Residue-free weather-resistant composite PE protective film for optical lens and preparation method of residual-free weather-resistant composite PE protective film

Abstract

The invention relates to the technical field of adhesives, and discloses a residue-free weather-resistant composite PE protective film for an optical lens and a preparation method of the residue-free weather-resistant composite PE protective film. The preparation method of the residue-free weather-resistant composite PE protective film for the optical lens comprises the following steps: preparing an adhesive by taking high-molecular-weight polyisobutene, high-performance methyl vinyl silicone rubber, low-molecular-weight polyisobutene and a plasticizer as raw materials; and coating the adhesive on a PE base film to obtain the residue-free weather-resistant composite PE protective film for the optical lens. The residue-free weather-resistant composite PE protective film for the optical lens has excellent weather resistance and transparency, and is residue-free in the use process.

Description

Technical Field

[0001] The present invention relates to the technical field of adhesives, and in particular to a residue-free weather-resistant composite PE protective film for optical lenses and a preparation method thereof. Background Art

[0002] As a core component of precision imaging, optical lenses require surface protective films that exhibit high light transmittance, scratch resistance, and environmental tolerance. Traditional optical lens protective films are made by combining a base material liner with an adhesive layer, which is low-cost and easy to process.

[0003] For example, Chinese patent application CN104927693A discloses a method for preparing an optical-grade PE protective film, comprising the following steps: mixing low-density polyethylene and metallocene polyethylene as the raw materials for each film layer in proportion, extruding and plasticizing, blow-molding, and cooling and shaping to obtain a co-extruded film of at least two layers; surface treating the inner layer surface of the co-extruded film; applying an acrylic pressure-sensitive adhesive solution on the surface-treated inner layer surface, and drying and aging to obtain a finished optical-grade PE protective film.

[0004] For example, Chinese patent application CN108728006A discloses an optical thin film protective film and a preparation method thereof, wherein the protective film includes a PE base film layer and an adhesive layer, wherein the adhesive layer is formed by coating glue on the surface of the PE base film layer and drying it, and the PE base film layer includes an A layer and a B layer, wherein the A layer is a PE layer, and the B layer is a PE layer to which organic or inorganic particles are added, and the A layer and the B layer are co-extruded to form a PE base film layer.

[0005] However, the weather resistance of the protective film in the above patent application needs to be improved. It is prone to aging in high temperature and high humidity environments, resulting in degradation of optical performance, thereby affecting the use of optical lenses. Summary of the Invention

[0006] In order to solve the above technical problems, the present invention provides a method for preparing a residue-free weather-resistant composite PE protective film for an optical lens, comprising the following steps: Step 1: low-density polyethylene, linear low-density polyethylene, lubricant, composite antioxidant, and zinc stearate are mixed to obtain a base material; the base material is subjected to extrusion granulation and film blowing to obtain a PE base film; Step 2: Modifying the methyl vinyl silicone rubber with methyl vinyl silicone rubber and a terpolymer in sequence to obtain a modified methyl vinyl silicone rubber; wherein the preparation method of the terpolymer comprises: reacting 2-amino-4-hydroxy-6-methylpyrimidine with isocyanoethyl methacrylate to obtain an intermediate product A; reacting magnolol with 1H,1H,2H,2H-perfluorododecanethiol to obtain an intermediate product B; and copolymerizing the intermediate product A, the intermediate product B, and 2-methylallylamine to obtain a terpolymer; Step 3, preparing POSS-SH using 3-mercaptopropyltrimethoxysilane as a raw material; reacting the modified methyl vinyl silicone rubber with POSS-SH to obtain high-performance methyl vinyl silicone rubber; Step 4: Prepare an adhesive using high molecular weight polyisobutylene, high performance methyl vinyl silicone rubber, low molecular weight polyisobutylene, and plasticizer as raw materials; apply the above adhesive on the PE base film to obtain a residue-free weather-resistant composite PE protective film for optical lenses.

[0007] Preferably, in step 1, the contents of the components in the base material are, by weight, 20-40 parts of low-density polyethylene, 30-50 parts of linear low-density polyethylene, 0.2-0.3 parts of lubricant, 6-14 parts of composite antioxidant, and 0.2-0.3 parts of zinc stearate.

