阅读说明：本技术 高抗冲击性abs塑料 (ABS plastic with high impact resistance ) 是由 张燕丹 于 2020-06-09 设计创作，主要内容包括：本发明公开了高抗冲击性ABS塑料。包括以下重量份组分：ABS树脂70-120份、导热填料0.1-2份、抗氧化剂2-4份、硅烷偶联剂5-10份、阻燃剂5-15份、抗紫外剂0.3-1份、引发剂1-4重量份、改性纳米纤维素5-10份。本发明通过添加助剂改性纳米纤维素,由于其高强、高模量、基体相容性好和纳米材料的特殊效应,用作增强剂能够有效的提高ABS塑料抗冲击性能,非常适合用于制造家电外壳。(The invention discloses ABS plastic with high impact resistance. The paint comprises the following components in parts by weight: 70-120 parts of ABS resin, 0.1-2 parts of heat-conducting filler, 2-4 parts of antioxidant, 5-10 parts of silane coupling agent, 5-15 parts of flame retardant, 0.3-1 part of anti-ultraviolet agent, 1-4 parts of initiator and 5-10 parts of modified nano-cellulose. According to the invention, the nano-cellulose is modified by adding the auxiliary agent, and due to the high strength, high modulus, good substrate compatibility and special effects of the nano-material, the ABS plastic used as a reinforcing agent can effectively improve the impact resistance of the ABS plastic, and is very suitable for manufacturing shells of household appliances.)

1. A preparation method of modified nano-cellulose is characterized by comprising the following steps:

weighing 5-10g of cotton pulp, adding the cotton pulp into 100-200mL of 50-70% sulfuric acid solution, stirring and reacting for 30-60min at 40-60 ℃, adding 50-150mL of water, centrifuging to remove sulfuric acid, and dialyzing until the pH value is 6-7 to obtain the nano-cellulose suspension;

adjusting the pH value of the nano-cellulose suspension to 3-4 by using 0.1-0.2mol/L hydrochloric acid, and heating at the temperature of 150 ℃ for 5-15min at 100-; adding 2-5g L-tartaric acid, and reacting for 20-40 min; centrifuging, washing with water, and vacuum drying to obtain the modified nanocellulose.

2. A preparation method of modified nano-cellulose is characterized by comprising the following steps:

weighing 5-10g of cotton pulp, adding the cotton pulp into 100-200mL of 50-70% sulfuric acid solution, stirring and reacting at 40-60 ℃ for 30-60min, pouring the product into 50-150mL of water after the reaction is finished, centrifuging to remove sulfuric acid, and dialyzing with deionized water until the pH value is 6-7 to obtain a nano-cellulose suspension;

adjusting the pH value of the nano-cellulose suspension to 3-4 by using 0.1-0.2mol/L hydrochloric acid, then placing the nano-cellulose suspension in an oil bath at the temperature of 100-150 ℃, heating the nano-cellulose suspension for 5-15min, adding 2-5g L-tartaric acid into the nano-cellulose suspension, continuing to react for 20-40min, after the reaction is finished, centrifuging the nano-cellulose suspension for 5-15min at the temperature of 2-5 ℃ of 10000-20000r/min, washing the precipitate by using water, and drying the precipitate in vacuum to obtain the modified nano-cellulose.

3. A modified nanocellulose, characterized by: prepared by the method of claim 1 or 2.

4. The high-impact-resistance ABS plastic is characterized by comprising the following components in parts by weight: 70-120 parts of ABS resin, 0.1-2 parts of heat-conducting filler, 2-4 parts of antioxidant, 5-10 parts of silane coupling agent, 5-15 parts of flame retardant, 0.3-1 part of anti-ultraviolet agent, 1-4 parts of initiator and 5-10 parts of modified nano cellulose described in claim 3.

Technical Field

The invention belongs to the technical field of plastics, and particularly relates to ABS plastic with high impact resistance and high heat dissipation performance.

Background

The ABS plastic is a terpolymer of acrylonitrile, butadiene and styrene, and the addition of the acrylonitrile provides high hardness and strength, heat resistance and corrosion resistance for the ABS; the butadiene endows ABS with high impact resistance, toughness, cold resistance and certain ductility; and the styrene ensures good high surface gloss, easy coloring and easy processing of the ABS. ABS plastic is one of the most widely used engineering thermoplastic plastics with the largest production quantity at present. ABS plastics are widely used for manufacturing shells of household appliances, such as shells of televisions, refrigerators and computers.

