CN112574509B - Waterproof plastic battery shell and preparation method thereof - Google Patents
Waterproof plastic battery shell and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a waterproof plastic battery shell which comprises the following raw materials in parts by weight: 80-100 parts of polypropylene, 50-80 parts of ABS plastic, 10-15 parts of modified cellulose nanofiber, 5-10 parts of ethylene-octene copolymer, 0.5-1 part of composite anti-aging agent, 3-5 parts of modified barium titanate, 1-3 parts of coupling agent, 1 part of dispersing agent and 5-10 parts of compatilizer; the invention also discloses a preparation method of the waterproof plastic battery shell, which overcomes the defects of low mechanical property, poor heat resistance, large shrinkage deformation and poor creep resistance of the traditional polypropylene material, and combines ABS plastic, and modified cellulose nanofiber with higher heat resistance and mechanical property, durable high-efficiency ultraviolet-absorbing composite anti-aging agent and modified barium titanate with ultrahigh dielectric constant are added to endow the battery shell material with excellent heat resistance, insulation, ageing resistance and impact resistance.
Description
Technical Field
The invention belongs to the technical field of plastic preparation, and particularly relates to a waterproof plastic battery shell and a preparation method thereof.
Background
At present, the electric vehicle is widely applied, and brings great convenience to the travel life of people. The storage battery is a core device and a power source of the electric vehicle, is particularly important for maintenance and repair of the storage battery, wherein the storage battery is afraid of entering water and being wet, particularly when the electric vehicle goes out in rainy days, the existing storage battery shell is fragile and easy to generate cracks, rainwater is easy to infiltrate, the battery is easy to corrode, the battery is damaged, repair and replacement are needed, and unnecessary troubles are brought to the use and repair of the main vehicle.
The existing plastic for the battery shell mainly comprises PP, ABS, PVC and other materials, wherein the cost performance of the modified PP is highest, but the existing battery shell is impact-resistant, ageing-resistant and poor in weather resistance, and inconvenience is brought to the life of people, so that the battery shell with good toughness, corrosion resistance and ageing resistance is a technical problem to be solved at present.
Disclosure of Invention
The invention aims to provide a waterproof plastic battery shell and a preparation method thereof.
The technical problems to be solved by the invention are as follows:
in the prior art, the plastic product for the battery shell mainly comprises PP, ABS, PVC and other materials, but the existing battery shell is poor in impact resistance, aging resistance and heat resistance, and inconvenience is brought to the life of people.
The aim of the invention can be achieved by the following technical scheme:
a waterproof plastic battery shell comprises the following raw materials in parts by weight: 80-100 parts of polypropylene, 50-80 parts of ABS plastic, 10-15 parts of modified cellulose nanofiber, 5-10 parts of ethylene-octene copolymer, 0.5-1 part of composite anti-aging agent, 3-5 parts of modified barium titanate, 1-3 parts of coupling agent, 1 part of dispersing agent and 5-10 parts of compatilizer;
the waterproof plastic battery shell is prepared by the following steps:
firstly, adding polypropylene, ABS plastic, ethylene-octene copolymer, coupling agent, dispersing agent and compatilizer into a reaction kettle, mixing for 30-60min at the temperature of 165-175 ℃ and the rotating speed of 200-300r/min, then adding modified cellulose nanofiber, modified barium titanate and composite anti-aging agent into the reaction kettle, and continuously mixing for 20min under the condition of unchanged temperature and rotating speed to obtain a mixture;
and secondly, transferring the mixture into a screw extruder for extrusion, bracing, cooling and granulating, controlling the temperature of the extruder from a feeding section to 180-225 ℃ of a machine head to obtain master batch, drying the master batch in a ventilating drying box at 90 ℃ for 6 hours, and then performing injection molding by an injection molding machine at 285 ℃ to obtain the waterproof plastic battery shell.
Further, the modified cellulose nanofiber is prepared by the steps of:
s11, adding eucalyptus pulp and deionized water into a beaker according to a mass ratio of 2:100, soaking for 24-48h, adding 2, 6-tetramethyl piperidine-1-oxygen free radical and sodium bromide into the beaker, stirring for 10min at a rotating speed of 60-100r/min, then dropwise adding sodium hypochlorite into the beaker, controlling the dropwise adding speed to be 1-3 drops/sec, adding sodium hydroxide solution with the concentration of 0.5mol/L into the beaker after the dropwise adding is finished, controlling the pH value to be 10, reacting for 4-6h at the rotating speed of 200-300r/min, adding absolute ethyl alcohol to terminate the reaction, carrying out vacuum suction filtration, washing a filter cake with deionized water for 3-5 times, transferring into a high-pressure homogenizer, circularly homogenizing for 3-5 times under the pressure of 25-60MPa, and finally carrying out freeze drying for 5-10h at the temperature of-45 ℃ to obtain an intermediate 1;
step S12, adding the intermediate 1 and toluene into a beaker, performing ultrasonic dispersion for 20min at the temperature of 20-30 ℃ and the frequency of 30-50kHz, then adding 2-bromoisobutyryl bromide into the beaker, continuing ultrasonic treatment for 10min with the constant frequency, performing suction filtration, washing a filter cake with N, N-dimethylformamide for 3-5 times, and drying in a vacuum drying oven at the temperature of 50 ℃ until the weight is constant to obtain an intermediate 2;
and S13, adding the intermediate 2, N-dimethylformamide, styrene and pentamethyldivinyl triamine into a three-neck flask, vacuumizing, charging nitrogen, adding copper chloride, heating to 100-110 ℃ in a water bath, reacting for 48 hours under the protection of nitrogen, stopping the reaction in an ice bath to obtain a mixed solution 3, wetting neutral alumina with tetrahydrofuran, filling the neutral alumina into a chromatographic column, adding the mixed solution 3 into the chromatographic column to obtain an intermediate 4, treating the intermediate 4 in a rotary evaporator at the temperature of 150-160 ℃ for 30min, transferring to absolute ethyl alcohol, precipitating for 10-15 hours, and finally drying in a vacuum drying box at the temperature of 50 ℃ for 12 hours to obtain the modified cellulose nanofiber.