[0008] Preferably, in the step one, the preparation method of the PE base film is as follows: the base material is extruded and granulated at a temperature of 200-220°C and a screw speed of 300-500rpm, and then extruded and blown at a temperature of 200-220°C, a screw speed of 20-30rpm, and a traction speed of 20-30m / min to obtain a PE base film with a thickness of 60-75μm.

[0009] Furthermore, in the step 1, the preparation method of the composite antioxidant specifically comprises: mixing citric acid, 3-fluoroaniline, and dimethyl sulfoxide, ultrasonically treating for 10-20 minutes, reacting at 175-185°C for 5-7 hours, centrifuging, washing, and drying after the reaction to obtain doped modified carbon dots; wherein the mass ratio of citric acid, 3-fluoroaniline, and dimethyl sulfoxide is (2-4):(2.3-4.6):(40-60); mixing 3-mercaptopropionic acid, ethanol, and sodium hydroxide in a mass ratio of (4.2-8.4):(28.8-57.6):(0.3-0.6), and stirring for 20-40 minutes. n, forming a mixed solution A; mixing the doped modified carbon dots, calcium nitrate, and deionized water in a mass ratio of (0.8-1.5): (6.6-13.2): (100-120), stirring for 20-40 minutes to obtain a mixed solution B; under stirring conditions, the mixed solution A, the mixed solution B, and a 0.8 mol / L sodium fluoride aqueous solution are mixed in a volume ratio of 40:15: (15-20), stirring for 40-80 minutes, and then hydrothermally treated at 155-165° C. for 20-30 hours, cooled to room temperature, centrifuged, and dried to obtain a composite nanomaterial; the composite nanomaterial is added to ethanol and heated at 300-500w The mixture was ultrasonically dispersed at a power of 10-30 min, heated to 50-70 ° C, added with a 0.2 g / mL eugenol / ethanol solution, and then added with a 0.5% by mass fraction azobisisobutyronitrile / ethanol solution, stirred for 3-5 h, and after the reaction, centrifuged, washed, and dried to obtain a composite antioxidant; wherein the mass ratio of the composite nanomaterial, eugenol / ethanol solution, and azobisisobutyronitrile / ethanol solution is (1-2): (20-40): (4-8); in the above process, citric acid and 3-fluoroaniline acted as carbon, fluorine, and nitrogen sources, while dimethyl sulfoxide acted as both solvent and sulfur source, and the fluorine-containing antioxidant was synthesized by a hydrothermal method. , nitrogen and sulfur doped modified carbon dots, and a large number of hydroxyl groups and amino groups are present on the surface of the doped modified carbon dots; further, the large number of hydroxyl groups and amino groups on the doped modified carbon dots are combined with calcium fluoride through hydrogen bonds, and nano calcium fluoride is connected to the doped modified carbon dots to obtain a composite nano material. In addition, in the preparation process of the composite nano material, 3-mercaptopropionic acid is added, and the carboxyl group of 3-mercaptopropionic acid can bond with the metal ion of nano calcium fluoride, and the 3-mercaptopropionic acid is chemically grafted on the surface of the composite nano material, thereby introducing a thiol group on the surface of the composite nano material, and the thiol group then reacts with the carbon-carbon double bond of eugenol, and the eugenol having a benzene ring and a phenolic hydroxyl structure is connected to the composite nano material.