The household electrical appliance may encounter a certain impact in the transportation path and the use process, and the ABS plastic serving as the household electrical appliance shell may cause the shell to be damaged when encountering strong impact.

Household appliances such as refrigerators, air conditioners and the like which provide cool and refreshing for people in daily life also need to be cooled, and because the household appliances can be burnt and scalded after long-time work, if the heat can not be effectively dissipated, the household appliances can be abnormal or damaged due to overhigh temperature, and the service life and the continuous working time are influenced. Most of the housings of home appliances are made of plastic, which generally has poor heat dissipation performance, for example, the thermal conductivity of ABS plastic is about 0.25W/(m · K). Therefore, some heat dissipation holes need to be reserved in the shell of the household appliance, so that the heat inside the household appliance can be discharged outside in time through the heat dissipation holes. The design of reserving the louvre also can bring harm to household electrical appliances, for example, impurity such as dust, water enters into electrical apparatus through the louvre very easily, leads to household electrical appliances work unusual or damage, influences life.

Therefore, in order to solve the problems that the impact resistance of the ABS plastic used for the housing of the electric appliance is yet to be further improved and the heat dissipation is poor due to low heat conductivity, it is necessary to develop an ABS plastic having high impact resistance and high heat conductivity.

Disclosure of Invention

In view of the above-mentioned drawbacks of the prior art, the technical problems to be solved by the present invention are: aiming at the problems of poor heat dissipation and low impact resistance of the household appliance shell manufactured by ABS plastics in the prior art, the high-impact-resistance ABS plastics for the household appliance shell are provided.

In order to solve the technical problems, the invention adopts the technical scheme that:

the high-impact-resistance ABS plastic comprises the following components in parts by weight: 70-120 parts of ABS resin, 0.1-2 parts of heat-conducting filler, 2-4 parts of antioxidant, 5-10 parts of silane coupling agent, 5-15 parts of flame retardant and 0.3-1 part of anti-ultraviolet agent.

The heat-conducting filler is a boron nitride multi-walled carbon nanotube hybrid material.

The antioxidant is one or more of hydroquinone, p-phenylenediamine and 2, 6-di-tert-butylphenol.

The silane coupling agent is one or more of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane and gamma- (methacryloyloxy) propyltrimethoxysilane.

The flame retardant is antimony trioxide or aluminum tripolyphosphate.

The uvioresistant agent is one or more of 2-hydroxy-4-n-octoxy benzophenone, 3, 5-di-tert-butyl-4-hydroxybenzoic acid n-hexadecyl ester and 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole.

The preparation method of the boron nitride multi-walled carbon nanotube hybrid material comprises the following steps:

s1, placing 0.5-2g of multi-walled carbon nanotubes in a mixed acid formed by 300-1000mL of concentrated sulfuric acid and concentrated nitric acid, wherein the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is (1-3): 1, oscillating for 8-12h in ultrasonic at 30-50 ℃, diluting with 500-1500mL of water, filtering out the multiwall carbon nanotube by using a 0.5-1 mu m porous filter membrane, washing to be neutral by using water, and then drying in vacuum for 10-30h at 60-100 ℃ to obtain the acidified multiwall carbon nanotube.

S2, uniformly mixing 3-8g of boron nitride powder and 80-120g of urea together, and mixing the mixture with stainless steel grinding balls according to the mass ratio of 1: (80-120), performing ball milling at a revolution speed of 200-.

S3 adding 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide 8-12g, N-hydroxysuccinimide 20-40g and acidified multi-walled carbon nano-tubes 0.8-1.2g into water 800-1500mL, and performing ultrasonic treatment for 1-3h to obtain the multi-walled carbon nano-tube suspension.

S4, adding 3-8g of amino-functionalized boron nitride into the obtained multi-walled carbon nanotube suspension to form a uniform mixture, reacting for 10-30h at 0 ℃ in an ice bath under stirring, performing suction filtration, and performing vacuum drying for 3-6h at 60-80 ℃ to obtain the boron nitride multi-walled carbon nanotube hybrid material.

Boron nitride has the advantages of light weight, low thermal expansion coefficient, good heat resistance, high thermal conductivity of 30-330W/(m K) and the like, and is widely applied to polymer heat conduction modification. However, boron nitride is an inorganic material and has poor compatibility with high polymer materials, and the boron nitride is easily layered after being mixed with the high polymer materials, so that the comprehensive performance of the high polymer materials is seriously influenced.

