcing agent; the problem of reduced processability of the composite material system caused by the addition of the flame retardant and the structural strength enhancer can be reduced by adding the adaptation modifier.
Further, the antistatic agent is linear alkyl sulfonate.
Further, the number of carbon in the molecular structure of the linear alkyl sulfonate is smaller than 14, so that the linear alkyl sulfonate can be more easily migrated to the surface of the composite material to exert antistatic performance.
Further, the adaptation modifier is an ethylene-acrylic ester-glycidyl methacrylate terpolymer, and the addition of the adaptation modifier can improve the toughness and the processability of a composite material system.
The preparation method of the ABS flame-retardant composite material with high impact resistance and low volume resistance comprises the following steps: the ABS resin, the styrene-butadiene copolymer, the flame retardant, the antistatic agent, the structural strength reinforcing agent and the adaptation modifier are mixed according to the weight parts: 100 parts of ABS resin, 20-30 parts of styrene-butadiene copolymer, 3-10 parts of flame retardant, 1-4 parts of antistatic agent, 0.5-2 parts of structural strength reinforcing agent and 1-5 parts of adaptation modifier; and (3) placing the mixed raw materials into a blender for high-speed blending for 15-20min, and then carrying out mixing and granulating by a screw extruder to obtain the composite material. The extrusion process conditions are as follows: and (3) melting and mixing the materials at 190-220 ℃ through a double-screw extruder.
Compared with the prior art, the invention has the beneficial effects that:
according to the ABS flame-retardant composite material with high impact resistance and low volume resistance, the antistatic property of an antistatic agent in the composite material is improved by adding the styrene-butadiene copolymer, and meanwhile, the toughness of a composite material system is improved; the structural strength reinforcing agent is added to improve the mechanical properties of the composite material such as impact resistance, stretching resistance and the like; the antistatic agent and the flame retardant are not interfered with each other, the inorganic component content in the flame retardant is small, the migration and diffusion effects on the antistatic agent are small, and the organic flame retardant has no adsorption effect on the antistatic agent, so that the flame retardant of the invention basically does not influence the performance of antistatic agent on the antistatic property, and conversely, the performance of the antistatic agent on the flame retardant is not influenced; the obtained ABS flame-retardant composite material with high impact resistance and low volume resistance has excellent impact strength, better/stable antistatic performance and excellent flame retardant performance.
Detailed Description
The invention will be further illustrated with reference to specific examples.
Example 1: the ABS flame-retardant composite material with high impact resistance and low volume resistance comprises the following raw materials of 100 parts of ABS resin, 25 parts of styrene-butadiene copolymer, 6 parts of flame retardant, 3 parts of antistatic agent, 1 part of structural strength enhancer and 3 parts of adaptation modifier.
Further, the butadiene content of the styrene-butadiene copolymer is more than 60%.
Further, the structural strength enhancer is hydrophobically modified powder of the optical rod waste; the preparation method of the hydrophobically modified powder of the optical rod waste material comprises the following steps: drying, crushing and sieving the optical fiber preform waste to obtain 50-60 mesh granules, roasting the obtained granules at 550 ℃ for 2 hours, taking out and placing the granules in a dryer for natural cooling to obtain nano powder, then placing the obtained nano powder in a dry heat environment for activation treatment, reacting the activated nano powder with a silane coupling agent in a xylene solution, centrifuging, taking a solid, washing and drying to obtain the optical fiber preform; the activation condition is that the mixture is activated for 15 hours at 155 ℃ in a drying oven; the reaction conditions with the silane coupling agent are as follows: the weight ratio of the activated nano powder to the silane coupling agent is 2:3, 5 parts by mass of the mixture of the activated nano powder and the silane coupling agent is placed in 30 parts by weight of dimethylbenzene, and the mixture reacts for 7 hours at 115 ℃; the washing is carried out by using sewage ethanol, the washing times are two times, the solid is centrifugally taken after each washing is finished, and finally the hydrophobically modified powder of the optical rod waste material is obtained after full drying.
Further, the flame retardant is a composite of tetrabromobisphenol A and antimony pentoxide, and the weight ratio of the tetrabromobisphenol A to the antimony pentoxide is 5:2; the antistatic agent is linear alkyl sulfonate; the number of carbon in the molecular structure of the linear alkyl sulfonate is less than 14; the adaptation modifier is an ethylene-acrylic ester-glycidyl methacrylate terpolymer.