[0010] Preferably, in the step 2, the preparation method of the modified methyl vinyl silicone rubber specifically comprises: adding ethyl isocyanate acrylate and Grubbs second-generation catalyst to tetrahydrofuran, mixing until uniform, and obtaining a modified liquid; adding methyl vinyl silicone rubber to tetrahydrofuran, stirring for 3-5 hours, and then adding the modified liquid dropwise at a rate of 0.8-1.2 mL / min, stirring and reacting at room temperature in a nitrogen atmosphere for 5.5-6.5 hours, washing and drying after the reaction to obtain functionalized methyl vinyl silicone rubber; wherein the mass ratio of ethyl isocyanate acrylate, Grubbs second-generation catalyst, and methyl vinyl silicone rubber is (1-2): ( 0.01-0.02):(10-15); adding the functionalized methyl vinyl silicone rubber to tetrahydrofuran, stirring for 3-5h, then adding the terpolymer, reacting at 50-60°C in a nitrogen atmosphere for 8-10h, washing, and drying after the reaction to obtain a modified methyl vinyl silicone rubber; wherein the mass ratio of the functionalized methyl vinyl silicone rubber, tetrahydrofuran, and the terpolymer is (10-15):(100-200):(2.5-5.5); in the above process, under the action of Grubbs second-generation catalyst, isocyanate ethyl acrylate and methyl vinyl silicone rubber react, and multiple methyl vinyl silicone rubbers are introduced into the structure of the methyl vinyl silicone rubber. isocyanate group to obtain functionalized methyl vinyl silicone rubber; the isocyanate group of the functionalized methyl vinyl silicone rubber reacts with the amino group in the terpolymer, and the terpolymer structure is introduced into the methyl vinyl silicone rubber to obtain modified methyl vinyl silicone rubber; further, in the step 2, the preparation method of the terpolymer specifically comprises: adding 2-amino-4-hydroxy-6-methylpyrimidine to dimethyl sulfoxide, and stirring at 140-160°C for 10-20 minutes, cooling to room temperature, and then adding isocyanoethyl methacrylate, stirring at room temperature for 12-14 hours, filtering, washing, and drying to obtain intermediate product A; wherein, 2 The mass ratio of magnolol to methanol is (2-4): (100-180): (2.7-5.4); magnolol is added to methanol, stirred for 20-40 minutes, heated to 50-60°C, 1H,1H,2H,2H-perfluorododecanethiol is added, and then 0.5% azobisisobutyronitrile / methanol solution is added, stirred for 5-6 hours, and rotary evaporated to obtain intermediate product B; wherein the mass ratio of magnolol to 1H,1H,2H,2H-perfluorododecanethiol, azobisisobutyronitrile / methanol solution and methanol is (2.4-4.8): (4.5-9):(6-10):(120-150); The intermediate product A, the intermediate product B, 2-methylallylamine, azobisisobutyronitrile, and N,N-dimethylformamide are mixed and stirred at room temperature for 1-2 hours, and then reacted at 75-85°C in a nitrogen atmosphere for 20-28 hours, cooled to room temperature, and the reaction mixture is precipitated in methanol at 0°C, filtered, and dried to obtain a terpolymer; wherein the mass ratio of the intermediate product A, the intermediate product B, 2-methylallylamine, azobisisobutyronitrile, and N,N-dimethylformamide is (3-5):(8-10):(0.8-1.2):(0.2-0.3):(150-200); the above During the process, 2-amino-4-hydroxy-6-methylpyrimidine and isocyanoethyl methacrylate react to obtain an intermediate product A containing a quadruple hydrogen bond; the carbon-carbon double bond at one end of magnolol reacts with the thiol group of 1H,1H,2H,2H-perfluorododecanethiol to obtain an intermediate product B; the intermediate product A, the intermediate product B, and 2-methylallylamine are polymerized under the action of azobisisobutyronitrile to obtain a ternary copolymer containing a quadruple hydrogen bond structure, a fluorine-containing long chain, and an amino group; preferably, in the step three, the preparation method of the high-performance methyl vinyl silicone rubber specifically comprises: 3-mercaptopropyltrimethoxysilane, methanol, and 30% hydrochloric acid by mass at a ratio of (10-15):(24 The method comprises the following steps: mixing the POSS-SH with the modified methyl vinyl silicone rubber in a volume ratio of 0-330): (20-30), stirring at 500-700 r / min, and reflux at 85-95° C. for 20-28 h, removing the solvent under reduced pressure, washing the obtained white sticky precipitate with methanol three times, dissolving it with tetrahydrofuran, and then adding acetonitrile and crystallizing it at 18-22° C. for 10-15 h. The obtained crystalline product is washed with acetone and then vacuum dried to obtain POSS-SH; adding POSS-SH to tetrahydrofuran, ultrasonically treating it for 20-40 min, and obtaining a POSS-SH dispersion; adding modified methyl vinyl silicone rubber to tetrahydrofuran, heating it to 50-60° C., and then mixing it with the above-mentioned POSS-SH. The dispersions are mixed and stirred for 20-40 minutes, followed by the addition of azobisisobutyronitrile, followed by stirring for 4-6 hours. After completion of the reaction, the mixture is washed and dried to obtain a high-performance methyl vinyl silicone rubber. The mass ratio of POSS-SH, modified methyl vinyl silicone rubber, and azobisisobutyronitrile is (2.5-4.5):(10-15):(0.1-0.2). In the above process, a mercapto-containing polyhedral oligomeric silsesquioxane, POSS-SH, is prepared using 3-mercaptopropyltrimethoxysilane as a raw material. The POSS-SH is then incorporated into the modified methyl vinyl silicone rubber via the reaction of the mercapto groups in the POSS-SH with the carbon-carbon double bonds in the high-performance methyl vinyl silicone rubber.