Further, the dosage ratio of 2, 6-tetramethyl piperidine-1-oxyl, sodium bromide, sodium hypochlorite, eucalyptus pulp and absolute ethyl alcohol in the step S11 is 0.1mmol:1mmol:10mmol:1g:10-15mL; the dosage ratio of the intermediate 1, toluene and 2-bromoisobutyryl bromide in the step S12 is 0.1-0.5g:100mL:2mL; the dosage ratio of the intermediate 2, the N, N-dimethylformamide, the styrene, the pentamethyldivinyl triamine and the cupric chloride in the step S13 is 0.05-0.1g:100mL:50mL:0.15mL:0.2g.
The cellulose nanofiber has the advantages that the cellulose nanofiber can be interweaved and entangled to form a network structure when the concentration is low due to the action of a large number of hydrogen bonds, the film forming property is good, the polymer mechanical property can be effectively enhanced, but the cellulose nanofiber contains a large number of hydroxyl groups, has strong hydrophilicity, is easy to cause agglomeration when a hydrophobic material is enhanced, and is poor in compatibility.
Further, the composite anti-aging agent is prepared by the following steps:
s21, adding absolute ethyl alcohol, hexadecylamine, potassium chloride solution with the concentration of 0.1mol/L and deionized water into a reaction kettle, stirring for 30min at the rotating speed of 150r/min, adding isopropyl titanate into the reaction kettle while stirring at the temperature of 25 ℃ at the rotating speed of 300-500r/min, continuously stirring for 20min, standing for 18h, washing a product with absolute ethyl alcohol for 3-5 times, drying for 12h at the temperature of 40-45 ℃ in a blast drying oven, and finally calcining for 2h at the temperature of 500 ℃ in a muffle furnace to obtain mesoporous titanium dioxide;
s22, adding 2-hydroxy-4-methoxybenzophenone and absolute ethyl alcohol into a beaker, performing ultrasonic dispersion for 10-20min at the frequency of 35kHz, then adding mesoporous titanium dioxide into the beaker, stirring for 30min at the rotating speed of 100-200r/min, filtering, washing a filter cake with deionized water until a washing solution is neutral, and drying in an oven at the temperature of 100-110 ℃ until the weight is constant, thus obtaining the composite anti-aging agent.
Further, in the step S21, the dosage ratio of the absolute ethanol, the hexadecylamine, the potassium chloride solution, the deionized water and the isopropyl titanate is 100mL:0.87g:0.4mL:0.5-0.6mL:2.2mL; the dosage ratio of the 2-hydroxy-4-methoxybenzophenone, the absolute ethanol and the mesoporous titanium dioxide in the step S22 is 1g:100-120mL:5-10g.
The method comprises the steps of taking hexadecylamine as a structure guiding agent, taking isopropyl titanate as a titanium source, taking absolute ethyl alcohol as a solvent, adopting a sol-gel method to prepare spherical mesoporous titanium dioxide, dispersing a 2-hydroxy-4-methoxybenzophenone ultraviolet light absorbent in the absolute ethyl alcohol to obtain ultraviolet light dispersion liquid, soaking the mesoporous titanium dioxide in the ultraviolet light dispersion liquid, and loading an organic anti-ultraviolet auxiliary agent on the mesoporous titanium dioxide because the mesoporous titanium dioxide has larger specific surface area, higher void ratio and stronger adsorptivity, thereby overcoming the defects that the organic anti-ultraviolet auxiliary agent has small molecular weight, is easy to migrate and volatilize from materials and cannot exert an anti-aging effect, improving the high temperature stability of the organic anti-ultraviolet auxiliary agent, and jointly ensuring that the battery shell has the anti-aging performance.
Further, the preparation method of the modified barium titanate comprises the following steps:
adjusting the pH value of tartaric acid to 9 by using a sodium hydroxide solution with the mass fraction of 40%, transferring the tartaric acid into a three-neck flask, stirring at the rotating speed of 250-280r/min, adding barium titanate powder into the three-neck flask while stirring, controlling the reaction temperature to be 50 ℃, performing suction filtration after the rotating speed is unchanged for 2 hours, washing a filter cake with deionized water for 3-5 times, and finally drying the filter cake in an oven at 80 ℃ for 4-6 hours to obtain modified barium titanate, wherein the dosage ratio of the tartaric acid to the barium titanate powder is 5-10mL:1g.
Further, the coupling agent is one or more of silane coupling agent KH-550, silane coupling agent KH-560 and silane coupling agent KH-570 mixed according to any proportion.
Further, the dispersing agent is one of triethyl hexyl phosphate and sodium dodecyl sulfate.
Further, the compatilizer is one of polypropylene grafted maleic anhydride and acrylonitrile-butadiene-styrene copolymer grafted maleic anhydride.