Example 2: the ABS flame-retardant composite material with high impact resistance and low volume resistance comprises the following raw materials of 100 parts of ABS resin, 20 parts of styrene-butadiene copolymer, 3 parts of flame retardant, 1 part of antistatic agent, 0.5 part of structural strength enhancer and 1 part of adaptation modifier in parts by mass.
Further, the butadiene content of the styrene-butadiene copolymer is more than 60%.
Further, the structural strength enhancer is hydrophobically modified powder of the optical rod waste; the preparation method of the hydrophobically modified powder of the optical rod waste material comprises the following steps: drying, crushing and sieving the optical fiber preform waste to obtain 50-60 mesh granules, roasting the obtained granules at 500 ℃ for 1.5 hours, taking out and placing the granules in a dryer for natural cooling to obtain nano powder, then placing the obtained nano powder in a dry heat environment for activation treatment, reacting the activated nano powder with a silane coupling agent in a xylene solution, centrifuging, taking a solid, washing and drying to obtain the optical fiber preform; the activation condition is that the mixture is activated for 12 hours at 150 ℃ in a drying oven; the reaction conditions with the silane coupling agent are as follows: the weight ratio of the activated nano powder to the silane coupling agent is 1:2, and 3 parts by mass of the mixture of the activated nano powder and the silane coupling agent is placed in 10 parts by weight of dimethylbenzene and reacts for 6 hours at 110 ℃; the washing is carried out by using sewage ethanol, the washing times are three times, the solid is centrifugally taken after each washing is finished, and finally the hydrophobically modified powder of the optical rod waste material is obtained after full drying.
Further, the flame retardant is a composite of tetrabromobisphenol A and antimony pentoxide, and the weight ratio of the tetrabromobisphenol A to the antimony pentoxide is 2:1; the antistatic agent is linear alkyl sulfonate; the number of carbon in the molecular structure of the linear alkyl sulfonate is less than 14; the adaptation modifier is an ethylene-acrylic ester-glycidyl methacrylate terpolymer.
Example 3: the ABS flame-retardant composite material with high impact resistance and low volume resistance comprises the following raw materials of 100 parts of ABS resin, 30 parts of styrene-butadiene copolymer, 10 parts of flame retardant, 4 parts of antistatic agent, 2 parts of structural strength reinforcing agent and 5 parts of adaptation modifier.
Further, the butadiene content of the styrene-butadiene copolymer is more than 60%.
Further, the structural strength enhancer is hydrophobically modified powder of the optical rod waste; the preparation method of the hydrophobically modified powder of the optical rod waste material comprises the following steps: drying, crushing and sieving the optical fiber preform waste to obtain 50-60 mesh granules, roasting the obtained granules at 600 ℃ for 2.5 hours, taking out and placing the granules in a dryer for natural cooling to obtain nano powder, then placing the obtained nano powder in a dry heat environment for activation treatment, reacting the activated nano powder with a silane coupling agent in a xylene solution, centrifuging, taking a solid, washing and drying to obtain the optical fiber preform; the activation condition is that the mixture is activated for 18 hours at 160 ℃ in a drying oven; the reaction conditions with the silane coupling agent are as follows: the weight ratio of the activated nano powder to the silane coupling agent is 1:1, 2 parts by mass of the mixture of the activated nano powder and the silane coupling agent is placed in 20 parts by weight of dimethylbenzene, and the mixture reacts for 8 hours at 120 ℃; the washing is carried out by using sewage ethanol, the washing times are three times, the solid is centrifugally taken after each washing is finished, and finally the hydrophobically modified powder of the optical rod waste material is obtained after full drying.
Further, the flame retardant is a composite of tetrabromobisphenol A and antimony pentoxide, and the weight ratio of the tetrabromobisphenol A to the antimony pentoxide is 3:1; the antistatic agent is linear alkyl sulfonate; the number of carbon in the molecular structure of the linear alkyl sulfonate is less than 14; the adaptation modifier is an ethylene-acrylic ester-glycidyl methacrylate terpolymer.
Example 4: the ABS flame-retardant composite material with high impact resistance and low volume resistance comprises the following raw materials of 100 parts of ABS resin, 22 parts of styrene-butadiene copolymer, 8 parts of flame retardant, 2 parts of antistatic agent, 1.5 parts of structural strength enhancer and 2 parts of adaptation modifier.