[0011] Preferably, in the step four, the preparation method of the residue-free weather-resistant composite PE protective film for optical lenses is as follows: high molecular weight polyisobutylene is taken and kneaded at a temperature of 160-180°C and a speed of 50-80r / min for 5-15min, and then high-performance methyl vinyl silicone rubber is added and kneaded at a temperature of 170-190°C and a speed of 50-80r / min for 20-30min, and then the substrate is obtained by tableting through a flat vulcanizer for standby use; low molecular weight polyisobutylene and plasticizer are mixed, stirred at 150-170°C in a nitrogen atmosphere, and then the above-mentioned substrate is added and continued to stir until the system becomes a uniform viscous liquid to obtain an adhesive; the above-mentioned adhesive is coated on the PE base film, and the thickness of the adhesive layer after drying is 10-20μm to obtain a residue-free weather-resistant composite PE protective film for optical lenses.

[0012] Preferably, in step 4, the contents of the components in the adhesive, measured in parts by weight, are: 60-100 parts of high molecular weight polyisobutylene, 10-50 parts of high performance methyl vinyl silicone rubber, 10-50 parts of low molecular weight polyisobutylene, and 30-70 parts of plasticizer; wherein the high molecular weight polyisobutylene includes high molecular weight polyisobutylene OPPANOL B50; the low molecular weight polyisobutylene includes low molecular weight polyisobutylene PB1300; and the plasticizer includes naphthenic oil N4010.

[0013] The method for preparing the residue-free weather-resistant composite PE protective film for an optical lens is used to prepare the residue-free weather-resistant composite PE protective film for an optical lens.

[0014] Compared with the prior art, the present invention has the following beneficial effects: 1. The non-residue weather-resistant composite PE protective film for optical lenses of the present invention is obtained by coating an adhesive on a PE base film. The combination of the two makes the non-residue weather-resistant composite PE protective film for optical lenses have excellent transparency and weather resistance, providing good protection for optical lenses, and no residual adhesive will be left when removed; 2. The PE base film of the present invention is added with a composite antioxidant, which is obtained by connecting nano-calcium fluoride modified with 3-mercaptopropionic acid to doped modified carbon dots and then modifying it with eugenol; the doped modified carbon dots contain fluorine, nitrogen, and sulfur and have a large number of hydroxyl and amino groups on the surface. Since the carbon dots have unique ultraviolet absorption properties, they can be used as anti-ultraviolet absorbers, and the n→π* transition of heteroatoms fluorine, nitrogen, and sulfur enhances the ultraviolet absorption intensity of the doped modified carbon dots; further, the large number of hydroxyl and amino groups on the doped modified carbon dots are hydrogen-bonded with calcium fluoride, and nano-calcium fluoride is connected to the doped modified carbon dots to obtain a composite nano-material. Since calcium fluoride itself has high transparency and a refractive index similar to that of polymers such as PE, it can keep the PE material highly transparent. Therefore, adding the composite nano-material By adding 3-mercaptopropionic acid into PE material, a transparent, uniform, and anti-aging transparent film can be prepared; at the same time, due to the unique toughening effect and thermal stability of the composite nanomaterial, the PE material has good toughness and thermal stability; in addition, in the preparation process of the composite nanomaterial, 3-mercaptopropionic acid is added. The carboxyl group of 3-mercaptopropionic acid can bond with the metal ion of nano-calcium fluoride, and the 3-mercaptopropionic acid is chemically grafted on the surface of the composite nanomaterial, thereby introducing a mercapto group on the surface of the composite nanomaterial. The mercapto group then reacts with the carbon-carbon double bond of eugenol, and the eugenol having a benzene ring and a phenolic hydroxyl structure is grafted on the composite nanomaterial, thereby improving the anti-ultraviolet performance of the composite nanomaterial and the compatibility of the composite nanomaterial with the PE matrix, thereby making the PE base film have excellent heat resistance, anti-ultraviolet performance, toughness and transparency; 3. The adhesive of the present invention contains components such as high molecular weight polyisobutylene, high performance methyl vinyl silicone rubber, and low molecular weight polyisobutylene. The high molecular weight polyisobutylene and high performance methyl vinyl silicone rubber are used to form the matrix of the adhesive, which has a dual-continuous phase network structure, plays a skeleton role, improves elasticity and cohesive strength, and uses low molecular weight polyisobutylene as a tackifier to provide appropriate viscosity.

