Special polyethylene isolation preservative film for rubber tire and preparation method thereof

Abstract

The application discloses a special polyethylene isolation preservative film for rubber tires and a preparation method thereof, and belongs to the technical field of rubber tire manufacturing, and is used for solving the technical problem of poor self-repairing performance and ultraviolet resistance of the polyethylene isolation preservative film in the prior art, wherein the preparation method of the special polyethylene isolation preservative film for rubber tires comprises the following steps: an epoxy modified nano titanium dioxide is obtained through a grafting 2-(2,4-dihydroxyphenyl)-2H-benzotriazole reaction of the epoxy modified nano titanium dioxide and AABA; an intermediate I is obtained through a reaction of liponic acid and the modified nano titanium dioxide; the intermediate I, chlorinated polyethylene, N,N-dimethylformamide and potassium carbonate are uniformly mixed in an argon atmosphere, heated and reacted, filtered, washed and dried to obtain modified polyethylene; the prepared polyethylene isolation preservative film not only has good wear resistance and ultraviolet resistance, but also has certain self-repairing function, so that the service life of the film is prolonged, and the cost of the tire is reduced.

Description

TECHNICAL FIELD

[0001] The present application relates to the rubber tire manufacturing technology field, specifically relates to a kind of rubber tire special polyethylene separating preservative film and preparation method thereof. BACKGROUND

[0002] In the preparation process of all steel radial tire, semi steel radial tire, after the rubber and various chemical raw materials are mixed, it is isolated from air and sunlight, to avoid the influence of the oxidation layer generated on the surface of rubber on the service life of tire. People usually use separating film to bond with rubber sheet, to play the role of isolation and preservation. Commonly used separating film is polyethylene (PE), and polyethylene is thermoplastic polyolefin. The polyethylene film prepared therefrom has the advantages of transparency and excellent mechanical properties, and is widely used in industrial packaging field.

[0003] Chinese patent CN101775169A discloses a kind of polyethylene separating film for tire production, which is prepared by mixing low-density polyethylene, high-density polyethylene, ultra-low-density polyethylene, film polyethylene (methyl) acrylic acid E(M) AA copolymer, linear low-density polyethylene, plasticizer, oleic acid amide and plastic type multifunctional processing aid according to the mass ratio of (20-30):(18-20):(15-24):(10-15):(12-20):(0.5-1):(0.4-0.7):(3-5). The separating film obtained by the application has excellent isolation performance, but the ultraviolet resistance of the polyethylene separating film needs to be further strengthened. Chinese patent CN103862767B discloses a kind of polyethylene separating film for repeated use in tire production and a preparation method thereof. The polyethylene separating film for repeated use in tire production includes outer layer film, intermediate layer film and inner layer film with a mass ratio of (30-40):(20-40):(30-40). The outer layer film and the inner layer film are both prepared by mixing low-density polyethylene, linear low-density polyethylene and maleic anhydride grafted polyethylene with a mass ratio of (25-60):(25-60):(9-50). The intermediate layer film is nylon non-woven fabric, polyester or polypropylene silk screen fabric. The three-layer composite polyethylene separating film obtained by the application blocks oxygen, but the polyethylene separating film prepared by the application does not have certain self-repairing performance. In summary, it is of great market value and practical significance to develop a polyethylene separating preservative film with good self-repairing performance and ultraviolet resistance. SUMMARY

[0004] To solve the above technical problems, the present application provides a kind of rubber tire special polyethylene separating preservative film and preparation method thereof, which solves the problem of poor self-repairing performance and ultraviolet resistance of polyethylene separating preservative film.

[0005] In order to achieve the above object, the application provides a preparation method of a special polyethylene isolation preservative film for rubber tires, comprising the following steps:

[0006] Step (1) uniformly mix anhydrous ethanol, nano-titanium dioxide and γ-(2,3-epoxypropoxy) propyl trimethoxysilane, heat, react, after the reaction is completed, perform suction filtration, wash, dry, and obtain epoxy-modified nano-titanium dioxide;

[0007] Step (2) mix N,N-dimethylformamide, acetoacetyl o-carboxyaniline, 2-(2,4-dihydroxyphenyl)-2H-benzotriazole, 4-dimethylamino pyridine and 1-ethyl-(3-dimethylaminopropyl) carbonyl diimide hydrochloride, react, after the reaction is completed, wash, dry, and obtain AABA grafted 2-(2,4-dihydroxyphenyl)-2H-benzotriazole;

[0008] Step (3) add the epoxy-modified nano-titanium dioxide and the AABA grafted 2-(2,4-dihydroxyphenyl)-2H-benzotriazole into anhydrous ethanol, stir and mix, react, after the reaction is completed, perform suction filtration, wash, dry, and obtain modified nano-titanium dioxide;

[0009] Step (4) add lipoic acid into acetone, add the modified nano-titanium dioxide, stir, uniformly mix, heat, react, after the reaction is completed, perform suction filtration, wash, dry, and obtain intermediate I;

[0010] In an argon atmosphere, uniformly mix the intermediate I, chlorinated polyethylene, N,N-dimethylformamide and potassium carbonate, heat, react, after the reaction is completed, filter, wash, dry, and obtain modified polyethylene;

[0011] Step (5) the outer layer film and the inner layer film are a blend of the modified polyethylene, linear low-density polyethylene, high-density polyethylene, polyethylene wax and sodium dodecyl sulfonate; the intermediate layer film is linear low-density polyethylene; the required raw materials of the three-layer film are sent to three extruders of a three-layer co-extrusion film blowing machine, heated and melted at 200-230 DEG C; the components of each layer are stacked on the upper part of the die through the flow channels of the die, and are compounded into a co-extrusion film; the film is blown, stretched into a thin film, air-cooled, shaped, surface treated, wound, cut, packaged, and a special polyethylene isolation preservative film for rubber tires is obtained.

[0012] Preferably, the preparation method of the chlorinated polyethylene comprises the following steps:

[0013] In a closed, anhydrous and anaerobic inert gas environment, mix dimethylvinylchlorosilane and n-hexane, pass in ethylene, add triethylaluminum, heat, perform copolymerization reaction, after the reaction is completed, perform reduced pressure distillation, dry, and obtain chlorinated polyethylene.

[0014] Preferably, the copolymerization reaction is carried out at 40-45℃, 0.1-0.2MPa for 30-50min.

[0015] Preferably, the ratio of dimethylvinylchlorosilane, n-hexane, ethylene and triethylaluminum is 1.5-2.5g:20-40mL:0.8-1mol:0.4-0.6g.

[0016] Preferably, the mass ratio of anhydrous ethanol, nano-titanium dioxide and γ-(2,3-epoxypropoxy) propyl trimethoxysilane is (1400-3000):(80-100):(30-70); the reaction temperature is 55-75℃, and the reaction time is 3-5h.