Further, the butadiene content of the styrene-butadiene copolymer is more than 60%.
Further, the structural strength enhancer is hydrophobically modified powder of the optical rod waste; the preparation method of the hydrophobically modified powder of the optical rod waste material comprises the following steps: drying, crushing and sieving the optical fiber preform waste to obtain 50-60 mesh granules, roasting the obtained granules at 520 ℃ for 2.2 hours, taking out and placing the granules in a dryer for natural cooling to obtain nano powder, placing the obtained nano powder in a dry heat environment for activation treatment, reacting the activated nano powder with a silane coupling agent in a xylene solution, centrifuging, taking a solid, washing and drying to obtain the optical fiber preform; the activation condition is that the mixture is activated for 16 hours at 155 ℃ in a drying oven; the reaction conditions with the silane coupling agent are as follows: the weight ratio of the activated nano powder to the silane coupling agent is 3:5, 8 parts by mass of the mixture of the activated nano powder and the silane coupling agent is placed in 50 parts by weight of dimethylbenzene, and the mixture reacts for 8 hours at 112 ℃; the washing is carried out by using sewage ethanol, the washing times are three times, the solid is centrifugally taken after each washing is finished, and finally the hydrophobically modified powder of the optical rod waste material is obtained after full drying.
Further, the flame retardant is a composite of tetrabromobisphenol A and antimony pentoxide, and the weight ratio of the tetrabromobisphenol A to the antimony pentoxide is 7:3; the antistatic agent is linear alkyl sulfonate; the number of carbon in the molecular structure of the linear alkyl sulfonate is less than 14; the adaptation modifier is an ethylene-acrylic ester-glycidyl methacrylate terpolymer.
Comparative example 1: the ABS flame-retardant composite material with high impact resistance and low volume resistance comprises the following raw materials of 100 parts of ABS resin, 6 parts of flame retardant, 3 parts of antistatic agent, 1 part of structural strength enhancer and 3 parts of adaptation modifier in parts by mass.
Further, the structural strength enhancer is hydrophobically modified powder of the optical rod waste; the preparation method of the hydrophobically modified powder of the optical rod waste material comprises the following steps: drying, crushing and sieving the optical fiber preform waste to obtain 50-60 mesh granules, roasting the obtained granules at 550 ℃ for 2 hours, taking out and placing the granules in a dryer for natural cooling to obtain nano powder, then placing the obtained nano powder in a dry heat environment for activation treatment, reacting the activated nano powder with a silane coupling agent in a xylene solution, centrifuging, taking a solid, washing and drying to obtain the optical fiber preform; the activation condition is that the mixture is activated for 15 hours at 155 ℃ in a drying oven; the reaction conditions with the silane coupling agent are as follows: the weight ratio of the activated nano powder to the silane coupling agent is 2:3, 5 parts by mass of the mixture of the activated nano powder and the silane coupling agent is placed in 30 parts by weight of dimethylbenzene, and the mixture reacts for 7 hours at 115 ℃; the washing is carried out by using sewage ethanol, the washing times are two times, the solid is centrifugally taken after each washing is finished, and finally the hydrophobically modified powder of the optical rod waste material is obtained after full drying.
Further, the flame retardant is a composite of tetrabromobisphenol A and antimony pentoxide, and the weight ratio of the tetrabromobisphenol A to the antimony pentoxide is 5:2; the antistatic agent is linear alkyl sulfonate; the number of carbon in the molecular structure of the linear alkyl sulfonate is less than 14; the adaptation modifier is an ethylene-acrylic ester-glycidyl methacrylate terpolymer.
Comparative example 2: the ABS flame-retardant composite material with high impact resistance and low volume resistance comprises the following raw materials of 100 parts of ABS resin, 25 parts of styrene-butadiene copolymer, 6 parts of flame retardant, 3 parts of antistatic agent and 3 parts of adaptation modifier in parts by mass.
Further, the butadiene content of the styrene-butadiene copolymer is more than 60%.
Further, the flame retardant is a composite of tetrabromobisphenol A and antimony pentoxide, and the weight ratio of the tetrabromobisphenol A to the antimony pentoxide is 5:2; the antistatic agent is linear alkyl sulfonate; the number of carbon in the molecular structure of the linear alkyl sulfonate is less than 14; the adaptation modifier is an ethylene-acrylic ester-glycidyl methacrylate terpolymer.