[0015] The high-performance methyl vinyl silicone rubber of the present invention contains a terpolymer chain and a POSS framework, and the terpolymer chain contains a quadruple hydrogen bond structure and a long fluorine-containing chain: 1) the quadruple hydrogen bond structure promotes more complex entanglement and cross-linking between molecular chains, thereby enhancing the mechanical properties, adhesion, and high-temperature and high-humidity resistance of the methyl vinyl silicone rubber, and improving the cohesive strength of the adhesive, thereby avoiding adhesive residue; 2) the long fluorine-containing chain improves the hydrophobicity of the high-performance methyl vinyl silicone rubber and has a positive impact on improving the cross-linking density of the system; 3) the POSS framework has high thermal stability and can improve the thermal stability of the polymer; therefore, the adhesive of the present invention has good viscosity and weather resistance; in addition, the high-performance methyl vinyl silicone rubber retains excellent transparency, and each component in the adhesive also has high transparency, so the adhesive of the present invention also has high transparency. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 Schematic diagram of the synthesis of the functionalized methyl vinyl silicone rubber of the present invention; Figure 2 Schematic diagram of the synthesis of intermediate product A of the present invention; Figure 3 Schematic diagram of the synthesis of intermediate product B of the present invention. DETAILED DESCRIPTION

[0017] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0018] Example 1 This embodiment discloses a method for preparing a composite antioxidant, comprising the following steps: mixing 3 g of citric acid, 3.5 g of 3-fluoroaniline, and 50 g of dimethyl sulfoxide, ultrasonically treating for 15 minutes, reacting at 180° C. for 6 hours, adding 150 g of ethanol to the mixture after the reaction, centrifuging at 12,000 r / min for 15 minutes, repeating the above washing and centrifuging operations until the supernatant becomes clear and transparent, and finally, vacuum drying the obtained solid product at 45° C. to obtain doped modified carbon dots; and 6.3 g of 3-mercaptopropionic acid, 43.2g ethanol, and 0.5g sodium hydroxide were mixed and stirred for 30min to form a mixed solution A; 1.1g doped modified carbon dots, 9.9g calcium nitrate, and 110g deionized water were mixed and stirred for 30min to obtain a mixed solution B; under stirring conditions, the mixed solution A, the mixed solution B, and a 0.8mol / L sodium fluoride aqueous solution were mixed in a volume ratio of 40:15:17.5, stirred for 60min, and then hydrothermally treated at 160℃ for 25h, cooled to room temperature, and the solid products were collected by centrifugation. The mixture was washed with deionized water and ethanol four times and dried in vacuum at 55°C to obtain a composite nanomaterial; 1.5 g of the composite nanomaterial was added to 35 g of ethanol, ultrasonically dispersed at a power of 400 w for 20 min, heated to 60°C, 30 g of 0.2 g / mL eugenol / ethanol solution was added, and then 6 g of 0.5% azobisisobutyronitrile / ethanol solution was added. The mixture was stirred for 4 h. After the reaction was completed, the solid product was collected by centrifugation, washed four times with ethanol, and dried in vacuum at 55°C to obtain a composite antioxidant.