[0017] Preferably, the mass ratio of N,N-dimethylformamide, acetoaceto-o-carboxyaniline, 2-(2,4-dihydroxyphenyl)-2H-benzotriazole, 4-dimethylaminopyridine and 1-ethyl-(3-dimethylaminopropyl) carbonyldiimidazole hydrochloride is (2000-4000):(80-100):(160-280):(14-26):(30-50); the reaction temperature is 10-18℃, and the reaction time is 4-8h.

[0018] Preferably, the mass ratio of epoxy-modified nano-titanium dioxide, AABA grafted 2-(2,4-dihydroxyphenyl)-2H-benzotriazole and anhydrous ethanol is (40-60):(140-260):(3000-5000); the reaction temperature is 60-80℃, and the reaction time is 2-4h.

[0019] Preferably, the mass ratio of lipoic acid, acetone and modified nano-titanium dioxide is (80-100):(1200-2400):(16-28); the reaction temperature is 90-110℃, and the reaction time is 20-28h.

[0020] Preferably, the mass ratio of intermediate I, chlorinated polyethylene, N,N-dimethylformamide and potassium carbonate is (200-280):(120-180):(2000-4000):(80-100); the reaction temperature is 55-65℃, and the reaction time is 34-46h.

[0021] Preferably, the mass ratio of modified polyethylene, linear low density polyethylene, high density polyethylene, polyethylene wax and antistatic agent is (40-80):(6-10):(12-24):(8-16):(2-6).

[0022] Preferably, the film blowing machine adopts a single screw extruder, the temperature of the extruder body is 160-220℃, the temperature of the die head is 170-230℃, and the screw rotation speed is 20-45r / min.

[0023] Preferably, the antistatic agent is one or more of fatty amine, sodium dodecyl sulfonate, glyceryl behenate.

[0024] Preferably, the blow-up ratio in the film blowing operation is 1-4.

[0025] Preferably, the stretching speed for stretching into a film is 7-21 m / min.

[0026] Preferably, the cooling line height in the air cooling setting is 0.4-0.8 m.

[0027] Preferably, the mass ratio of the outer layer film, the intermediate layer film and the inner layer film is (35-55):(20-32):(35-55).

[0028] Compared with the prior art, the present application has the following beneficial effects:

[0029] 1. In the present application, the nano-titanium dioxide has certain heat resistance, can enhance the thermal stability and mechanical properties of the base material, and under ultraviolet light irradiation, the nano-titanium dioxide can absorb and scatter ultraviolet light, and after modification of the nano-silicon dioxide, it can effectively prevent its agglomeration, so as to realize uniform dispersion and maintain the stability of the function, and the gamma-(2,3-epoxypropoxy) propyl trimethoxysilane as an organic silane can effectively improve the thermal stability due to the high strength of the silicon-oxygen bond. In the present application, the addition of 2-(2,4-dihydroxyphenyl)-2H-benzotriazole expands the absorption range of ultraviolet rays, has higher absorption efficiency, improves the anti-ultraviolet performance, and slows down aging. The acetoacetyl group (-COCH2CO-) in acetoaceto-o-carboxyaniline is a strong conjugated group, has a strong electron-withdrawing effect, and produces conjugation with the aromatic ring of the aniline group, enhancing the absorption of ultraviolet light by the molecule, especially in the ultraviolet A (UVA) and ultraviolet B (UVB) spectral range. The conjugation effect makes acetoaceto-o-carboxyaniline have stronger anti-ultraviolet performance under ultraviolet irradiation. The hydroxyl group in 2-(2,4-dihydroxyphenyl)-2H-benzotriazole reacts with the carboxyl group in acetoaceto-o-carboxyaniline to obtain AABA grafted 2-(2,4-dihydroxyphenyl)-2H-benzotriazole; the amino group in AABA grafted 2-(2,4-dihydroxyphenyl)-2H-benzotriazole undergoes ring-opening reaction with the epoxy group in the epoxy-modified titanium dioxide to obtain modified nano-titanium dioxide with a tertiary amine group; adding it to the base material can increase its heat resistance, anti-ultraviolet performance and good compatibility with the base material.

[0030] 2. In the present application, the chlorinated polyethylene obtained by copolymerization of dimethyl vinyl chlorosilane and ethylene has better heat resistance than polyethylene; the ionic bond formed between the tertiary amine group in the modified nano-titanium dioxide and the carboxyl group in thioctic acid improves the stability of thioctic acid; the hydroxyl group in intermediate I can react with the chlorine group in chlorinated polyethylene to generate ether group which is more resistant to heat and water, thereby enhancing the crosslinking degree and stability of the polymer, increasing the compatibility of intermediate I with chlorinated polyethylene, and further improving the ultraviolet resistance and self-repairing performance; intermediate I is crosslinked by hydrogen bond, disulfide bond, and ionic bond composed of carboxyl group and tertiary amine group, so that the matrix material has excellent mechanical properties; the dynamic disulfide bond, dynamic hydrogen bond, and ionic bond in thioctic acid endow the matrix material with a certain degree of self-repairing performance; and the ionic bond formed between the tertiary amine group in the modified nano-titanium dioxide and the carboxyl group in thioctic acid can be aggregated over time or under the action of heating, so that the performance of the polymer is enhanced after repair.

[0031] 3. In the present application, the rubber tire special polyethylene isolation and preservation film prepared from the modified polyethylene, linear low density polyethylene, high density polyethylene, polyethylene wax, and antistatic agent, and the intermediate layer film prepared from linear low density polyethylene has good barrier property, stability, ultraviolet resistance, tensile property, and certain self-repairing performance, so that the service life is improved when slight damage occurs, the self-repairing function can reduce the frequency of maintenance and replacement, reduce the overall cost, protect the tire surface, and maintain the freshness of the tire surface; and the application of the self-repairing technology in the tire material can enhance the safety and reliability of the tire during use. BRIEF DESCRIPTION OF DRAWINGS

[0032] Figure 1 The preparation process flow chart of the rubber tire special polyethylene isolation and preservation film in the present application;

[0033] Figure 2 The preparation process flow chart of the modified polyethylene in the present application;

[0034] Figure 3 The reaction schematic diagram of acetoaceto-o-carboxyaniline and 2-(2,4-dihydroxyphenyl)-2H-benzotriazole for preparing AABA grafted 2-(2,4-dihydroxyphenyl)-2H-benzotriazole in the present application;

[0035] Figure 4 The reaction schematic diagram of epoxy modified nano-titanium dioxide and AABA grafted 2-(2,4-dihydroxyphenyl)-2H-benzotriazole for preparing modified nano-titanium dioxide in the present application;

[0036] Figure 5 The column chart of the ultraviolet resistance test results of examples 1-5 and comparative examples 1-3 in the present application;

[0037] Figure 6 Repair test column chart for example 1 and comparative examples 1-3 in the present application. DETAILED DESCRIPTION

[0038] The technical solutions of the present application will be clearly and completely described below in combination with examples. Obviously, the described examples are only some of the examples of the present application, but not all the examples. Based on the examples in the present application, all the other examples obtained by those skilled in the art without creative labor are within the protection scope of the present application.