A preparation method of a waterproof plastic battery shell comprises the following steps:
firstly, adding polypropylene, ABS plastic, ethylene-octene copolymer, coupling agent, dispersing agent and compatilizer into a reaction kettle, mixing for 30-60min at the temperature of 165-175 ℃ and the rotating speed of 200-300r/min, then adding modified cellulose nanofiber, modified barium titanate and composite anti-aging agent into the reaction kettle, and continuously mixing for 20min under the condition of unchanged temperature and rotating speed to obtain a mixture;
and secondly, transferring the mixture into a screw extruder for extrusion, bracing, cooling and granulating, controlling the temperature of the extruder from a feeding section to 180-225 ℃ of a machine head to obtain master batch, drying the master batch in a ventilating drying box at 90 ℃ for 6 hours, and then performing injection molding by an injection molding machine at 285 ℃ to obtain the waterproof plastic battery shell.
The invention has the beneficial effects that:
the invention takes polypropylene and ABS plastic as main materials, prepares a waterproof plastic battery shell by adding modified cellulose nanofiber, modified barium titanate, composite antioxidant and other conventional auxiliary agents, overcomes the defects of low mechanical property, poor heat resistance, large shrinkage deformation and poor creep resistance of the traditional polypropylene material, combines the characteristics of high chemical corrosion resistance and high mechanical property of the ABS plastic, adds the modified cellulose nanofiber with high heat resistance and high durability and high efficiency of absorbing ultraviolet rays as well as the composite antioxidant with ultra-high dielectric constant and the modified barium titanate with ultra-high dielectric constant, endows the battery shell material with excellent heat resistance, insulation, ageing resistance and impact resistance, slows down or avoids the phenomena of breakage, cracking and the like of a battery bottle due to the existence of the excellent properties, protects the battery better from being damaged, wherein the cellulose nanofiber is a natural polymer nanomaterial with high length-diameter ratio extracted from the traditional fiber, has the advantages of excellent mechanical property, biodegradability, wide source, environmental friendliness and the like, can be interwoven and entangled to form a network structure under the action of a large number of hydrogen bonds of molecular chains when the concentration is low, has good film forming property, can effectively enhance the physical property of polymer, but contains a large number of hydroxyl groups, has strong hydrophilicity, easily causes agglomeration when a hydrophobic material is enhanced, has poor compatibility, utilizes eucalyptus pulp to produce sodium hypobromite with higher oxidizing property in situ through sodium bromide and sodium hypochlorite, combines an oxidation method with homogenization treatment to obtain the cellulose nanofiber, namely an intermediate 1, and then utilizes 2-bromoisobutyryl bromide for organic modification, eliminating reaction between Br of 2-bromo isobutyryl bromide and cellulose nanofiber OH to obtain an intermediate 2, grafting styrene onto the intermediate 2 through atom transfer radical polymerization to obtain an intermediate 3, purifying through a chromatographic column, removing an organic solvent and the like to obtain a modified cellulose nanofiber, wherein the existence of polystyrene not only improves the hydrophobicity of the cellulose nanofiber and increases the compatibility of the cellulose nanofiber with organic matters, but also further improves the thermal stability, impact resistance and other mechanical properties of the cellulose nanofiber due to the existence of a rigid group benzene ring; the method comprises the steps of taking hexadecylamine as a structure guiding agent, taking isopropyl titanate as a titanium source, taking absolute ethyl alcohol as a solvent, adopting a sol-gel method to prepare spherical mesoporous titanium dioxide, dispersing a 2-hydroxy-4-methoxybenzophenone ultraviolet light absorbent in the absolute ethyl alcohol to obtain ultraviolet light dispersion liquid, soaking the mesoporous titanium dioxide in the ultraviolet light dispersion liquid, and loading an organic anti-ultraviolet auxiliary agent on the mesoporous titanium dioxide because the mesoporous titanium dioxide has larger specific surface area, higher void ratio and stronger adsorptivity, thereby overcoming the defects that the organic anti-ultraviolet auxiliary agent has small molecular weight, is easy to migrate and volatilize from materials and cannot exert an anti-aging effect, improving the high temperature stability of the organic anti-ultraviolet auxiliary agent, and jointly ensuring that the battery shell has the anti-aging performance.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A waterproof plastic battery shell comprises the following raw materials in parts by weight: 80 parts of polypropylene, 50 parts of ABS plastic, 10 parts of modified cellulose nanofiber, 5 parts of ethylene-octene copolymer, 0.5 part of composite anti-aging agent, 3 parts of modified barium titanate, 1 part of coupling agent, 1 part of dispersing agent and 5 parts of compatilizer;
the waterproof plastic battery shell is prepared by the following steps:
firstly, adding polypropylene, ABS plastic, ethylene-octene copolymer, a coupling agent, a dispersing agent and a compatilizer into a reaction kettle, mixing for 30min at the temperature of 165 ℃ and the rotating speed of 200r/min, then adding modified cellulose nanofiber, modified barium titanate and a composite anti-aging agent into the reaction kettle, and continuously mixing for 20min under the condition of unchanged temperature and rotating speed to obtain a mixture;
and transferring the mixture into a screw extruder for extrusion, bracing, cooling and granulating, controlling the temperature of the extruder from a feeding section to 180 ℃ of a machine head to obtain a master batch, drying the master batch in a ventilating drying box at 90 ℃ for 6 hours, and then performing injection molding by an injection molding machine at 285 ℃ to obtain the waterproof plastic battery shell.
