CN115976474A - Thermal-shock-resistant metallized film and preparation method thereof - Google Patents
Thermal-shock-resistant metallized film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a thermal shock resistant metallized film and a preparation method thereof, wherein the thermal shock resistant metallized film consists of a base film and a metal film, and the base film comprises the following components: polypropylene resin, polytetrafluoroethylene, glass fiber, nano argil, a flame-retardant synergist, an anti-aging agent, a crosslinking agent and a lubricant. By modifying the nano argil, the uniform dispersion of the nano argil in a polypropylene matrix is improved, the crosslinking of the nano argil and polypropylene resin is promoted, the molecular structure of the polypropylene film matrix is greatly improved, the rigidity of a polypropylene molecular chain is increased, and the high-temperature impact resistance of the nano argil is greatly improved.
Description
Technical Field
The invention relates to the technical field of capacitor films, in particular to a thermal shock resistant metallized film and a preparation method thereof.
Background
With the development of new energy technology, capacitors are widely applied in the fields of wind power, rail transit, electric automobiles, solar power generation, smart power grids, medical equipment, high-power frequency converters and the like. The metallized film capacitor is a capacitor which is produced by using an organic plastic film (abbreviated as an electrical film or a base film) having a thickness of not more than 10 μm as a dielectric, forming a metallized film by depositing a metal film having a thickness of only several tens of nanometers on the surface thereof as an electrode by vacuum deposition, and then winding the metallized film into a columnar shape, and the films used for the metallized film capacitor include polyester, polypropylene, polycarbonate and the like, and there are laminate types other than the wound type. The metallized film capacitor has the characteristics of high withstand voltage, high insulation resistance, good impedance frequency characteristic, high capacity stability, low loss tangent and the like.
The metallized film is the heart of the capacitor, so the metallized film manufactured by the capacitor can ensure the long-term stable work of the whole machine only by taking the organic plastic film which has high frequency resistance, high temperature resistance and can bear large current impact as a medium.
The existing metallized film is easy to break down at high temperature, a capacitor core wound by the existing metallized film is compact in structure, heat is not easy to dissipate, the metallized film is easier to break down when the existing metallized film continuously works in an environment with higher temperature, and the phenomenon that the multilayer metallized film is continuously broken down to cause large-area burn is also caused, a large amount of gas is generated, the shell of the capacitor can expand and deform, and even explode when the capacitor is serious, so that fire disasters are caused.
The Chinese patent application CN103865148A discloses a composite polyethylene capacitor metallized film and a preparation method thereof, and the composite polyethylene capacitor metallized film is characterized by being prepared from the following raw materials in parts by weight: 200 parts of low-density polyethylene, 20-23 parts of metallocene linear low-density polyethylene, 1-2 parts of diphenylmethane diisocyanate, 4-5 parts of isobornyl acrylate, 1-2 parts of phenyl glycidyl ether, 2-3 parts of aromatic urethane acrylate and 5-6 parts of an auxiliary agent; the invention has simple processing technology, and the film capacitor manufactured by the method has small contact resistance, thereby ensuring good product characteristics; the addition of the auxiliary agent enhances the barrier property and the air tightness of the film, has good pressure resistance and impact resistance, has the characteristics of high heat sealing strength and good heat sealing performance, is puncture-resistant, flame-retardant and long in service life. However, the film has the defects of low flame retardance, mechanical properties and dielectric properties when used as the heart of a capacitor.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, an object of the present invention is to provide a metallized film having excellent dielectric breakdown strength and thermal shock resistance at high temperatures.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
a metallized film resistant to thermal shock comprises a base film and a metal layer.
Preferably, the base film comprises the following components: polypropylene resin, polytetrafluoroethylene, glass fiber, nano argil, a flame-retardant synergist, an anti-aging agent, a cross-linking agent and a lubricant.
Preferably, the base film comprises the following components in parts by mass: 80-100 parts of polypropylene resin, 1-10 parts of polytetrafluoroethylene, 5-10 parts of glass fiber, 10-15 parts of nano argil, 1-5 parts of flame retardant synergist, 0.5-1.5 parts of anti-aging agent, 0.5-1.5 parts of cross-linking agent and 0.5-1.5 parts of lubricating agent.