[0039] Example 1

[0040] The present embodiment provides a preparation method of a special polyethylene isolation preservative film for rubber tires, comprising the following steps:

[0041] Step (1) uniformly mix anhydrous ethanol, nano-titanium dioxide and γ-(2,3-epoxypropoxy) propyl trimethoxysilane according to a mass ratio of 1400:80:30, react at a temperature of 55℃ for 5h, after the reaction is completed, perform suction filtration, wash with deionized water, and dry at a temperature of 60℃ for 6h to obtain epoxy-modified nano-titanium dioxide;

[0042] Step (2) mix N,N-dimethylformamide, acetoaceto-o-carboxyaniline, 2-(2,4-dihydroxyphenyl)-2H-benzotriazole, 4-dimethylamino pyridine and 1-ethyl-(3-dimethylaminopropyl) carbonyl diimide hydrochloride according to a mass ratio of 2000:80:160:14:30, react at a temperature of 10℃ for 8h, after the reaction is completed, wash with anhydrous ethanol, and dry at a temperature of 30℃ for 4h to obtain AABA grafted 2-(2,4-dihydroxyphenyl)-2H-benzotriazole;

[0043] Step (3) mix the epoxy-modified nano-titanium dioxide, the AABA grafted 2-(2,4-dihydroxyphenyl)-2H-benzotriazole and anhydrous ethanol according to a mass ratio of 40:140:3000, stir at a rotating speed of 120r / min for 18min, react at a temperature of 60℃ for 4h, after the reaction is completed, perform suction filtration, wash with anhydrous ethanol, and dry at a temperature of 80℃ for 5h to obtain modified nano-titanium dioxide;

[0044] Step (4) mix thioctic acid, acetone and the modified nano-titanium dioxide according to a mass ratio of 80:1200:16, stir at a rotating speed of 100r / min for 20min, react at a temperature of 90℃ for 28h, after the reaction is completed, perform suction filtration, wash with anhydrous ethanol, and dry to obtain intermediate I;

[0045] Mixing intermediate I, chlorinated polyethylene, N,N-dimethylformamide and potassium carbonate uniformly according to the mass ratio of 200:120:2000:80, reacting for 46h at the temperature of 55℃, filtering, washing with deionized water, and drying at the temperature of 40℃ for 4.5h to obtain the modified polyethylene;

[0046] The outer layer film and the inner layer film are a blend of modified polyethylene, linear low density polyethylene, high density polyethylene, polyethylene wax and sodium dodecyl sulfonate; the intermediate layer film is linear low density polyethylene; the required raw materials for the three-layer film are fed into three extruders of a three-layer co-extrusion film blowing machine and heated and melted at 200℃; a single screw extruder is used, the temperature of the extruder body is 160℃, the temperature of the die head is 170℃, the screw rotation speed is 45r / min, the components of each layer are laminated on the upper part of the die head through the flow channels of the die head, and the co-extrusion film is compounded; the film is stretched into a thin film at a stretching speed of 7m / min according to a blowing ratio of 1; air cooling is used for shaping, the height of the cooling line is 0.4m; the surface of the cooled film is subjected to corona treatment, the treatment current is 150A, the maximum output power is 12kW, the film is wound, cut and packaged to obtain a rubber tire special polyethylene isolation preservative film with a thickness of 90μm;

[0047] The modified polyethylene, linear low density polyethylene, high density polyethylene, polyethylene wax and sodium dodecyl sulfonate in the outer layer film and the inner layer film are mixed uniformly according to the mass ratio of 40:6:12:8:2.

[0048] The mass ratio of the outer layer film, the intermediate layer film and the inner layer film is 35:20:35.

[0049] Example 2

[0050] The embodiment provides a preparation method of a rubber tire special polyethylene isolation preservative film, which comprises the following steps:

[0051] Mixing anhydrous ethanol, nano-titanium dioxide and γ-(2,3-epoxypropoxy) propyl trimethoxysilane uniformly according to the mass ratio of 1800:85:40, reacting for 4.5h at the temperature of 60℃, filtering, washing with deionized water, and drying at the temperature of 65℃ for 5.5h to obtain epoxy-modified nano-titanium dioxide.

[0052] Step (2) N,N-dimethylformamide, acetoacetyl-o-carboxyaniline, 2-(2,4-dihydroxyphenyl)-2H-benzotriazole, 4-dimethylamino pyridine and 1-ethyl-(3-dimethylamino propyl) carbodiimide hydrochloride were mixed in a mass ratio of 2500:85:190:17:35, reacted for 7 h at a temperature of 12°C, washed with anhydrous ethanol, and dried at a temperature of 35°C for 3.5 h to obtain AABA grafted 2-(2,4-dihydroxyphenyl)-2H-benzotriazole;

[0053] Step (3) The modified nano-titanium dioxide, AABA grafted 2-(2,4-dihydroxyphenyl)-2H-benzotriazole and anhydrous ethanol were mixed in a mass ratio of 45:170:3500, stirred at a speed of 135 r / min for 16 min, reacted for 3.5 h at a temperature of 65°C, filtered, washed with anhydrous ethanol, and dried at a temperature of 85°C for 4.5 h to obtain the modified nano-titanium dioxide;

[0054] Step (4) The lipoic acid, acetone and the modified nano-titanium dioxide were mixed in a mass ratio of 85:1500:19, stirred at a speed of 115 r / min for 18 min, reacted for 26 h at a temperature of 95°C, filtered, washed with anhydrous ethanol, and dried to obtain intermediate I;

[0055] In an argon atmosphere, the intermediate I, chlorinated polyethylene, N,N-dimethylformamide and potassium carbonate were mixed uniformly in a mass ratio of 220:135:2500:85, reacted for 43 h at a temperature of 57°C, filtered, washed with deionized water, and dried at a temperature of 45°C for 4 h to obtain the modified polyethylene;

[0056] Step (5) The outer layer film and the inner layer film are a blend of the modified polyethylene, linear low density polyethylene, high density polyethylene, polyethylene wax and sodium dodecyl sulfonate; the intermediate layer film is linear low density polyethylene; the raw materials for the three-layer film are fed into three extruders of a three-layer co-extrusion film blowing machine and heated and melted at 207°C; a single screw extruder is used, the temperature of the extruder body is 175°C, the temperature of the die head is 185°C, the screw rotation speed is 39 r / min, the components of each layer are combined layer by layer on the upper part of the die head through the flow channels of the die head to form a co-extruded film; the film is blown at a blowing ratio of 1 and stretched into a film at a stretching speed of 11 m / min; air cooling is used for shaping, the height of the cooling line is 0.5 m; the surface of the cooled film is subjected to corona treatment, the treatment current is 160 A, the maximum output power is 14 kW, the film is wound, cut and packaged to obtain a polyethylene isolation and preservation film for rubber tires with a thickness of 90 μm;

[0057] The modified polyethylene, the linear low density polyethylene, the high density polyethylene, the polyethylene wax and the sodium dodecyl sulfonate in the outer layer film and the inner layer film are in a mass ratio of 50:7:15:10:3.