The modified cellulose nanofiber is prepared by the following steps:
s11, adding eucalyptus pulp and deionized water into a beaker according to a mass ratio of 2:100, soaking for 24 hours, adding 2, 6-tetramethyl piperidine-1-oxygen free radical and sodium bromide into the beaker, stirring for 10 minutes at a rotating speed of 60r/min, adding sodium hypochlorite into the beaker dropwise, controlling the dropwise adding speed to be 1 drop/second, adding sodium hydroxide solution with the concentration of 0.5mol/L into the beaker after the dropwise adding is finished to control the pH value to be 10, reacting for 4 hours at a rotating speed of 200r/min, adding absolute ethyl alcohol, terminating the reaction, vacuum filtering, washing a filter cake with deionized water for 3 times, transferring into a high-pressure homogenizer, circularly homogenizing for 3 times under the pressure of 25MPa, and finally freeze-drying for 5 hours at the temperature of-45 ℃ to obtain an intermediate 1;
step S12, adding the intermediate 1 and toluene into a beaker, performing ultrasonic dispersion for 20min at the temperature of 20 ℃ and the frequency of 30kHz, then adding 2-bromoisobutyryl bromide into the beaker, continuing ultrasonic for 10min with the frequency unchanged, performing suction filtration, washing a filter cake with N, N-dimethylformamide for 3 times, and drying in a vacuum drying oven at the temperature of 50 ℃ to constant weight to obtain an intermediate 2;
step S13, adding an intermediate 2, N-dimethylformamide, styrene and pentamethyldivinyl triamine into a three-neck flask, vacuumizing, charging nitrogen, adding copper chloride, heating to 100 ℃ in a water bath, reacting for 48 hours under the protection of nitrogen, stopping the reaction in an ice bath to obtain a mixed solution 3, wetting neutral alumina with tetrahydrofuran, filling the neutral alumina into a chromatographic column, adding the mixed solution 3 into the chromatographic column to obtain an intermediate 4, treating the intermediate 4 in a rotary evaporator at the temperature of 150 ℃ for 30min, transferring to absolute ethyl alcohol, precipitating for 10 hours, and finally drying in a vacuum drying box at the temperature of 50 ℃ for 12 hours to obtain the modified cellulose nanofiber.
The dosage ratio of the 2, 6-tetramethyl piperidine-1-oxygen free radical, sodium bromide, sodium hypochlorite, eucalyptus pulp and absolute ethyl alcohol in the step S11 is 0.1mmol:1mmol:10mmol:1g:10mL; the ratio of the amount of intermediate 1, toluene and 2-bromoisobutyryl bromide used in step S12 was 0.1g:100mL:2mL; the ratio of the amounts of intermediate 2, N-dimethylformamide, styrene, pentamethyldivinyl triamine and copper chloride used in step S13 was 0.05g:100mL:50mL:0.15mL:0.2g.
The composite anti-aging agent is prepared by the following steps:
s21, adding absolute ethyl alcohol, hexadecylamine, potassium chloride solution with the concentration of 0.1mol/L and deionized water into a reaction kettle, stirring for 30min at the rotating speed of 150r/min, adding isopropyl titanate into the reaction kettle while stirring at the rotating speed of 300r/min at the temperature of 25 ℃, continuing stirring for 20min, standing for 18h, washing a product with absolute ethyl alcohol for 3 times, drying for 12h at the temperature of 40 ℃ in a forced air drying oven, and finally calcining for 2h at the temperature of 500 ℃ in a muffle furnace to obtain mesoporous titanium dioxide;
s22, adding 2-hydroxy-4-methoxybenzophenone and absolute ethyl alcohol into a beaker, performing ultrasonic dispersion for 10min at the frequency of 35kHz, then adding mesoporous titanium dioxide into the beaker, stirring for 30min at the rotating speed of 100r/min, filtering, washing a filter cake with deionized water until a washing solution is neutral, and drying in a drying oven at the temperature of 100 ℃ until the weight is constant, thus obtaining the composite anti-aging agent.
The dosage ratio of the absolute ethyl alcohol, the hexadecylamine, the potassium chloride solution, the deionized water and the isopropyl titanate in the step S21 is 100mL:0.87g:0.4mL:0.5mL:2.2mL; the dosage ratio of the 2-hydroxy-4-methoxybenzophenone, the absolute ethanol and the mesoporous titanium dioxide in the step S22 is 1g:100mL:5g.
The preparation method of the modified barium titanate comprises the following steps:
adjusting the pH value of tartaric acid to 9 by using a sodium hydroxide solution with the mass fraction of 40%, transferring the tartaric acid into a three-neck flask, stirring at the rotating speed of 250r/min, adding barium titanate powder into the three-neck flask while stirring, controlling the reaction temperature to be 50 ℃, performing suction filtration after the rotating speed is unchanged for 2 hours, washing a filter cake with deionized water for 3 times, and finally drying in an oven at 80 ℃ for 4 hours to obtain modified barium titanate, wherein the dosage ratio of the tartaric acid to the barium titanate powder is 5mL:1g.
The coupling agent is silane coupling agent KH-550, the dispersing agent is triethyl hexyl phosphoric acid, and the compatilizer is polypropylene grafted maleic anhydride.