Preferably, the nano argil is modified nano argil, and the preparation method comprises the following steps:
1) Adding the nano argil into a dilute sulfuric acid solution for reaction, filtering, washing, drying, mixing with water and sodium dodecyl sulfate, and uniformly stirring to obtain pretreated nano argil;
2) Mixing styrene, 1-bromoethylbenzene, ferric chloride, allylaniline and anisole, heating for reaction, cooling an aluminum peroxide column after the reaction is finished, adding a column passing solution into a methanol water solution, and stirring, filtering and drying to obtain a polymer monomer;
3) Mixing and heating a polymer monomer, 2,2' -azobisisobutyronitrile, chloroform, pretreated nano argil and 1,3-butadiene for reaction, cooling to room temperature after the reaction is finished, and filtering, washing and drying to obtain the modified nano argil.
Further preferably, the preparation method of the modified nano argil comprises the following steps:
1) Roasting 100-200g of nano argil at 200-300 ℃ for 2-4h, cooling to 20-40 ℃, grinding, sieving with a 500-600 mesh sieve, adding into 400-1000mL of 10-20wt% dilute sulfuric acid solution, heating to 80-90 ℃, reacting for 2-4h, filtering, collecting a filter cake, washing the filter cake with water until the pH value is 6.5-7.5, and drying at 60-80 ℃ for 6-8h; then mixing with 100-150mL of water and 10-20g of sodium dodecyl sulfate, and uniformly stirring to obtain pretreated nano argil;
2) Under the nitrogen atmosphere, mixing 40-50g of styrene, 0.5-1.5g of 1-bromoethylbenzene, 0.1-0.3g of ferric chloride, 0.5-2g of allylaniline and 40-50g of anisole, heating to 100-120 ℃ for reaction for 1-2h, cooling to room temperature after the reaction is finished to obtain a reaction mixture, passing the reaction mixture through an alumina column, adding column-passing liquid into 150-250mL of 70-99wt% methanol aqueous solution, stirring for 10-20min, filtering, collecting a filter cake, and drying the filter cake at 60-80 ℃ for 6-8h to obtain a polymer monomer;
3) Under the atmosphere of nitrogen, mixing and stirring uniformly 12-15g of the polymer monomer obtained in the step 2), 8-12g2,2' -azobisisobutyronitrile, 300-500mL of chloroform, 20-30g of the pretreated nano argil obtained in the step 1) and 6-10g of 1, 3-butadiene, heating to 50-80 ℃, reacting for 20-24h, cooling to room temperature after the reaction is finished, filtering, washing a filter cake for 2-3 times by using anhydrous methanol, and drying at 40-60 ℃ for 8-10h to obtain the modified nano argil.
Preferably, the flame retardant synergist is one or more of antimony trioxide, sodium antimonate, antimony phosphate and antimony phosphite.
Preferably, the anti-aging agent is one of phosphite antioxidant, hindered phenol oxidant and thioester antioxidant;
more preferably, the anti-aging agent is a mixture of antioxidant 168 and antioxidant 1010 with the mass ratio of 1-2:2-3.
Preferably, the cross-linking agent is one or more of benzoyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne.
Preferably, the lubricant is one of methyl silicone oil and white oil.
Polypropylene is the most used dielectric material in power capacitors, has the advantages of high breakdown field strength, low dielectric loss, wide source and the like, but has low dielectric constant, is inflammable, can be decomposed under the action of high temperature and oxidation, has poor impact resistance and high temperature resistance, limits the energy storage of polypropylene and further more extensive application of the polypropylene. At present, one main research direction for improving the dielectric constant of a dielectric material is to add inorganic nano particles, nano argil is a mineral nano raw material, silt mainly composed of hydromica, kaolinite, montmorillonite, quartz and feldspar has good thermal stability and chemical stability, the addition of argil can not only play a role in enhancing and improving the adhesion force, but also can improve the flame retardance, insulation, wear resistance, corrosion resistance and other functions of a product, but argil surface is hydrophilic and oleophobic, agglomeration is generated in a polypropylene matrix and is difficult to uniformly disperse, and a good reinforcing effect cannot be achieved.