[0058] The mass ratio of the outer layer film, the middle layer film and the inner layer film is 40:23:40.

[0059] Embodiment 3

[0060] The embodiment provides a preparation method of a special polyethylene isolation preservative film for rubber tires.

[0061] Step (1) uniformly mix anhydrous ethanol, nano titanium dioxide and γ-(2,3-epoxypropoxy) propyl trimethoxysilane according to a mass ratio of 2200:90:50, react at 65 DEG C for 4h, after the reaction, perform suction filtration, wash with deionized water, and dry at 70 DEG C for 5h to obtain epoxy-modified nano titanium dioxide.

[0062] Step (2) mix N,N-dimethylformamide, acetoacetyl o-carboxyaniline, 2-(2,4-dihydroxyphenyl)-2H-benzotriazole, 4-dimethylamino pyridine and 1-ethyl-(3-dimethylaminopropyl) carbonyl diimide hydrochloride according to a mass ratio of 3000:90:220:20:40, react at 14 DEG C for 6h, after the reaction, wash with anhydrous ethanol, and dry at 40 DEG C for 3h to obtain AABA grafted 2-(2,4-dihydroxyphenyl)-2H-benzotriazole.

[0063] Step (3) mix the epoxy-modified nano titanium dioxide, the AABA grafted 2-(2,4-dihydroxyphenyl)-2H-benzotriazole and anhydrous ethanol according to a mass ratio of 50:200:4000, stir at a rotating speed of 150 r / min for 14 min, react at 70 DEG C for 3h, after the reaction, perform suction filtration, wash with anhydrous ethanol, and dry at 90 DEG C for 4h to obtain modified nano titanium dioxide.

[0064] Step (4) mix thioctic acid, acetone and the modified nano titanium dioxide according to a mass ratio of 90:1800:22, stir at a rotating speed of 130 r / min for 16 min, react at 100 DEG C for 24h, after the reaction, perform suction filtration, wash with anhydrous ethanol, and dry to obtain intermediate I.

[0065] In an argon atmosphere, uniformly mix the intermediate I, chlorinated polyethylene, N,N-dimethylformamide and potassium carbonate according to a mass ratio of 240:150:3000:90, react at 60 DEG C for 40h, after the reaction, perform filtration, wash with deionized water, and dry at 50 DEG C for 3.5h to obtain modified polyethylene.

[0066] Step (5) the outer layer film and the inner layer film are a blend of modified polyethylene, linear low density polyethylene, high density polyethylene, polyethylene wax and sodium dodecyl sulfonate; the intermediate layer film is linear low density polyethylene, the raw materials required for the three-layer film are fed into three extruders of a three-layer co-extrusion film blowing machine, heated and melted at 215℃; a single screw extruder is used, the temperature of the extruder body is 190℃, the temperature of the die head is 200℃, the screw rotation speed is 32r / min, the components of each layer are superimposed on the upper part of the die head through the flow channels of the die head, and are compounded into a co-extrusion film; the film is stretched into a thin film at a stretching speed of 14m / min according to a blowing ratio of 2; air cooling is used for shaping, the height of the cooling line is 0.6m; the surface of the cooled film is treated by corona discharge, the treatment current is 170A, the maximum output power is 16kW, the film is wound, cut and packaged, and a polyethylene isolation preservative film with a thickness of 90μm for rubber tires is obtained;

[0067] wherein the modified polyethylene, the linear low density polyethylene, the high density polyethylene, the polyethylene wax and the sodium dodecyl sulfonate in the outer layer film and the inner layer film are in a mass ratio of 60:8:18:12:4;

[0068] wherein the mass ratio of the outer layer film, the intermediate layer film and the inner layer film is 45:26:45.

[0069] Example 4

[0070] The embodiment provides a preparation method of a polyethylene isolation preservative film for rubber tires, comprising the following steps:

[0071] Step (1) uniformly mix anhydrous ethanol, nano-titanium dioxide and γ-(2,3-epoxypropoxy) propyl trimethoxysilane according to a mass ratio of 2600:95:60, react at 70℃ for 3.5h, after the reaction is completed, perform suction filtration, wash with deionized water, and dry at 75℃ for 4.5h to obtain epoxy-modified nano-titanium dioxide;

[0072] Step (2) mix N,N-dimethylformamide, acetoaceto-o-carboxyaniline, 2-(2,4-dihydroxyphenyl)-2H-benzotriazole, 4-dimethylamino pyridine and 1-ethyl-(3-dimethylaminopropyl) carbonyl diimide hydrochloride according to a mass ratio of 3500:95:250:23:45, react at 16℃ for 5h, after the reaction is completed, perform anhydrous ethanol washing, and dry at 45℃ for 2.5h to obtain AABA grafted 2-(2,4-dihydroxyphenyl)-2H-benzotriazole;

[0073] Step (3) the epoxy modified nano titanium dioxide, AABA grafted 2-(2,4-dihydroxyphenyl)-2H-benzotriazole and anhydrous ethanol are mixed in a mass ratio of 55:230:4500, stirred at a speed of 165 r / min for 12 min, and reacted at a temperature of 75℃ for 2.5 h. After the reaction is completed, filtration is performed, anhydrous ethanol is used for washing, and drying is performed at a temperature of 95℃ for 3.5 h to obtain modified nano titanium dioxide;

[0074] Step (4) lipoic acid, acetone and modified nano titanium dioxide are mixed in a mass ratio of 95:2100:25, stirred at a speed of 145 r / min for 14 min, and reacted at a temperature of 105℃ for 22 h. After the reaction is completed, filtration is performed, anhydrous ethanol is used for washing, and drying is performed to obtain intermediate I;