Example 2
A waterproof plastic battery shell comprises the following raw materials in parts by weight: 90 parts of polypropylene, 70 parts of ABS plastic, 12 parts of modified cellulose nanofiber, 8 parts of ethylene-octene copolymer, 0.8 part of composite anti-aging agent, 4 parts of modified barium titanate, 2 parts of coupling agent, 1 part of dispersing agent and 8 parts of compatilizer;
the waterproof plastic battery shell is prepared by the following steps:
firstly, adding polypropylene, ABS plastic, ethylene-octene copolymer, a coupling agent, a dispersing agent and a compatilizer into a reaction kettle, mixing for 45min at the temperature of 170 ℃ and the rotating speed of 250r/min, then adding modified cellulose nanofiber, modified barium titanate and a composite anti-aging agent into the reaction kettle, and continuously mixing for 20min under the condition of unchanged temperature and rotating speed to obtain a mixture;
and transferring the mixture into a screw extruder for extrusion, bracing, cooling and granulating, controlling the temperature of the extruder from a feeding section to a machine head temperature of 200 ℃ to obtain a master batch, drying the master batch in a ventilating drying box at 90 ℃ for 6 hours, and then performing injection molding by an injection molding machine at an injection molding temperature of 285 ℃ to obtain the waterproof plastic battery shell.
The modified cellulose nanofiber is prepared by the following steps:
s11, adding eucalyptus pulp and deionized water into a beaker according to a mass ratio of 2:100, soaking for 36 hours, adding 2, 6-tetramethyl piperidine-1-oxygen free radical and sodium bromide into the beaker, stirring for 10 minutes at a rotating speed of 80r/min, adding sodium hypochlorite into the beaker dropwise, controlling the dropwise adding speed to be 2 drops/sec, adding sodium hydroxide solution with the concentration of 0.5mol/L into the beaker after the dropwise adding is finished to control the pH value to be 10, reacting for 5 hours at the rotating speed of 250r/min, adding absolute ethyl alcohol, terminating the reaction, vacuum filtering, washing a filter cake with deionized water for 4 times, transferring into a high-pressure homogenizer, circularly homogenizing for 4 times under the pressure of 40MPa, and finally freeze-drying for 8 hours at the temperature of-45 ℃ to obtain an intermediate 1;
step S12, adding the intermediate 1 and toluene into a beaker, performing ultrasonic dispersion for 20min at the temperature of 25 ℃ and the frequency of 40kHz, then adding 2-bromoisobutyryl bromide into the beaker, continuing ultrasonic for 10min with the frequency unchanged, performing suction filtration, washing a filter cake with N, N-dimethylformamide for 4 times, and drying in a vacuum drying oven at the temperature of 50 ℃ to constant weight to obtain an intermediate 2;
and S13, adding the intermediate 2, N-dimethylformamide, styrene and pentamethyldivinyl triamine into a three-neck flask, vacuumizing, charging nitrogen, adding copper chloride, heating to 105 ℃ in a water bath, reacting for 48 hours under the protection of nitrogen, stopping the reaction in an ice bath to obtain a mixed solution 3, wetting neutral alumina with tetrahydrofuran, filling the neutral alumina into a chromatographic column, adding the mixed solution 3 into the chromatographic column to obtain an intermediate 4, treating the intermediate 4 in a rotary evaporator at the temperature of 155 ℃ for 30min, transferring to absolute ethyl alcohol, precipitating for 12 hours, and finally drying in a vacuum drying box at the temperature of 50 ℃ for 12 hours to obtain the modified cellulose nanofiber.
The dosage ratio of the 2, 6-tetramethyl piperidine-1-oxygen free radical, sodium bromide, sodium hypochlorite, eucalyptus pulp and absolute ethyl alcohol in the step S11 is 0.1mmol:1mmol:10mmol:1g:12mL; the ratio of the amount of intermediate 1, toluene and 2-bromoisobutyryl bromide used in step S12 was 0.3g:100mL:2mL; the ratio of the amounts of intermediate 2, N-dimethylformamide, styrene, pentamethyldivinyl triamine and copper chloride used in step S13 was 0.08g:100mL:50mL:0.15mL:0.2g.
The composite anti-aging agent is prepared by the following steps:
s21, adding absolute ethyl alcohol, hexadecylamine, potassium chloride solution with the concentration of 0.1mol/L and deionized water into a reaction kettle, stirring for 30min at the rotating speed of 150r/min, adding isopropyl titanate into the reaction kettle while stirring at the rotating speed of 400r/min at the temperature of 25 ℃, continuing stirring for 20min, standing for 18h, washing a product with absolute ethyl alcohol for 4 times, drying for 12h at the temperature of 42 ℃ in a forced air drying box, and finally calcining for 2h at the temperature of 500 ℃ in a muffle furnace to obtain mesoporous titanium dioxide;
s22, adding 2-hydroxy-4-methoxybenzophenone and absolute ethyl alcohol into a beaker, performing ultrasonic dispersion for 15min at the frequency of 35kHz, then adding mesoporous titanium dioxide into the beaker, stirring for 30min at the rotating speed of 150r/min, filtering, washing a filter cake with deionized water until a washing solution is neutral, and drying in an oven at the temperature of 105 ℃ until the weight is constant, thus obtaining the composite anti-aging agent.
The dosage ratio of the absolute ethyl alcohol, the hexadecylamine, the potassium chloride solution, the deionized water and the isopropyl titanate in the step S21 is 100mL:0.87g:0.4mL:0.5mL:2.2mL; the dosage ratio of the 2-hydroxy-4-methoxybenzophenone, the absolute ethanol and the mesoporous titanium dioxide in the step S22 is 1g:110mL:8g.