The multi-wall carbon nanotube is a good heat conduction carbon material, and researches show that the heat conductivity coefficient of a single multi-wall carbon nanotube at room temperature is more than 3000W/(m K), which is far more than the heat conductivity coefficient of some well-known good heat conduction materials. The multi-walled carbon nano-tube has high surface energy and is easy to agglomerate, and the introduction of the nano-grade filler has great influence on the viscosity of the polymer material in the processing process, thereby influencing the dispersion state of the filler in the polymer and further influencing the comprehensive performance of the polymer material.

The polymer material can further improve the heat-conducting property by adding more than two different fillers and utilizing respective advantages of the fillers. But because interface thermal resistance is generated among different fillers, heat conduction is hindered, and the heat conduction performance of the material is reduced. The boron nitride and the multi-walled carbon nanotube are connected through a covalent bond, so that the interface thermal resistance and phonon scattering between the heat-conducting filler and the heat-conducting filler can be effectively reduced, and the heat conductivity coefficient of the high polymer material is improved.

The preparation method of the ABS plastic comprises the following steps:

drying the ABS resin in an oven; preheating a screw cylinder and an injection mold of an injection molding machine; feeding the dried ABS resin into a screw cylinder of an injection molding machine, and heating to a molten state; adding heat-conducting filler, antioxidant, lubricant, silane coupling agent, flame retardant and anti-ultraviolet agent into molten ABS resin, fully and uniformly mixing, spraying into a mold, and cooling the mold to room temperature after completion; and opening the mold to take out the product in the mold, and air-drying and granulating to obtain the ABS plastic.

The drying temperature is 80-85 ℃, and the drying time is 2-4 h.

The rear temperature of the screw cylinder is 180-220 ℃, the middle temperature of the screw cylinder is 190-230 ℃, and the front temperature of the screw cylinder is 190-230 ℃.

The temperature of the mould is 30-70 ℃.

On the basis of the technical scheme, the invention also provides a technical scheme that:

the high-impact-resistance ABS plastic comprises the following components in parts by weight: 70-120 parts of ABS resin, 0.1-2 parts of heat-conducting filler, 2-4 parts of antioxidant, 5-10 parts of silane coupling agent, 5-15 parts of flame retardant, 0.3-1 part of anti-ultraviolet agent and 1-4 parts of initiator.

The heat-conducting filler is a mesh-boron nitride multi-walled carbon nanotube hybrid material.

The antioxidant is one or more of hydroquinone, p-phenylenediamine and 2, 6-di-tert-butylphenol.

The silane coupling agent is one or more of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane and gamma- (methacryloyloxy) propyltrimethoxysilane.

The flame retardant is antimony trioxide or aluminum tripolyphosphate.

The uvioresistant agent is one or more of 2-hydroxy-4-n-octoxy benzophenone, 3, 5-di-tert-butyl-4-hydroxybenzoic acid n-hexadecyl ester and 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole.

The initiator is one or more of lauroyl peroxide and dicumyl peroxide.

The preparation method of the reticular-boron nitride multi-walled carbon nanotube hybrid material comprises the following steps:

s1, placing 0.5-2g of multi-walled carbon nanotubes in a mixed acid formed by 300-1000mL of concentrated sulfuric acid and concentrated nitric acid, wherein the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is (1-3): 1, oscillating for 8-12h in ultrasonic at 30-50 ℃, diluting with 500-1500mL of water, filtering out the multiwall carbon nanotube by using a 0.5-1 mu m porous filter membrane, washing to be neutral by using water, and then drying in vacuum for 10-30h at 60-100 ℃ to obtain the acidified multiwall carbon nanotube.

S2, uniformly mixing 3-8g of boron nitride powder and 80-120g of urea together, and mixing the mixture with stainless steel grinding balls according to the mass ratio of 1: (80-120), performing ball milling at a revolution speed of 200-.

S3 adding 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide 8-12g, N-hydroxysuccinimide 20-40g and acidified multi-walled carbon nano-tubes 0.8-1.2g into 800-1500mL water, and carrying out ultrasonic treatment for 1-3h to obtain the multi-walled carbon nano-tube suspension.

S4, adding 3-8g of amino-functionalized boron nitride and 3-8g of triethylene tetramine into the obtained multi-walled carbon nanotube suspension to form a uniform mixture, reacting for 10-30h at 0 ℃ in an ice bath under stirring, performing suction filtration, and performing vacuum drying for 3-6h at 60-80 ℃ to obtain the mesh-boron nitride multi-walled carbon nanotube hybrid material.