The invention also discloses a preparation method of the thermal shock resistant metallized film, which comprises the following steps:
s1, weighing the raw materials according to a formula, and placing polypropylene resin, polytetrafluoroethylene, glass fiber, nano argil, a flame retardant synergist, an anti-aging agent, a cross-linking agent and a lubricant into a kneading machine to be uniformly mixed to obtain a mixture;
s2, feeding the mixture into an extruder for melting, cooling and shaping, biaxial stretching, thickness detection, fixed-width edge cutting, roughened surface corona treatment and rolling to obtain a base film;
and S3, evaporating a metal layer on the base film in a vacuum evaporation manner to obtain the thermal shock resistant metallized film.
Preferably, the thickness of the base film obtained in step S2 is 1 to 10 μm.
Preferably, the melting temperature in step S2 is 230 to 270 ℃.
Preferably, the metal layer is one or more of metal aluminum, zinc, magnesium, tin, copper oxide or simple substance; further preferably, the metal layer is nano alumina.
Compared with the prior art, the invention has the following beneficial effects: according to the invention, the modified nano argil is introduced into the polypropylene film, and the nano argil is copolymerized with the polymer monomer and 1,3-butadiene, so that the high free energy of the surface of the nano argil is reduced, the hydrophobicity of the nano argil is improved, the polarity of the nano argil is reduced, the uniform dispersion of the nano argil in a polypropylene matrix is improved, the crosslinking of the nano argil and polypropylene resin is promoted, the molecular structure of the polypropylene film matrix is greatly improved, the rigidity of a polypropylene molecular chain is increased, the high temperature resistance of the polypropylene molecular chain is greatly improved, the dielectric property of the polypropylene film is also improved, and the uniformly dispersed nano argil can also be used as a nano flame retardant, so that the mechanical property of a metallized film is improved and the flame retardant property of the metallized film is also improved.
Detailed Description
For the sake of brevity, the articles used in the following examples are all commercially available products unless otherwise specified, and the methods used are conventional methods unless otherwise specified.
The invention uses part of raw materials with the following sources:
polypropylene resin with a density of 0.963g/cm 3 The shrinkage is 1.25%, the melt flow rate is 2.8g/10min, and the brand PP is P348S.
Polytetrafluoroethylene with bulk specific gravity of 250-500g/L, melting point of 330 deg.C, particle size of 3-5 μm, and specific gravity of 2.2g/cm 3 。
The glass fiber has a single fiber diameter of 13 microns and a chopped length of 12-18cm.
The nano argil has a particle size of less than 500nm, an oil absorption of 50 +/-5 g/100g and a water content of less than or equal to 1.5%.
Example 1
A method for preparing a thermal shock resistant metallized film comprising the steps of:
s1, 100g of polypropylene resin, 10g of polytetrafluoroethylene, 10g of glass fiber, 15g of modified nano argil, 5g of antimony phosphate, 1g of anti-aging agent, 1g of dicumyl peroxide and 1g of methyl silicone oil are placed in a kneader and stirred for 20min at the conditions of 700rpm and 80 ℃ to be uniformly mixed, and a mixture is obtained; the anti-aging agent is a mixture of antioxidant 168 and antioxidant 1010 with the mass ratio of 2:3;
s2, feeding the mixture into an extruder, melting at 250 ℃, cooling and shaping, stretching in two directions, detecting thickness, cutting edges in a fixed width mode, carrying out corona treatment on a roughened surface, and rolling to obtain a base film; the thickness of the base film is 5 μm;
and S3, evaporating and plating nano aluminum oxide on the base film in a vacuum evaporation mode to obtain the thermal shock resistant metallized film.