The preparation method of the modified barium titanate comprises the following steps:
adjusting the pH value of tartaric acid to 9 by using a sodium hydroxide solution with the mass fraction of 40%, transferring the tartaric acid into a three-neck flask, stirring at the rotating speed of 270r/min, adding barium titanate powder into the three-neck flask while stirring, controlling the reaction temperature to be 50 ℃, performing suction filtration after the rotating speed is unchanged for 2 hours, washing a filter cake with deionized water for 4 times, and finally drying in an oven at 80 ℃ for 5 hours to obtain modified barium titanate, wherein the dosage ratio of the tartaric acid to the barium titanate powder is 8mL:1g.
The coupling agent is silane coupling agent KH-550, the dispersing agent is triethyl hexyl phosphoric acid, and the compatilizer is polypropylene grafted maleic anhydride.
Example 3
A waterproof plastic battery shell comprises the following raw materials in parts by weight: 100 parts of polypropylene, 80 parts of ABS plastic, 15 parts of modified cellulose nanofiber, 10 parts of ethylene-octene copolymer, 1 part of composite anti-aging agent, 5 parts of modified barium titanate, 3 parts of coupling agent, 1 part of dispersing agent and 10 parts of compatilizer;
the waterproof plastic battery shell is prepared by the following steps:
firstly, adding polypropylene, ABS plastic, ethylene-octene copolymer, a coupling agent, a dispersing agent and a compatilizer into a reaction kettle, mixing for 60min at the temperature of 175 ℃ and the rotating speed of 300r/min, then adding modified cellulose nanofiber, modified barium titanate and a composite anti-aging agent into the reaction kettle, and continuously mixing for 20min under the condition of unchanged temperature and rotating speed to obtain a mixture;
and transferring the mixture into a screw extruder for extrusion, bracing, cooling and granulating, controlling the temperature of the extruder from a feeding section to the temperature of a machine head to 225 ℃ to obtain a master batch, drying the master batch in a ventilating drying box at 90 ℃ for 6 hours, and then performing injection molding by an injection molding machine at the injection molding temperature of 285 ℃ to obtain the waterproof plastic battery shell.
The modified cellulose nanofiber is prepared by the following steps:
s11, adding eucalyptus pulp and deionized water into a beaker according to a mass ratio of 2:100, soaking for 48 hours, adding 2, 6-tetramethylpiperidine-1-oxygen free radical and sodium bromide into the beaker, stirring for 10 minutes at a rotating speed of 100r/min, adding sodium hypochlorite into the beaker dropwise, controlling the dropwise adding speed to be 3 drops/sec, adding sodium hydroxide solution with the concentration of 0.5mol/L into the beaker after the dropwise adding is finished to control the pH value to be 10, reacting for 6 hours at the rotating speed of 200-300r/min, adding absolute ethyl alcohol to terminate the reaction, vacuum filtering, washing a filter cake with deionized water for 5 times, transferring into a high-pressure homogenizer, circularly homogenizing for 5 times under the pressure of 60MPa, and finally freeze-drying for 10 hours at the temperature of minus 45 ℃ to obtain an intermediate 1;
step S12, adding the intermediate 1 and toluene into a beaker, performing ultrasonic dispersion for 20min at the temperature of 30 ℃ and the frequency of 50kHz, then adding 2-bromoisobutyryl bromide into the beaker, continuing ultrasonic treatment for 10min with the frequency unchanged, performing suction filtration, washing a filter cake with N, N-dimethylformamide for 5 times, and drying in a vacuum drying oven at the temperature of 50 ℃ to constant weight to obtain an intermediate 2;
and S13, adding the intermediate 2, N-dimethylformamide, styrene and pentamethyldivinyl triamine into a three-neck flask, vacuumizing, charging nitrogen, adding copper chloride, heating to 110 ℃ in a water bath, reacting for 48 hours under the protection of nitrogen, stopping the reaction in an ice bath to obtain a mixed solution 3, wetting neutral alumina with tetrahydrofuran, filling the neutral alumina into a chromatographic column, adding the mixed solution 3 into the chromatographic column to obtain an intermediate 4, treating the intermediate 4 in a rotary evaporator at 160 ℃ for 30min, transferring to absolute ethyl alcohol, precipitating for 15 hours, and finally drying in a vacuum drying box at 50 ℃ for 12 hours to obtain the modified cellulose nanofiber.
The dosage ratio of the 2, 6-tetramethyl piperidine-1-oxygen free radical, sodium bromide, sodium hypochlorite, eucalyptus pulp and absolute ethyl alcohol in the step S11 is 0.1mmol:1mmol:10mmol:1g:15mL; the ratio of the amount of intermediate 1, toluene and 2-bromoisobutyryl bromide used in step S12 was 0.5g:100mL:2mL; the ratio of the amounts of intermediate 2, N-dimethylformamide, styrene, pentamethyldivinyl triamine and copper chloride used in step S13 was 0.1g:100mL:50mL:0.15mL:0.2g.