[0075] In an argon atmosphere, intermediate I, chlorinated polyethylene, N,N-dimethylformamide and potassium carbonate are uniformly mixed in a mass ratio of 260:165:3500:95, and reacted at a temperature of 63℃ for 37 h. After the reaction is completed, filtration is performed, deionized water is used for washing, and drying is performed at a temperature of 55℃ for 3 h to obtain modified polyethylene;

[0076] Step (5) the outer layer film and the inner layer film are a blend of modified polyethylene, linear low-density polyethylene, high-density polyethylene, polyethylene wax and sodium dodecyl sulfonate; the intermediate layer film is linear low-density polyethylene. The raw materials required for the three-layer film are fed into three extruders of a three-layer co-extrusion film blowing machine and heated and melted at 223℃. A single-screw extruder is used, the temperature of the extruder body is 205℃, the temperature of the die head is 215℃, the screw rotation speed is 26 r / min, and the components of each layer are combined layer by layer on the upper part of the die head through the flow channels of the die head to form a co-extruded film. The film is stretched into a thin film at a stretching speed of 17 m / min according to a blowing ratio of 3. Air cooling is used for shaping, and the height of the cooling line is 0.7 m. The surface of the cooled film is subjected to corona treatment, the treatment current is 190 A, the maximum output power is 18 kW, the film is wound, cut and packaged to obtain a polyethylene isolation and preservation film for rubber tires with a thickness of 90 μm;

[0077] In the outer layer film and the inner layer film, the mass ratio of modified polyethylene, linear low-density polyethylene, high-density polyethylene, polyethylene wax and sodium dodecyl sulfonate is 70:9:21:14:5;

[0078] In the outer layer film, the intermediate layer film and the inner layer film, the mass ratio is 50:29:50.

[0079] Example 5

[0080] The embodiment provides a preparation method of a polyethylene isolation and preservation film for rubber tires, which comprises the following steps:

[0081] Step (1) anhydrous ethanol, nano-titanium dioxide, γ-(2,3-epoxypropoxy) propyl trimethoxysilane were mixed uniformly according to the mass ratio of 3000:100:70, and reacted at 75°C for 3h. After the reaction was completed, the mixture was filtered, washed with deionized water, and dried at 80°C for 4h to obtain epoxy-modified nano-titanium dioxide;

[0082] Step (2) N,N-dimethylformamide, acetoacetyl-o-carboxyaniline, 2-(2,4-dihydroxyphenyl)-2H-benzotriazole, 4-dimethylamino pyridine and 1-ethyl-(3-dimethylaminopropyl) carbonyl diimide hydrochloride were mixed according to the mass ratio of 4000:100:280:26:50, and reacted at 18°C for 4h. After the reaction was completed, the mixture was washed with anhydrous ethanol, and dried at 50°C for 2h to obtain AABA grafted 2-(2,4-dihydroxyphenyl)-2H-benzotriazole;

[0083] Step (3) epoxy-modified nano-titanium dioxide, AABA grafted 2-(2,4-dihydroxyphenyl)-2H-benzotriazole and anhydrous ethanol were mixed according to the mass ratio of 60:260:5000, stirred at a speed of 180r / min for 10min, and reacted at 80°C for 2h. After the reaction was completed, the mixture was filtered, washed with anhydrous ethanol, and dried at 100°C for 3h to obtain modified nano-titanium dioxide;

[0084] Step (4) lipoic acid, acetone and modified nano-titanium dioxide were mixed according to the mass ratio of 100:2400:28, stirred at a speed of 160r / min for 12min, and reacted at 110°C for 20h. After the reaction was completed, the mixture was filtered, washed with anhydrous ethanol, and dried to obtain intermediate I;

[0085] In an argon atmosphere, intermediate I, chlorinated polyethylene, N,N-dimethylformamide and potassium carbonate were mixed uniformly according to the mass ratio of 280:180:4000:100, and reacted at 65°C for 34h. After the reaction was completed, the mixture was filtered, washed with deionized water, and dried at 60°C for 2.5h to obtain modified polyethylene;

[0086] Step (5) the outer layer film and the inner layer film are a blend of modified polyethylene, linear low density polyethylene, high density polyethylene, polyethylene wax and sodium dodecyl sulfonate; the intermediate layer film is linear low density polyethylene, the raw materials required for the three-layer film are fed into three extruders of a three-layer co-extrusion film blowing machine, heated and melted at 230 DEG C; a single screw extruder is used, the temperature of the extruder body is 220 DEG C, the temperature of the die head is 230 DEG C, the screw rotation speed is 20 r / min, the components of each layer are superimposed on the upper part of the die head through the flow channels of the die head, and are compounded into a co-extrusion film; the film is stretched into a thin film at a stretching speed of 21 m / min according to a blowing ratio of 4; air cooling is used for shaping, and the height of the cooling line is 0.8 m; the surface of the cooled film is treated by corona discharge, the treatment current is 200 A, the maximum output power is 20 kW, the film is wound, cut and packaged, and a polyethylene isolation preservative film with a thickness of 90 μm for rubber tires is obtained;

[0087] wherein the modified polyethylene, the linear low density polyethylene, the high density polyethylene, the polyethylene wax and the sodium dodecyl sulfonate in the outer layer film and the inner layer film are in a mass ratio of 80:10:24:16:6;

[0088] wherein the mass ratio of the outer layer film, the intermediate layer film and the inner layer film is 55:32:55.

[0089] Example 6

[0090] The embodiment provides a preparation method of chlorinated polyethylene, comprising the following steps:

[0091] In a closed, waterless, oxygenless and inert gas environment, dimethyl vinyl chlorosilane and n-hexane are mixed, ethylene is introduced, triethyl aluminum is added, and copolymerization is carried out at 40 DEG C and 0.1 MPa for 50 min; after the reaction is completed, the temperature is reduced to 55 DEG C under reduced pressure, and distillation is carried out for 6 h; and then drying is carried out at 40 DEG C for 8 h to obtain chlorinated polyethylene.

[0092] wherein the amount ratio of dimethyl vinyl chlorosilane, n-hexane, ethylene and triethyl aluminum is 1.5 g:20 mL:0.8 mol:0.4 g.

[0093] Comparative Example 1

[0094] The comparative example provides a preparation method of a polyethylene isolation preservative film for rubber tires, comprising the following steps:

[0095] Step (1) dehydrated ethanol, nano titanium dioxide and gamma-(2,3-epoxypropoxy) propyl trimethoxysilane are uniformly mixed in a mass ratio of 1400:80:30, and then reacted at 55 DEG C for 5 h; after the reaction is completed, filtration is carried out, and then washing is carried out with deionized water; and then drying is carried out at 60 DEG C for 6 h to obtain epoxy-modified nano titanium dioxide.