The preparation method of the modified nano argil comprises the following steps:
1) Roasting 200g of nano argil at 250 ℃ for 3h, cooling to 30 ℃, grinding, sieving with a 500-mesh sieve, adding the obtained product into 500mL of a 15wt% dilute sulfuric acid solution, heating to 80 ℃ for reaction for 3h, filtering, collecting a filter cake, washing the filter cake with water until the pH value is 7, and drying at 70 ℃ for 7h; then mixing with 150mL of water and 20g of sodium dodecyl sulfate and uniformly stirring to obtain pretreated nano argil;
2) Mixing 45g of styrene, 1.2g of 1-bromoethylbenzene, 0.2g of ferric chloride, 1.5g of allylaniline and 45g of anisole in a nitrogen atmosphere, heating to 110 ℃ for reaction for 2 hours, cooling to room temperature after the reaction is finished to obtain a reaction mixture, allowing the reaction mixture to pass through an alumina column, adding a column-passing solution into 200mL of 99wt% methanol aqueous solution, stirring for 15 minutes, filtering, collecting a filter cake, and drying the filter cake at 70 ℃ for 8 hours to obtain a polymer monomer;
3) Under the nitrogen atmosphere, 14.5g of the polymer monomer obtained in the step 2), 10.3g of 2,2' -azobisisobutyronitrile, 400mL of chloroform, 25g of the pretreated nano argil obtained in the step 1) and 8.8g of 1, 3-butadiene are mixed and stirred uniformly, then heated to 60 ℃ for reaction for 24 hours, after the reaction is finished, the mixture is cooled to room temperature, filtered, the filter cake is washed by absolute methanol for 3 times and then dried at 60 ℃ for 10 hours to obtain the modified nano argil.
Comparative example 1
A method for preparing a thermal shock resistant metallized film comprising the steps of:
s1, 100g of polypropylene resin, 10g of polytetrafluoroethylene, 10g of glass fiber, 15g of modified nano argil, 5g of antimony phosphate, 1g of anti-aging agent, 1g of dicumyl peroxide and 1g of methyl silicone oil are placed in a kneader and stirred for 20min at the conditions of 700rpm and 80 ℃ to be uniformly mixed, and a mixture is obtained; the anti-aging agent is a mixture of antioxidant 168 and antioxidant 1010 with the mass ratio of 2:3;
s2, feeding the mixture into an extruder, melting at 250 ℃, cooling and shaping, stretching in two directions, detecting thickness, cutting edges in a fixed width mode, carrying out corona treatment on a roughened surface, and rolling to obtain a base film; the thickness of the base film is 5 μm;
and S3, evaporating and plating nano aluminum oxide on the base film in a vacuum evaporation mode to obtain the thermal shock resistant metallized film.
The preparation method of the modified nano argil comprises the following steps:
1) Roasting 200g of nano argil at 250 ℃ for 3h, cooling to 30 ℃, grinding, sieving with a 500-mesh sieve, adding the obtained product into 500mL of a 15wt% dilute sulfuric acid solution, heating to 80 ℃ for reaction for 3h, filtering, collecting a filter cake, washing the filter cake with water until the pH value is 7, and drying at 70 ℃ for 7h; then mixing the pretreated nano argil with 150mL of water and 20g of sodium dodecyl sulfate and uniformly stirring to obtain pretreated nano argil;
2) Mixing 45g of styrene, 1.2g of 1-bromoethylbenzene, 0.2g of ferric chloride, 1.5g of allylaniline and 45g of anisole in a nitrogen atmosphere, heating to 110 ℃ for reaction for 2 hours, cooling to room temperature after the reaction is finished to obtain a reaction mixture, allowing the reaction mixture to pass through an alumina column, adding a column-passing solution into 200mL of 99wt% methanol aqueous solution, stirring for 15 minutes, filtering, collecting a filter cake, and drying the filter cake at 70 ℃ for 8 hours to obtain a polymer monomer;
3) Under the nitrogen atmosphere, 14.5g of the polymer monomer obtained in the step 2), 10.3g of 2,2' -azobisisobutyronitrile, 400mL of chloroform and 25g of the pretreated nano argil obtained in the step 1) are mixed and stirred uniformly, then the mixture is heated to 60 ℃ to react for 24 hours, after the reaction is finished, the mixture is cooled to room temperature, filtered, and a filter cake is washed by absolute methanol for 3 times and then dried at 60 ℃ for 10 hours to obtain the modified nano argil.