The composite anti-aging agent is prepared by the following steps:
s21, adding absolute ethyl alcohol, hexadecylamine, potassium chloride solution with the concentration of 0.1mol/L and deionized water into a reaction kettle, stirring for 30min at the rotating speed of 150r/min, adding isopropyl titanate into the reaction kettle while stirring at the rotating speed of 350r/min at the temperature of 25 ℃, continuing stirring for 20min, standing for 18h, washing a product with absolute ethyl alcohol for 3-5 times, drying for 12h at the temperature of 45 ℃ in a blast drying box, and finally calcining for 2h at the temperature of 500 ℃ in a muffle furnace to obtain mesoporous titanium dioxide;
s22, adding 2-hydroxy-4-methoxybenzophenone and absolute ethyl alcohol into a beaker, performing ultrasonic dispersion for 20min at the frequency of 35kHz, then adding mesoporous titanium dioxide into the beaker, stirring for 30min at the rotating speed of 200r/min, filtering, washing a filter cake with deionized water until a washing solution is neutral, and drying in an oven at the temperature of 110 ℃ until the weight is constant, thus obtaining the composite anti-aging agent.
The dosage ratio of the absolute ethyl alcohol, the hexadecylamine, the potassium chloride solution, the deionized water and the isopropyl titanate in the step S21 is 100mL:0.87g:0.4mL:0.6mL:2.2mL; the dosage ratio of the 2-hydroxy-4-methoxybenzophenone, the absolute ethanol and the mesoporous titanium dioxide in the step S22 is 1g:120mL:10g.
The preparation method of the modified barium titanate comprises the following steps:
adjusting the pH value of tartaric acid to 9 by using a sodium hydroxide solution with the mass fraction of 40%, transferring the tartaric acid into a three-neck flask, stirring at the rotating speed of 280r/min, adding barium titanate powder into the three-neck flask while stirring, controlling the reaction temperature to be 50 ℃, performing suction filtration after the rotating speed is unchanged for 2 hours, washing a filter cake with deionized water for 5 times, and finally drying the filter cake in an oven at 80 ℃ for 6 hours to obtain modified barium titanate, wherein the dosage ratio of the tartaric acid to the barium titanate powder is 10mL:1g.
The coupling agent is silane coupling agent KH-550, the dispersing agent is triethyl hexyl phosphoric acid, and the compatilizer is polypropylene grafted maleic anhydride.
Comparative example 1
The modified cellulose nanofibers of example 1 were removed, and the remaining raw materials and preparation process were unchanged.
Comparative example 2
The composite anti-aging agent in example 2 was removed, and the remaining raw materials and preparation process were unchanged.
Comparative example 3
The comparative example is a battery shell material commonly used in the market.
The battery shell materials of examples 1-3 and comparative examples 1-3 were subjected to performance testing, the test results are shown in the following table:
as can be seen from the table, the performances of the battery shell prepared by the method in the invention are better than those of the battery shell prepared by the method in the comparative examples 1-3 in the mechanical performance test, the thermal deformation test and the aging resistance test, so that the battery shell has high temperature resistance, aging resistance and impact resistance, and has great application value in the field of battery packaging.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the invention or beyond the scope of the appended claims.
Claims (5)
1. The waterproof plastic battery shell is characterized by comprising the following raw materials in parts by weight: 80-100 parts of polypropylene, 50-80 parts of ABS plastic, 10-15 parts of modified cellulose nanofiber, 5-10 parts of ethylene-octene copolymer, 0.5-1 part of composite anti-aging agent, 3-5 parts of modified barium titanate, 1-3 parts of coupling agent, 1 part of dispersing agent and 5-10 parts of compatilizer;
the waterproof plastic battery shell is prepared by the following steps:
firstly, adding polypropylene, ABS plastic, ethylene-octene copolymer, coupling agent, dispersing agent and compatilizer into a reaction kettle, mixing for 30-60min at the temperature of 165-175 ℃ and the rotating speed of 200-300r/min, then adding modified cellulose nanofiber, modified barium titanate and composite anti-aging agent into the reaction kettle, and continuously mixing for 20min under the condition of unchanged temperature and rotating speed to obtain a mixture;
transferring the mixture into a screw extruder for extrusion, bracing, cooling and granulating, controlling the temperature of the extruder from a feeding section to 180-225 ℃ of a machine head to obtain master batch, drying the master batch in a ventilating drying box at 90 ℃ for 6 hours, and then performing injection molding by an injection molding machine at 285 ℃ to obtain the waterproof plastic battery shell;
the modified cellulose nanofiber is prepared by the following steps:
s11, adding eucalyptus pulp and deionized water into a beaker according to a mass ratio of 2:100, soaking for 24-48h, adding 2, 6-tetramethyl piperidine-1-oxygen free radical and sodium bromide into the beaker, stirring for 10min at a rotating speed of 60-100r/min, then dropwise adding sodium hypochlorite into the beaker, controlling the dropwise adding speed to be 1-3 drops/sec, adding sodium hydroxide solution with the concentration of 0.5mol/L into the beaker after the dropwise adding is finished, controlling the pH value to be 10, reacting for 4-6h at the rotating speed of 200-300r/min, adding absolute ethyl alcohol to terminate the reaction, carrying out vacuum suction filtration, washing a filter cake with deionized water for 3-5 times, transferring into a high-pressure homogenizer, circularly homogenizing for 3-5 times under the pressure of 25-60MPa, and finally carrying out freeze drying for 5-10h at the temperature of-45 ℃ to obtain an intermediate 1;