Amino groups at two ends of each triethylene tetramine molecule and carboxyl on the surface of the multi-wall carbon nano tube are subjected to chemical reaction, so that the multi-wall carbon nano tubes are bridged into a whole through covalent bonds, the triethylene tetramine is just like a line, the multi-wall carbon nano tubes are just like points, and the triethylene tetramine and the multi-wall carbon nano tubes are connected into a net through point lines to form a whole, and heat conduction is facilitated.

The preparation method of the ABS plastic comprises the following steps:

drying the ABS resin in an oven; preheating a screw cylinder and an injection mold of an injection molding machine; feeding the dried ABS resin into a screw cylinder of an injection molding machine, and heating to a molten state; adding heat-conducting filler, initiator, antioxidant, lubricant, silane coupling agent, flame retardant and anti-ultraviolet agent into molten ABS resin, fully and uniformly mixing, spraying into a mold, and cooling the mold to room temperature after completion; and opening the mold to take out the product in the mold, and air-drying and granulating to obtain the ABS plastic.

The drying temperature is 80-85 ℃, and the drying time is 2-4 h.

The rear temperature of the screw cylinder is 180-220 ℃, the middle temperature of the screw cylinder is 190-230 ℃, and the front temperature of the screw cylinder is 190-230 ℃.

The temperature of the mould is 30-70 ℃.

The ABS resin is subjected to grafting reaction by adopting a melt grafting method, double bonds in the net-shaped boron nitride multi-walled carbon nanotube hybrid material and double bonds in the ABS can react, a certain promotion effect is achieved on the solidification process of the ABS resin, the net-shaped boron nitride multi-walled carbon nanotube hybrid material is favorably dispersed in the ABS resin matrix, and good interface combination is formed between two phases, so that the boron nitride multi-walled carbon nanotube/ABS resin composite material which is uniformly dispersed and has good interface combination can be obtained, and the improvement of the heat conductivity of the composite material can be better promoted.

Preferably, on the basis of the above technical solution, the present invention further provides a technical solution:

the high-impact-resistance ABS plastic comprises the following components in parts by weight: 70-120 parts of ABS resin, 0.1-2 parts of heat-conducting filler, 2-4 parts of antioxidant, 5-10 parts of silane coupling agent, 5-15 parts of flame retardant, 0.3-1 part of anti-ultraviolet agent, 1-4 parts of initiator and 5-10 parts of modified nano-cellulose.

The heat-conducting filler is a mesh-boron nitride multi-walled carbon nanotube hybrid material.

The antioxidant is one or more of hydroquinone, p-phenylenediamine and 2, 6-di-tert-butylphenol.

The silane coupling agent is one or more of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane and gamma- (methacryloyloxy) propyltrimethoxysilane.

The flame retardant is antimony trioxide or aluminum tripolyphosphate.

The uvioresistant agent is one or more of 2-hydroxy-4-n-octoxy benzophenone, 3, 5-di-tert-butyl-4-hydroxybenzoic acid n-hexadecyl ester and 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole.

The initiator is one or more of lauroyl peroxide and dicumyl peroxide.

The preparation method of the reticular-boron nitride multi-walled carbon nanotube hybrid material comprises the following steps:

s1, placing 0.5-2g of multi-walled carbon nanotubes in a mixed acid formed by 300-1000mL of concentrated sulfuric acid and concentrated nitric acid, wherein the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is (1-3): 1, oscillating for 8-12h in ultrasonic at 30-50 ℃, diluting with 500-1500mL of water, filtering out the multiwall carbon nanotube by using a 0.5-1 mu m porous filter membrane, washing to be neutral by using water, and then drying in vacuum for 10-30h at 60-100 ℃ to obtain the acidified multiwall carbon nanotube.

S2, uniformly mixing 3-8g of boron nitride powder and 80-120g of urea together, and mixing the mixture with stainless steel grinding balls according to the mass ratio of 1: (80-120), performing ball milling at a revolution speed of 200-.

S3 adding 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide 8-12g, N-hydroxysuccinimide 20-40g and acidified multi-walled carbon nano-tubes 0.8-1.2g into 800-1500mL water, and carrying out ultrasonic treatment for 1-3h to obtain the multi-walled carbon nano-tube suspension. S4, adding 3-8g of amino-functionalized boron nitride and 3-8g of triethylene tetramine into the obtained multi-walled carbon nanotube suspension to form a uniform mixture, reacting for 10-30h at 0 ℃ in an ice bath under stirring, performing suction filtration, and performing vacuum drying for 3-6h at 60-80 ℃ to obtain the mesh-boron nitride multi-walled carbon nanotube hybrid material.