Comparative example 2
A method for preparing a thermal shock resistant metallized film comprising the steps of:
s1, 100g of polypropylene resin, 10g of polytetrafluoroethylene, 10g of glass fiber, 15g of modified nano argil, 5g of antimony phosphate, 1g of anti-aging agent, 1g of dicumyl peroxide and 1g of methyl silicone oil are placed in a kneader and stirred for 20min at the conditions of 700rpm and 80 ℃ to be uniformly mixed, and a mixture is obtained; the anti-aging agent is a mixture of antioxidant 168 and antioxidant 1010 with the mass ratio of 2:3;
s2, feeding the mixture into an extruder, melting at 250 ℃, cooling and shaping, stretching in two directions, detecting thickness, cutting edges in a fixed width mode, carrying out corona treatment on a roughened surface, and rolling to obtain a base film; the thickness of the base film is 5 μm;
and S3, evaporating and plating nano aluminum oxide on the base film in a vacuum evaporation mode to obtain the thermal shock resistant metallized film.
The preparation method of the modified nano argil comprises the following steps:
1) Roasting 200g of nano argil at 250 ℃ for 3h, cooling to 30 ℃, grinding, sieving with a 500-mesh sieve, adding the obtained product into 500mL of a 15wt% dilute sulfuric acid solution, heating to 80 ℃ for reaction for 3h, filtering, collecting a filter cake, washing the filter cake with water until the pH value is 7, and drying at 70 ℃ for 7h; then mixing the pretreated nano argil with 150mL of water and 20g of sodium dodecyl sulfate and uniformly stirring to obtain pretreated nano argil;
2) Under the atmosphere of nitrogen, 10.3g of 2,2' -azobisisobutyronitrile, 400mL of chloroform, 25g of the pretreated nano argil obtained in the step 1) and 8.8g of 1, 3-butadiene are mixed and stirred uniformly, then heated to 60 ℃ for reaction for 24 hours, cooled to room temperature after the reaction is finished, filtered, the filter cake is washed by absolute methanol for 3 times and then dried at 60 ℃ for 10 hours to obtain the modified nano argil.
Comparative example 3
A method for preparing a thermal shock resistant metallized film comprising the steps of:
s1, 100g of polypropylene resin, 10g of polytetrafluoroethylene, 10g of glass fiber, 15g of nano argil, 5g of antimony phosphate, 1g of anti-aging agent, 1g of dicumyl peroxide and 1g of methyl silicone oil are placed in a kneader and stirred for 20min at the conditions of 700rpm and 80 ℃ to be uniformly mixed to obtain a mixture; the anti-aging agent is a mixture of antioxidant 168 and antioxidant 1010 with the mass ratio of 2:3;
s2, feeding the mixture into an extruder, melting at 250 ℃, cooling and shaping, stretching in two directions, detecting thickness, cutting edges in a fixed width mode, carrying out corona treatment on a roughened surface, and rolling to obtain a base film; the thickness of the base film is 5 μm;
and S3, evaporating and plating nano aluminum oxide on the base film in a vacuum evaporation mode to obtain the thermal shock resistant metallized film.
Comparative example 4
A method for preparing a thermal shock resistant metallized film comprising the steps of:
s1, 100g of polypropylene resin, 10g of polytetrafluoroethylene, 10g of glass fiber, 5g of antimony phosphate, 1g of anti-aging agent, 1g of dicumyl peroxide and 1g of methyl silicone oil are placed in a kneader and are stirred for 20min at the temperature of 80 ℃ at 700rpm to be uniformly mixed to obtain a mixture; the anti-aging agent is a mixture of antioxidant 168 and antioxidant 1010 with the mass ratio of 2:3;
s2, feeding the mixture into an extruder, melting at 250 ℃, cooling and shaping, stretching in two directions, detecting thickness, cutting edges in a fixed width mode, carrying out corona treatment on a roughened surface, and rolling to obtain a base film; the thickness of the base film is 5 μm;
and S3, evaporating and plating nano aluminum oxide on the base film in a vacuum evaporation mode to obtain the thermal shock resistant metallized film.