step S12, adding the intermediate 1 and toluene into a beaker, performing ultrasonic dispersion for 20min at the temperature of 20-30 ℃ and the frequency of 30-50kHz, then adding 2-bromoisobutyryl bromide into the beaker, continuing ultrasonic treatment for 10min with the constant frequency, performing suction filtration, washing a filter cake with N, N-dimethylformamide for 3-5 times, and drying in a vacuum drying oven at the temperature of 50 ℃ until the weight is constant to obtain an intermediate 2;
step S13, adding an intermediate 2, N-dimethylformamide, styrene and pentamethyldivinyl triamine into a three-neck flask, vacuumizing, charging nitrogen, adding copper chloride, heating to 100-110 ℃ in a water bath, reacting for 48 hours under the protection of nitrogen, stopping the reaction in an ice bath to obtain a mixed solution 3, wetting neutral alumina with tetrahydrofuran, filling the neutral alumina into a chromatographic column, adding the mixed solution 3 into the chromatographic column to obtain an intermediate 4, treating the intermediate 4 in a rotary evaporator at the temperature of 150-160 ℃ for 30min, transferring to absolute ethyl alcohol, precipitating for 10-15 hours, and finally drying in a vacuum drying box at the temperature of 50 ℃ for 12 hours to obtain the modified cellulose nanofiber;
the composite anti-aging agent is prepared by the following steps:
s21, adding absolute ethyl alcohol, hexadecylamine, potassium chloride solution with the concentration of 0.1mol/L and deionized water into a reaction kettle, stirring for 30min at the rotating speed of 150r/min, adding isopropyl titanate into the reaction kettle while stirring at the temperature of 25 ℃ at the rotating speed of 300-500r/min, continuously stirring for 20min, standing for 18h, washing a product with absolute ethyl alcohol for 3-5 times, drying for 12h at the temperature of 40-45 ℃ in a blast drying oven, and finally calcining for 2h at the temperature of 500 ℃ in a muffle furnace to obtain mesoporous titanium dioxide;
s22, adding 2-hydroxy-4-methoxybenzophenone and absolute ethyl alcohol into a beaker, performing ultrasonic dispersion for 10-20min at the frequency of 35kHz, then adding mesoporous titanium dioxide into the beaker, stirring for 30min at the rotating speed of 100-200r/min, filtering, washing a filter cake with deionized water until a washing solution is neutral, and drying in an oven at the temperature of 100-110 ℃ until the weight is constant to obtain the composite anti-aging agent;
the preparation method of the modified barium titanate comprises the following steps:
adjusting the pH value of tartaric acid to 9 by using a sodium hydroxide solution with the mass fraction of 40%, transferring the tartaric acid into a three-neck flask, stirring at the rotating speed of 250-280r/min, adding barium titanate powder into the three-neck flask while stirring, controlling the reaction temperature to be 50 ℃, performing suction filtration after the rotating speed is unchanged for 2 hours, washing a filter cake with deionized water for 3-5 times, and finally drying the filter cake in an oven at 80 ℃ for 4-6 hours to obtain modified barium titanate, wherein the dosage ratio of the tartaric acid to the barium titanate powder is 5-10mL:1g.
2. The waterproof plastic battery case according to claim 1, wherein the dosage ratio of 2, 6-tetramethylpiperidine-1-oxyl, sodium bromide, sodium hypochlorite, eucalyptus pulp and absolute ethyl alcohol in the step S11 is 0.1mmol:1mmol:10mmol:1g:10-15mL; the dosage ratio of the intermediate 1, toluene and 2-bromoisobutyryl bromide in the step S12 is 0.1-0.5g:100mL:2mL; the dosage ratio of the intermediate 2, the N, N-dimethylformamide, the styrene, the pentamethyldivinyl triamine and the cupric chloride in the step S13 is 0.05-0.1g:100mL:50mL:0.15mL:0.2g.
3. The waterproof plastic battery case of claim 1, wherein in step S21, the dosage ratio of the absolute ethanol, the hexadecylamine, the potassium chloride solution, the deionized water and the isopropyl titanate is 100mL:0.87g:0.4mL:0.5-0.6mL:2.2mL; the dosage ratio of the 2-hydroxy-4-methoxybenzophenone, the absolute ethanol and the mesoporous titanium dioxide in the step S22 is 1g:100-120mL:5-10g.
4. The waterproof plastic battery shell as claimed in claim 1, wherein the coupling agent is one or more of silane coupling agent KH-550, silane coupling agent KH-560 and silane coupling agent KH-570, the dispersing agent is one of triethyl hexyl phosphoric acid and sodium dodecyl sulfate, and the compatilizer is one of polypropylene grafted maleic anhydride and acrylonitrile-butadiene-styrene copolymer grafted maleic anhydride.
5. The method for preparing the waterproof plastic battery shell as claimed in claim 1, which is characterized by comprising the following steps:
firstly, adding polypropylene, ABS plastic, ethylene-octene copolymer, coupling agent, dispersing agent and compatilizer into a reaction kettle, mixing for 30-60min at the temperature of 165-175 ℃ and the rotating speed of 200-300r/min, then adding modified cellulose nanofiber, modified barium titanate and composite anti-aging agent into the reaction kettle, and continuously mixing for 20min under the condition of unchanged temperature and rotating speed to obtain a mixture;
and secondly, transferring the mixture into a screw extruder for extrusion, bracing, cooling and granulating, controlling the temperature of the extruder from a feeding section to 180-225 ℃ of a machine head to obtain master batch, drying the master batch in a ventilating drying box at 90 ℃ for 6 hours, and then performing injection molding by an injection molding machine at 285 ℃ to obtain the waterproof plastic battery shell.
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