[0019] Example 2 The present embodiment discloses a preparation method of a ternary copolymer, comprising the following steps: adding 3 g of 2-amino-4-hydroxy-6-methylpyrimidine to 140 g of dimethyl sulfoxide, stirring at 150° C. for 15 min, cooling to room temperature, adding 4.1 g of isocyanoethyl methacrylate, stirring and reacting at room temperature for 13 h, collecting a white precipitate by filtration, washing with n-hexane, and finally drying the precipitate in a vacuum at 28° C. to obtain an intermediate product A; adding 3.6 g of magnolol to 135 g of methanol, stirring for 30 min, heating to 55° C., adding 6.8 g of 1H,1H,2H,2H-perfluorododecanethiol, and then adding 8 g of a 0.5% by mass azobisisobutyronitrile / methanol solution, stirring and reacting for 5.5 h, and after the reaction, rotary evaporation at 75° C. to obtain an intermediate product B; and adding 4 g of the intermediate product A, 9 g of the intermediate product B, 1 g of 2-methylallylamine, 0.25 g of azobisisobutyronitrile, and 175 g of N,N-dimethylformamide was mixed, stirred at room temperature for 1.5 h, then reacted at 80°C for 24 h in a nitrogen atmosphere, cooled to room temperature, and the reaction mixture was precipitated in methanol at 0°C, filtered, and dried at 55°C to obtain a terpolymer.

[0020] Example 3 This embodiment discloses a method for preparing a residue-free weather-resistant composite PE protective film for an optical lens, comprising the following steps: Step 1: Mix 20 parts of low-density polyethylene, 30 parts of linear low-density polyethylene, 0.2 parts of lubricant, 6 parts of composite antioxidant, and 0.2 parts of zinc stearate by weight to obtain a base material; extrude and granulate the base material at a temperature of 200° C. and a screw speed of 300 rpm, and then extrude and blow film at a temperature of 200° C., a screw speed of 20 rpm, and a pulling speed of 20 m / min to obtain a PE base film with a thickness of 60 μm; Step 2: Add 1 g of ethyl isocyanate acrylate and 0.01 g of Grubbs second-generation catalyst to 20 g of tetrahydrofuran and mix until uniform to obtain a modified solution; add 10 g of methyl vinyl silicone rubber to 100 g of tetrahydrofuran and stir for 5 h, then add the modified solution dropwise at a rate of 0.8 mL / min, and stir at room temperature in a nitrogen atmosphere for 5.5 h. After the reaction is completed, the product is washed 3 times with dimethyl sulfoxide and dried to obtain a functionalized methyl vinyl silicone rubber; add 10 g of functionalized methyl vinyl silicone rubber to 100 g of tetrahydrofuran and stir for 3 h, then add 2.5 g of the terpolymer and react at 50° C. in a nitrogen atmosphere for 10 h. After the reaction is completed, the product is washed 3 times with N,N-dimethylformamide and dried to obtain a modified methyl vinyl silicone rubber; Step 3: 10 mL of 3-mercaptopropyltrimethoxysilane, 240 mL of methanol and 20 mL of 30% hydrochloric acid were mixed, stirred at 500 r / min, and refluxed at 85 ° C for 28 h. The solvent was removed under reduced pressure. The obtained white sticky precipitate was washed three times with methanol, dissolved with 5 mL of tetrahydrofuran, and then 200 mL of acetonitrile was added. Crystallization was carried out at 18 ° C for 15 h. The obtained crystalline product was washed with acetone and vacuum dried to obtain POSS-SH; 2.5 g of POSS-SH was added to 30 g of tetrahydrofuran and ultrasonically treated for 20 min to obtain a POSS-SH dispersion; 10 g of modified methyl vinyl silicone rubber was added to 100 g of tetrahydrofuran, heated to 50 ° C, and then mixed with the above-mentioned POSS-SH dispersion, stirred for 20 min, and then 0.1 g of azobisisobutyronitrile was added. The reaction was stirred for 4 h. After the reaction, the obtained product was washed 3 times with N, N-dimethylformamide and dried to obtain high-performance methyl vinyl silicone rubber. Step 4: Take 60 parts of high molecular weight polyisobutylene OPPANOL B50 by weight, and knead them at a temperature of 160°C and a speed of 50 r / min for 15 minutes. Then add 10 parts of high-performance methyl vinyl silicone rubber and knead them at a temperature of 170°C and a speed of 50 r / min for 30 minutes. Then, press the sheet on a flat vulcanizer to obtain a base sheet for later use; mix 10 parts of low molecular weight polyisobutylene PB1300 and 30 parts of cyclohexane oil N4010, stir at 150°C in a nitrogen atmosphere, add the above-mentioned base sheet and continue stirring until the system becomes a uniform viscous liquid to obtain an adhesive; apply the above-mentioned adhesive on the PE base film, and the thickness of the adhesive layer after drying is 15 μm to obtain a residue-free weather-resistant composite PE protective film for optical lenses.