Test example 1
And (3) testing tensile strength: according to the requirements of GB/T10003-2008 ' common-use biaxially oriented polypropylene (BOPP) film ', reference is made to GB/T1040.3-2006 ' determination part 3 of plastic tensile property: test method of film and sheet test conditions the base films obtained in example 1 and comparative examples 1 to 4 were subjected to a test of tensile strength, a sample size was 150mm in length and 15mm in width, a jig interval was 100mm, a test speed was 250mm/min, each sample was measured 3 times, test results were averaged, and the test results are shown in table 1:
table 1 tensile strength test results of base film
As can be seen from the experimental results of table 1, the base film prepared in example 1 has the best tensile properties, and example 1 is different from other comparative examples in that the nano clay to which the polymer monomer, 1,3-butadiene, is added is reacted under the condition of 2,2' -azobisisobutyronitrile initiator, which may cause the phenomenon because the high free energy of the surface of the nano clay is reduced, the hydrophobicity thereof is improved, the polarity thereof is reduced, the uniform dispersion thereof in the polypropylene matrix is improved, the mechanical properties of the base film are improved, and thus the base film has better tensile properties by combining the polymer.
Test example 2
And (3) testing breakdown strength: the metallized films having a thickness of 9 μm obtained in example 1 and comparative examples 1 to 4 were subjected to a DC breakdown test in silicone oil using a hemispherical electrode having a diameter of 12.7mm at a voltage-increasing rate of 500V/s. At least 30 effective breakdown points are obtained from each sample, weibull statistical analysis is carried out on the at least 30 breakdown field strength data, a scale parameter of Weibull distribution, namely the breakdown field strength when the breakdown probability is 63.2%, is selected as a characteristic breakdown field strength for judgment, and the test result is shown in Table 2:
measurement of dielectric constant: the low-frequency dielectric property test is carried out by adopting an Agilent HP4294B alternating-current impedance analyzer, the test frequency range is 0.1-100MHz, the test object is a metalized film with the thickness of 9 mu m prepared in example 1 and comparative examples 1-4, and the test principle is a parallel plate capacitor. And (4) testing at room temperature, namely coating silver paste on the upper surface and the lower surface of a sample to be tested, drying in an oven at 80 ℃, and testing. The dielectric constant value is obtained by converting the capacitance and the dielectric constant, and the conversion formula is shown as epsilon r ＝(C×d)/(S×ε 0 ). Wherein epsilon r Is the dielectric constant of the sample, C is the capacitance value obtained by testing the sample, d is the thickness of the sample, epsilon 0 The dielectric constant in vacuum is usually 8.85X 10 -12 F/m, S is the area of the sample. The high-frequency dielectric property is tested by an Agilent HP8722ET vector network analyzer. The material was tested by the resonant cavity method and the stripline method, the high-frequency dielectric properties and the microwave dielectric properties both refer to data measured at a frequency of 10GHz, and the test results are shown in table 2:
TABLE 2 breakdown Strength and dielectric constant test results
From the experimental results in table 2, it can be seen that the metallized film prepared in example 1 has the highest breakdown strength and dielectric constant, which may be caused by the high free energy of the surface of the nano kaolin combined with the polymer being reduced, the hydrophobicity being increased, the polarity being decreased, the uniform dispersion in the polypropylene matrix being improved, the dielectric property of the metallized film being improved, the crosslinking with the polypropylene resin being promoted, the molecular structure of the polypropylene film matrix being greatly improved, the rigidity of the polypropylene molecular chain being increased, the high temperature resistance being greatly improved, and the uniformly dispersed nano kaolin being further used as a nano flame retardant, being capable of avoiding combustion at high temperature and improving the thermal shock property of the metallized film.
Claims (10)
1. A metallized film that is resistant to thermal shock, comprising: the metal film is composed of a base film and a metal layer.
2. The thermal shock resistant metallized film of claim 1, wherein said base film comprises the following composition: polypropylene resin, polytetrafluoroethylene, glass fiber, nano argil, a flame-retardant synergist, an anti-aging agent, a crosslinking agent and a lubricant.
3. The thermal shock resistant metallized film of claim 1 or 2, wherein the base film comprises the following components in parts by mass: 80-100 parts of polypropylene resin, 1-10 parts of polytetrafluoroethylene, 5-10 parts of glass fiber, 10-15 parts of nano argil, 1-5 parts of flame retardant synergist, 0.5-1.5 parts of anti-aging agent, 0.5-1.5 parts of cross-linking agent and 0.5-1.5 parts of lubricating agent.