The preparation method of the modified nano-cellulose comprises the following steps:

weighing 5-10g of cotton pulp, adding the cotton pulp into 100-200mL of 50-70% sulfuric acid solution, stirring and reacting at 40-60 ℃ for 30-60min, pouring the product into 50-150mL of water after the reaction is finished, removing a large amount of sulfuric acid by using a centrifuge through water exchange/centrifugation circulation, and dialyzing the obtained suspension by using deionized water until the pH value is 6-7 to obtain the nano-cellulose suspension.

Adjusting the pH value of the nano-cellulose suspension to 3-4 by using 0.1-0.2mol/L hydrochloric acid, then placing the nano-cellulose suspension in an oil bath at the temperature of 100-150 ℃ for heating, adding 2-5g L-tartaric acid into the nano-cellulose suspension after 5-15min, and continuing to react for 20-40 min. After the reaction is finished, centrifuging for 5-15min at 2-5 ℃ 10000-.

The nano-cellulose is obtained by extracting cellulose in natural biomass by mechanical, chemical or other methods. The commonly obtained cellulose has the diameter within 100 nanometers, the density of 1.6g/cm3, high purity and outstanding mechanical property, the tensile strength is about 7.5Gpa, the axial elastic modulus is more than 100GPa, and the transverse elastic modulus is more than 10 GPa. The nano-cellulose has the great advantage of high strength and reproducibility, and is an ideal reinforcing phase material for composite materials.

Because a large number of hydroxyl groups exist on the surface of the nano-cellulose, hydrogen bonds are easily formed to be gathered together, the dimension is changed into a micron-sized structure, some characteristics of the nano-material are lost, and uniform dispersion is difficult in the using process. In addition, since nanocellulose has polarity, it has weak interfacial adhesion when used for reinforcing non-polar high polymer. Therefore, when the nano-cellulose composite material is prepared, the nano-cellulose composite material needs to be subjected to surface modification or matrix material modification, so that the interface compatibility between the nano-cellulose and the matrix is improved. Changing the hydrophilicity of the nano-cellulose into hydrophobicity is an effective means for avoiding self-aggregation. The invention solves the problem that a large number of hydroxyl groups exist on the surface of the nano-cellulose, and hydrogen bonds are easily formed to gather together, so that the nano-cellulose cannot be uniformly dispersed in the using process through esterification modification.

The preparation method of the ABS plastic comprises the following steps:

drying the ABS resin in an oven; preheating a screw cylinder and an injection mold of an injection molding machine; feeding the dried ABS resin into a screw cylinder of an injection molding machine, and heating to a molten state; adding heat-conducting filler, an initiator, an antioxidant, a lubricant, a silane coupling agent, a flame retardant, an anti-ultraviolet agent and nano-cellulose into molten ABS resin, fully and uniformly mixing, spraying into a mold, and cooling the mold to room temperature after completion; and opening the mold to take out the product in the mold, and air-drying and granulating to obtain the ABS plastic.

The drying temperature is 80-85 ℃, and the drying time is 2-4 h.

The rear temperature of the screw cylinder is 180-220 ℃, the middle temperature of the screw cylinder is 190-230 ℃, and the front temperature of the screw cylinder is 190-230 ℃.

The temperature of the mould is 30-70 ℃.

The invention has the beneficial effects that:

1. the ABS plastic prepared by the invention has high heat conductivity coefficient and good heat dissipation performance, can obtain higher heat conductivity coefficient under the condition of adding a small amount of heat-conducting filler, and hardly influences the comprehensive performance of the ABS plastic.

2. The boron nitride multi-walled carbon nanotube hybrid material prepared by connecting the boron nitride and the multi-walled carbon nanotube through covalent bonds can effectively reduce the interface thermal resistance and phonon scattering between the heat-conducting filler and the heat-conducting filler, and effectively improve the heat conductivity coefficient of ABS plastic.

3. Through the grafting reaction, the reticular boron nitride multi-walled carbon nanotube hybrid material is connected with ABS through a covalent bond, so that the problem of poor dispersibility of the inorganic/carbon-based heat conduction material in the ABS matrix is solved, good interface combination is formed between two phases, and the improvement of the heat conduction performance of the ABS plastic is further improved.

4. The nano-cellulose modified by adding the auxiliary agent can be used as a reinforcing agent to effectively improve the impact resistance of ABS plastics due to the high strength, high modulus, good substrate compatibility and special effects of nano materials.

Detailed Description