[0096] Step (2) N,N-dimethylformamide, acetoacetyl-o-carboxyaniline, 2-(2,4-dihydroxyphenyl)-2H-benzotriazole, 4-dimethylamino pyridine and 1-ethyl-(3-dimethylamino propyl) carbodiimide hydrochloride were mixed in a mass ratio of 2000:80:160:14:30, reacted for 8h at a temperature of 10℃, washed with anhydrous ethanol, and dried for 4h at a temperature of 30℃ to obtain AABA grafted 2-(2,4-dihydroxyphenyl)-2H-benzotriazole;

[0097] Step (3) The modified nanometer titanium dioxide, AABA grafted 2-(2,4-dihydroxyphenyl)-2H-benzotriazole and anhydrous ethanol were mixed in a mass ratio of 40:140:3000, stirred at a speed of 120r / min for 18min, reacted for 4h at a temperature of 60℃, filtered, washed with anhydrous ethanol, and dried for 5h at a temperature of 80℃ to obtain the modified nanometer titanium dioxide;

[0098] Step (4) The lipoic acid, acetone and the modified nanometer titanium dioxide were mixed in a mass ratio of 80:1200:16, stirred at a speed of 100r / min for 20min, reacted for 28h at a temperature of 90℃, filtered, washed with anhydrous ethanol, and dried to obtain intermediate I;

[0099] In an argon atmosphere, the intermediate I, polyethylene and N,N-dimethylformamide were physically mixed uniformly in a mass ratio of 200:120:2080, washed with deionized water, and dried for 4.5h at a temperature of 40℃ to obtain the modified polyethylene;

[0100] Step (5) The outer layer film and the inner layer film were a blend of the modified polyethylene, linear low density polyethylene, high density polyethylene, polyethylene wax and sodium dodecyl sulfonate; the intermediate layer film was linear low density polyethylene; the raw materials for the three-layer film were fed into three extruders of a three-layer co-extrusion film blowing machine and heated and melted at 200℃; a single screw extruder was used, the temperature of the extruder body was 160℃, the temperature of the die head was 170℃, the screw rotation speed was 45r / min, and the components of each layer were combined layer by layer on the upper part of the die head through the flow channels of the die head to form a co-extrusion film; the film was stretched into a thin film at a stretching speed of 7m / min according to a blowing ratio of 1; air cooling was used for shaping, and the height of the cooling line was 0.4m; the surface of the cooled film was subjected to corona treatment, the treatment current was 150A, the maximum output power was 12kW, the film was wound, cut and packaged to obtain a rubber tire special polyethylene isolation and preservation film with a thickness of 90μm;

[0101] In the outer layer film and the inner layer film, the modified polyethylene, linear low density polyethylene, high density polyethylene, polyethylene wax and sodium dodecyl sulfonate were in a mass ratio of 40:6:12:8:2;

[0102] The mass ratio of the outer layer film, the intermediate layer film and the inner layer film is 35:20:35.

[0103] Comparative Example 2

[0104] The present comparative example provides a preparation method of a special polyethylene preservative film for rubber tires, comprising the following steps:

[0105] Step (1) uniformly mix anhydrous ethanol, nano-titanium dioxide and γ-(2,3-epoxypropoxy) propyl trimethoxysilane according to a mass ratio of 1400:80:30, react at a temperature of 55°C for 5h, after the reaction is completed, perform suction filtration, wash with deionized water, and dry at a temperature of 60°C for 6h to obtain epoxy-modified nano-titanium dioxide;

[0106] Step (2) mix N,N-dimethylformamide, acetoaceto-o-carboxyaniline, 2-(2,4-dihydroxyphenyl)-2H-benzotriazole, 4-dimethylamino pyridine and 1-ethyl-(3-dimethylaminopropyl) carbonyl diimide hydrochloride according to a mass ratio of 2000:80:160:14:30, react at a temperature of 10°C for 8h, after the reaction is completed, wash with anhydrous ethanol, and dry at a temperature of 30°C for 4h to obtain AABA grafted 2-(2,4-dihydroxyphenyl)-2H-benzotriazole;

[0107] Step (3) mix the epoxy-modified nano-titanium dioxide, the AABA grafted 2-(2,4-dihydroxyphenyl)-2H-benzotriazole and anhydrous ethanol according to a mass ratio of 40:140:3000, stir at a rotation speed of 120r / min for 18min, react at a temperature of 60°C for 4h, after the reaction is completed, perform suction filtration, wash with anhydrous ethanol, and dry at a temperature of 80°C for 5h to obtain modified nano-titanium dioxide;

[0108] Step (4) mix thioctic acid, the modified nano-titanium dioxide, polyethylene and N,N-dimethylformamide according to a mass ratio of 166:34:120:2080, stir at a rotation speed of 100r / min for 20min, wash with deionized water, and dry at a temperature of 40°C for 4.5h to obtain modified polyethylene;

[0109] Step (5) the outer layer film and the inner layer film are a blend of modified polyethylene, linear low density polyethylene, high density polyethylene, polyethylene wax and sodium dodecyl sulfonate; the intermediate layer film is linear low density polyethylene, the raw materials required for the three-layer film are fed into three extruders of a three-layer co-extrusion film blowing machine, heated and melted at 200℃; a single screw extruder is used, the temperature of the extruder body is 160℃, the temperature of the die head is 170℃, the screw rotation speed is 45r / min, the components of each layer are laminated on the upper part of the die head through the flow channels of the die head, and are compounded into a co-extrusion film; the film is stretched into a thin film at a stretching speed of 7m / min according to a blowing ratio of 1; air cooling is used for shaping, and the cooling line height is 0.4m; the surface of the cooled film is treated by corona discharge, the treatment current is 150A, the maximum output power is 12kW, the film is wound, cut and packaged, and a polyethylene isolation preservative film with a thickness of 90μm for rubber tires is obtained;

[0110] wherein the modified polyethylene, the linear low density polyethylene, the high density polyethylene, the polyethylene wax and the sodium dodecyl sulfonate in the outer layer film and the inner layer film are in a mass ratio of 40:6:12:8:2;

[0111] wherein the mass ratio of the outer layer film, the intermediate layer film and the inner layer film is 35:20:35.