The preparation method of the ABS flame-retardant composite material with high impact resistance and low volume resistance described in the above examples 1-4 and comparative examples 1-2 comprises the following steps: the ABS resin, the styrene-butadiene copolymer, the flame retardant, the antistatic agent, the structural strength reinforcing agent and the adaptation modifier are weighed and mixed according to the weight parts defined in each embodiment; and (3) placing the mixed raw materials into a blender for high-speed blending for 18min, and then carrying out mixing and granulating by a screw extruder to obtain the composite material. The extrusion process conditions are as follows: and (3) melting and mixing the materials at 190-220 ℃ through a double-screw extruder, cooling the extruded strips to normal temperature through a circulating water tank, and granulating the cooled extruded strips after drying by blowing with a blower to obtain the ABS flame-retardant composite material.
Comparative example 3: taking the same ABS resin as that used in the above examples 1-4 and comparative examples 1-2 as a raw material, placing the ABS resin in a blender for high-speed blending for 18min, and then mixing and granulating by a screw extruder to obtain the composite material of the example; the extrusion process conditions are as follows: and (3) melting and mixing the materials at 190-220 ℃ through a double-screw extruder, cooling the extruded strips to normal temperature through a circulating water tank, and granulating the cooled extruded strips after drying through blowing by a blower to obtain the ABS composite material of the embodiment.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. The ABS flame-retardant composite material with high impact resistance and low volume resistance is characterized in that: the raw materials comprise, by mass, 100 parts of ABS resin, 20-30 parts of styrene-butadiene copolymer, 3-10 parts of flame retardant, 1-4 parts of antistatic agent, 0.5-2 parts of structural strength reinforcing agent and 1-5 parts of adaptation modifier;
the butadiene content of the styrene-butadiene copolymer is more than 60 percent;
the structural strength enhancer is hydrophobically modified powder of the optical rod waste;
the preparation method of the hydrophobically modified powder of the optical rod waste material comprises the following steps: drying, crushing and sieving the optical fiber preform waste to obtain 50-60 mesh granules, roasting the obtained granules at 500-600 ℃ for 1.5-2.5 hours, taking out and naturally cooling in a dryer to obtain nano powder, then placing the obtained nano powder in a dry heat environment for activation treatment, reacting the activated nano powder with a silane coupling agent in a xylene solution, centrifuging, taking a solid, washing and drying to obtain the optical fiber preform;
the activation condition is that the activation is carried out for 12 to 18 hours at the temperature of 150 to 160 ℃ in a drying oven; the reaction conditions with the silane coupling agent are as follows: the weight ratio of the activated nano powder to the silane coupling agent is 1:1-2, 2-3 parts by mass of the mixture of the activated nano powder and the silane coupling agent is placed in 10-20 parts by weight of dimethylbenzene, and the mixture reacts for 6-8 hours at the temperature of 110-120 ℃.
2. The high impact low volume resistance ABS flame retardant composite of claim 1 wherein: the flame retardant is a composite of tetrabromobisphenol A and antimony pentoxide, and the weight ratio of the tetrabromobisphenol A to the antimony pentoxide is 2-3:1.
3. The high impact low volume resistance ABS flame retardant composite of claim 1 wherein: the antistatic agent is linear alkyl sulfonate.
4. A high impact low volume resistance ABS flame retardant composite according to claim 3 wherein: the number of carbon in the molecular structure of the linear alkyl sulfonate is less than 14.
5. The high impact low volume resistance ABS flame retardant composite of claim 1 wherein: the adaptation modifier is an ethylene-acrylic ester-glycidyl methacrylate terpolymer.
6. The method for preparing the high-impact low-volume resistance ABS flame-retardant composite material according to any one of claims 1 to 5, which is characterized by comprising the following steps: the ABS resin, the styrene-butadiene copolymer, the flame retardant, the antistatic agent, the structural strength reinforcing agent and the adaptation modifier are mixed according to the weight parts: 100 parts of ABS resin, 20-30 parts of styrene-butadiene copolymer, 3-10 parts of flame retardant, 1-4 parts of antistatic agent, 0.5-2 parts of structural strength reinforcing agent and 1-5 parts of adaptation modifier; and (3) placing the mixed raw materials into a blender for high-speed blending for 15-20min, and then carrying out mixing and granulating by a screw extruder to obtain the composite material.
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