4. The thermal shock resistant metallized film of claim 2 or 3, wherein said nano-clay is a modified nano-clay prepared by the method comprising:
1) Adding the nano argil into a dilute sulfuric acid solution for reaction, filtering, washing, drying, mixing with water and sodium dodecyl sulfate, and uniformly stirring to obtain pretreated nano argil;
2) Mixing styrene, 1-bromoethylbenzene, ferric chloride, allylaniline and anisole, heating for reaction, cooling an aluminum peroxide column after the reaction is finished, adding a column passing solution into a methanol water solution, and stirring, filtering and drying to obtain a polymer monomer;
3) Mixing and heating a polymer monomer, 2,2' -azobisisobutyronitrile, chloroform, pretreated nano argil and 1,3-butadiene for reaction, cooling to room temperature after the reaction is finished, and filtering, washing and drying to obtain the modified nano argil.
5. The thermal shock resistant metallized film of claim 4, wherein said modified nano-clay is prepared by a process comprising the steps of:
1) Roasting 100-200g of nano argil at 200-300 ℃ for 2-4h, cooling to 20-40 ℃, grinding, sieving with a 500-600 mesh sieve, adding into 400-1000mL of 10-20wt% dilute sulfuric acid solution, heating to 80-90 ℃, reacting for 2-4h, filtering, collecting a filter cake, washing the filter cake with water until the pH value is 6.5-7.5, and drying at 60-80 ℃ for 6-8h; then mixing with 100-150mL of water and 10-20g of sodium dodecyl sulfate, and uniformly stirring to obtain pretreated nano argil;
2) Under the nitrogen atmosphere, mixing 40-50g of styrene, 0.5-1.5g of 1-bromoethylbenzene, 0.1-0.3g of ferric chloride, 0.5-2g of allylaniline and 40-50g of anisole, heating to 100-120 ℃, reacting for 1-2h, cooling to room temperature after the reaction is finished to obtain a reaction mixture, passing the reaction mixture through an alumina column, adding column-passing liquid into 150-250mL of 70-99wt% methanol aqueous solution, stirring for 10-20min, filtering, collecting a filter cake, and drying the filter cake at 60-80 ℃ for 6-8h to obtain a polymer monomer;
3) Under the atmosphere of nitrogen, mixing and stirring uniformly 12-15g of the polymer monomer obtained in the step 2), 8-12g2,2' -azobisisobutyronitrile, 300-500mL of chloroform, 20-30g of the pretreated nano argil obtained in the step 1) and 6-10g of 1, 3-butadiene, heating to 50-80 ℃, reacting for 20-24h, cooling to room temperature after the reaction is finished, filtering, washing a filter cake for 2-3 times by using anhydrous methanol, and drying at 40-60 ℃ for 8-10h to obtain the modified nano argil.
6. The thermal shock resistant metallized film of claim 2 or 3, wherein: the flame-retardant synergist is one or more of antimony trioxide, sodium antimonate, antimony phosphate and antimony phosphite.
7. The thermal shock resistant metallized film of claim 2 or 3, wherein: the anti-aging agent is one of phosphite antioxidant, hindered phenol oxidant and thioester antioxidant.
8. The thermal shock resistant metallized film of claim 2 or 3, wherein: the cross-linking agent is one or more of benzoyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne.
9. A method of making a thermal shock resistant metallized film according to any one of claims 1 to 8, comprising the steps of:
s1, placing polypropylene resin, polytetrafluoroethylene, glass fiber, nano argil, a flame-retardant synergist, an anti-aging agent, a cross-linking agent and a lubricant into a kneading machine, and uniformly mixing to obtain a mixture;
s2, feeding the mixture into an extruder for melting, cooling and shaping, biaxial stretching, thickness detection, fixed-width edge cutting, roughened surface corona treatment and rolling to obtain a base film;
and S3, evaporating a metal layer on the base film in a vacuum evaporation mode to obtain the thermal shock resistant metallized film.
10. The method of making a thermal shock resistant metallized film of claim 9, wherein: the thickness of the base film obtained in the step S2 is 1-10 μm.
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