[0112] Comparative Example 3

[0113] The present comparative example provides a preparation method of a polyethylene isolation preservative film for rubber tires, comprising the following steps:

[0114] Step (1) N,N-dimethylformamide, acetoacetyl-o-carboxyaniline, 2-(2,4-dihydroxyphenyl)-2H-benzotriazole, 4-dimethylamino pyridine and 1-ethyl-(3-dimethylaminopropyl) carbonyl diimide hydrochloride are mixed in a mass ratio of 2000:80:160:14:30, reacted at a temperature of 10℃ for 8h, washed with anhydrous ethanol, and dried at a temperature of 30℃ for 4h to obtain AABA grafted 2-(2,4-dihydroxyphenyl)-2H-benzotriazole;

[0115] Step (2) lipoic acid, AABA grafted 2-(2,4-dihydroxyphenyl)-2H-benzotriazole, polyethylene and N,N-dimethylformamide are mixed in a mass ratio of 166:26:120:2088, stirred at a rotation speed of 100r / min for 20min, washed with deionized water, and dried at a temperature of 40℃ for 4.5h to obtain modified polyethylene;

[0116] Step (3) the outer layer film and the inner layer film are a blend of modified polyethylene, linear low density polyethylene, high density polyethylene, polyethylene wax and sodium dodecyl sulfonate; the intermediate layer film is linear low density polyethylene, the raw materials required for the three-layer film are sent to three extruders of a three-layer co-extrusion film blowing machine, heated and melted at 200 DEG C; a single screw extruder is used, the temperature of the extruder body is 160 DEG C, the temperature of the die head is 170 DEG C, the screw rotation speed is 45 r / min, the components of each layer are laminated on the upper part of the die head through the flow channels of the die head, and are compounded into a co-extruded film; the film is stretched into a thin film at a stretching speed of 7 m / min according to a blowing ratio of 1; air cooling is used for shaping, the height of the cooling line is 0.4 m; the surface of the cooled film is treated by corona discharge, the treatment current is 150 A, the maximum output power is 12 kW, the film is wound, cut and packaged, and a polyethylene isolation preservative film with a thickness of 90 μm for rubber tires is obtained;

[0117] In the outer layer film and the inner layer film, the modified polyethylene, the linear low density polyethylene, the high density polyethylene, the polyethylene wax and the sodium dodecyl sulfonate are in a mass ratio of 40:6:12:8:2;

[0118] The mass ratio of the outer layer film, the intermediate layer film and the inner layer film is 35:20:35.

[0119] The chlorinated polyethylene used in Examples 1-5 is prepared by the method of Example 6.

[0120] In the examples and comparative examples, the linear low density polyethylene (LLDPE) is purchased from SINOPEC Yangzi Petrochemical Co., Ltd., with a brand name of DFDA-7042 and a melt index of 2.2 g / 10 min and a density of 0.92 g / cm 3 ; the high density polyethylene is from Shandong Guangchuan Plastic Co., Ltd., with a product number of 2911; the polyethylene wax is from Shanghai Zhenli Shu Network Technology Co., Ltd., with a product name of AC-629A; the sodium dodecyl sulfonate is from Guangzhou Jishengxiang Chemical Co., Ltd., with a product number of 55442 and a CAS number of 2386-53-0; the nano titanium dioxide is purchased from Xuancheng Jingrui New Material Co., Ltd., with a model number of JR05 and an average particle size of 5 nm; the acetoaceto-o-carboxyaniline (AABA) is from Shanghai Liming Chemical Co., Ltd., with a model number of 565754 and a content of 99%; the lipoic acid is from Xi'an Xinmengchen Biological Technology Co., Ltd., with a single product number of 23; and the others are commercially available products.

[0121] The polyethylene isolation preservative film for rubber tires prepared in Examples 1-5 and Comparative Examples 1-3 is subjected to corresponding tests, and the test results are shown as follows:

[0122] (1) Anti-ultraviolet performance test: a UV-3600 spectrophotometer from Shimadzu, Japan was used for the test, and the test was performed in accordance with the national standard GB / T 2680-2021, and the test results are shown in Table 1.

[0123] Table 1

[0124]

[0125] As can be seen from the test results in Table 1, the rubber tire special polyethylene isolation preservative film corresponding to Examples 1-5 has excellent ultraviolet absorption performance, the added nano titanium dioxide itself has a certain ultraviolet absorption performance, the higher the content, the better the dispersion performance, and the ultraviolet absorption performance is more outstanding; the introduced 2-(2,4-dihydroxyphenyl)-2H-benzotriazole also has excellent ultraviolet absorption performance, increases the ultraviolet absorption range, and improves the absorption efficiency. In Example 1, the hydroxyl group contained in intermediate I reacts with the chlorine group in chlorinated polyethylene to form an ether bond that is more resistant to water and heat, and has better thermal stability. At the same time, intermediate I has better compatibility with the matrix material, which is more conducive to ultraviolet absorption performance. In Comparative Example 1, intermediate I and polyethylene are physically mixed, and the dispersion is not as good as that of Example 1, so the anti-ultraviolet performance of Comparative Example 1 is lower than that of Example 1. In Comparative Example 1, the thioctic acid and the tertiary amine group in the modified nano titanium dioxide form an ionic bond for crosslinking, which gives it excellent mechanical properties. In addition, the dynamic disulfide bond and ionic bond contained in intermediate I give the matrix material certain self-repairing ability. Once it is missing, the anti-ultraviolet performance naturally decreases due to the decrease in repairability, so the anti-ultraviolet performance of Comparative Example 2 is lower than that of Comparative Example 1. Comparative Example 3 lacks nano titanium dioxide compared to Comparative Example 2, so its anti-ultraviolet performance naturally decreases.

[0126] (2) Mechanical property test: the mechanical properties of the rubber tire special polyethylene isolation preservative film in Examples 1 and Comparative Examples 1-3 were tested in accordance with the test standard GB / T 1040.3-2006 "Determination of tensile properties of plastics - Part 3: test conditions for films and sheets"; each was tested three times, and the test results are shown in Table 2.

[0127] Table 2

[0128]

[0129] As shown in Table 2, the tensile strength of the rubber tire special polyethylene isolation preservative film prepared in Example 1 of the present application is 30.8 MPa. In Comparative Example 1, the intermediate I and the chlorinated polyethylene are connected by ether bond, and the thermal stability of the modified polyethylene obtained thereby is further improved. The nitrogen atoms and oxygen atoms contained therein are prone to form hydrogen bonds, and the internal crosslinking is increased, and the tensile strength is increased. Conversely, the tensile strength is reduced. Therefore, the tensile strength of Comparative Example 1 is lower than that of Example 1. In Comparative Example 2, compared with Comparative Example 1, the thioctic acid and the modified nano titanium dioxide are not used to form ionic bonds for crosslinking, and the degree of internal crosslinking is lower, and the tensile strength is reduced. In Comparative Example 3, compared with Comparative Example 2, the inorganic nano titanium dioxide is not used, and therefore the tensile strength of Comparative Example 3 is lower than that of Comparative Example 2.

[0130] (3) Repair performance test: the rubber tire special polyethylene isolation preservative film in Example 1 and Comparative Examples 1-3 is scratched with a razor blade, the scratch width is 10 μm, and the scratch penetrates into the tinplate substrate. Then, the scratched rubber tire special polyethylene isolation preservative film is placed in an oven at a temperature of 75°C for self-repairing for 24 h, and then taken out from the oven, and the rubber tire special polyethylene isolation preservative film is naturally cooled to room temperature. Each group is tested three times, and the repair rate is recorded, and the average value is taken. The specific test results are shown in Table 3.

[0131] Table 3

[0132]

[0133] As shown in Table 3, the repair rate of the rubber tire special polyethylene isolation preservative film in Example 1 reaches 96.25%. In Example 1, the intermediate I and the chlorinated polyethylene are connected by ether bond, and the compatibility of the two is good, and the intermediate I with repair performance can play a role. Once the dispersibility is reduced, the repair performance is reduced, and therefore the repair performance of Comparative Example 1 is lower than that of Example 1. In Comparative Example 2, compared with Comparative Example 1, the thioctic acid exists in a metastable state, and due to the reverse ring-closing depolymerization, the compatibility of the base material is poor, and the tertiary amine group in the thioctic acid and the modified nano titanium dioxide does not form ionic bonds, and the repair performance is reduced, and therefore the repair rate value in Comparative Example 2 is lower than that in Comparative Example 1. In Comparative Example 3, compared with Comparative Example 2, the stability and dispersibility of the thioctic acid are reduced, and the repair performance is reduced, and therefore the repair performance in Comparative Example 3 is lower than that in Comparative Example 2.

[0134] Although the embodiments of the present application have been shown and described, it should be understood by those skilled in the art that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of the present application, and any equivalent changes and improvements made within the scope of the present application should still fall within the scope of the present application.

Claims

1. A method for preparing a polyethylene insulating and preservative film specifically for rubber tires, characterized in that, Includes the following steps: Step (1) Mix anhydrous ethanol, nano titanium dioxide and γ-(2,3-epoxypropoxy)propyltrimethoxysilane evenly, heat, react, filter, wash and dry to obtain epoxy-modified nano titanium dioxide. Step (2) N,N-dimethylformamide, acetoacetyl-o-carboxyaniline, 2-(2,4-dihydroxyphenyl)-2H-benzotriazole, 4-dimethylaminopyridine and 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride were mixed and reacted. After the reaction was completed, the mixture was washed and dried to obtain AABA-grafted 2-(2,4-dihydroxyphenyl)-2H-benzotriazole. Step (3) Epoxy-modified nano-titanium dioxide and AABA-grafted 2-(2,4-dihydroxyphenyl)-2H-benzotriazole were added to anhydrous ethanol, stirred and mixed, reacted, and after the reaction was completed, filtered, washed and dried to obtain modified nano-titanium dioxide. Step (4) Add lipoic acid to acetone, add modified nano titanium dioxide, stir, mix evenly, heat, react, after the reaction is completed, filter, wash, dry, and obtain intermediate I; In an argon atmosphere, intermediate I, chlorinated polyethylene, N,N-dimethylformamide and potassium carbonate are mixed evenly, heated and reacted. After the reaction is completed, the mixture is filtered, washed and dried to obtain modified polyethylene. Step (5) The outer and inner layers are a blend of modified polyethylene, linear low-density polyethylene, high-density polyethylene, polyethylene wax and antistatic agent; the middle layer is linear low-density polyethylene. The raw materials required for the three-layer film are sent to the three extruders of the three-layer co-extrusion blown film machine and heated and melted at 200-230℃. Each layer component is stacked layer by layer on the upper part of the die through each flow channel of the die head to form a co-extruded film. The film is blown, stretched into a thin film, air-cooled and shaped, surface treated, rolled up, cut and packaged to obtain a polyethylene isolation and preservation film for rubber tires. The preparation method of chlorinated polyethylene includes the following steps: In a closed, anhydrous, and oxygen-free inert gas environment, dimethylvinylchlorosilane and n-hexane were mixed, ethylene was introduced, triethylaluminum was added, and the mixture was heated to carry out a copolymerization reaction. After the reaction was completed, the mixture was distilled under reduced pressure and dried to obtain chlorinated polyethylene.

2. The method for preparing a polyethylene insulating and preservative film for rubber tires according to claim 1, characterized in that, The copolymerization reaction was carried out at 40-45℃ and 0.1-0.2MPa for 30-50 minutes.

3. The method for preparing a polyethylene insulating and preservative film for rubber tires according to claim 1, characterized in that, The mass ratio of anhydrous ethanol, nano-titanium dioxide, and γ-(2,3-epoxypropoxy)propyltrimethoxysilane was (1400-3000):(80-100):(30-70); the reaction temperature was 55-75℃, and the reaction time was 3-5h.

4. The method for preparing a polyethylene insulating and preservative film for rubber tires according to claim 1, characterized in that, The mass ratio of N,N-dimethylformamide, acetoacetyl-o-carboxyaniline, 2-(2,4-dihydroxyphenyl)-2H-benzotriazole, 4-dimethylaminopyridine, and 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride is (2000-4000):(80-100):(160-280):(14-26):(30-50); the reaction temperature is 10-18℃, and the reaction time is 4-8h.

5. The method for preparing a polyethylene insulating and preservative film for rubber tires according to claim 1, characterized in that, The mass ratio of epoxy-modified nano-titanium dioxide, AABA-grafted 2-(2,4-dihydroxyphenyl)-2H-benzotriazole, and anhydrous ethanol was (40-60):(140-260):(3000-5000); the reaction temperature was 60-80℃, and the reaction time was 2-4h.

6. The method for preparing a polyethylene insulating and preservative film for rubber tires according to claim 1, characterized in that, The mass ratio of lipoic acid, acetone and modified nano-titanium dioxide is (80-100):(1200-2400):(16-28); the reaction temperature is 90-110℃ and the reaction time is 20-28h.

7. The method for preparing a polyethylene insulating and preservative film for rubber tires according to claim 1, characterized in that, The mass ratio of intermediate I, chlorinated polyethylene, N,N-dimethylformamide and potassium carbonate is (200-280):(120-180):(2000-4000):(80-100); the reaction temperature is 55-65℃ and the reaction time is 34-46h.

8. The method for preparing a polyethylene insulating and preservative film for rubber tires according to claim 1, characterized in that, The mass ratio of modified polyethylene, linear low-density polyethylene, high-density polyethylene, polyethylene wax and antistatic agent is (40-80):(6-10):(12-24):(8-16):(2-6).

9. The method for preparing a polyethylene insulating and preservative film for rubber tires according to claim 1, characterized in that, The blown film machine uses a single-screw extruder with an extruder body temperature of 160-220℃, a die head temperature of 170-230℃, and a screw speed of 20-45 r / min.

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