[0021] Example 4 This embodiment discloses a method for preparing a residue-free weather-resistant composite PE protective film for an optical lens, comprising the following steps: Step 1: Mix 40 parts of low-density polyethylene, 50 parts of linear low-density polyethylene, 0.3 parts of lubricant, 14 parts of composite antioxidant, and 0.3 parts of zinc stearate by weight to obtain a base material; extrude and granulate the base material at a temperature of 220° C. and a screw speed of 500 rpm, and then extrude and blow film at a temperature of 220° C., a screw speed of 30 rpm, and a pulling speed of 30 m / min to obtain a PE base film with a thickness of 75 μm; Step 2: Add 2 g of ethyl isocyanate acrylate and 0.02 g of Grubbs second-generation catalyst to 30 g of tetrahydrofuran and mix until uniform to obtain a modified solution; add 15 g of methyl vinyl silicone rubber to 200 g of tetrahydrofuran and stir for 5 h, then add the modified solution dropwise at a rate of 1.2 mL / min, and stir at room temperature in a nitrogen atmosphere for 6.5 h. After the reaction is completed, the product is washed 5 times with dimethyl sulfoxide and dried to obtain a functionalized methyl vinyl silicone rubber; add 15 g of functionalized methyl vinyl silicone rubber to 200 g of tetrahydrofuran and stir for 5 h, then add 5.5 g of the terpolymer and react at 60 ° C in a nitrogen atmosphere for 10 h. After the reaction is completed, the product is washed 5 times with N, N-dimethylformamide and dried to obtain a modified methyl vinyl silicone rubber; Step 3: 15 mL of 3-mercaptopropyltrimethoxysilane, 330 mL of methanol and 30 mL of 30% hydrochloric acid were mixed, stirred at 700 r / min, and refluxed at 95 ° C for 20 h. The solvent was removed under reduced pressure. The obtained white sticky precipitate was washed three times with methanol, dissolved with 8 mL of tetrahydrofuran, and then 300 mL of acetonitrile was added. Crystallization took place at 22 ° C for 10 h. The obtained crystalline product was washed with acetone and vacuum dried to obtain POSS-SH; 4.5 g of POSS-SH was added to 50 g of tetrahydrofuran and ultrasonically treated for 40 min to obtain a POSS-SH dispersion; 15 g of modified methyl vinyl silicone rubber was added to 150 g of tetrahydrofuran, heated to 60 ° C, and then mixed with the above-mentioned POSS-SH dispersion, stirred for 40 min, and then 0.2 g of azobisisobutyronitrile was added and stirred for 4 h. After the reaction, the obtained product was washed 5 times with N, N-dimethylformamide and dried to obtain high-performance methyl vinyl silicone rubber; Step 4: Take 100 parts of high molecular weight polyisobutylene OPPANOL B50 by weight, and knead them at a temperature of 180°C and a speed of 80 r / min for 5 minutes. Then add 50 parts of high-performance methyl vinyl silicone rubber and knead them at a temperature of 190°C and a speed of 80 r / min for 20 minutes. Then, press the sheet through a flat vulcanizer to obtain a base sheet for later use; mix 50 parts of low molecular weight polyisobutylene PB1300 and 70 parts of cyclohexane oil N4010, stir at 170°C in a nitrogen atmosphere, add the above-mentioned base sheet and continue stirring until the system becomes a uniform viscous liquid to obtain an adhesive; apply the above-mentioned adhesive on the PE base film, and the thickness of the adhesive layer after drying is 15 μm to obtain a residue-free weather-resistant composite PE protective film for optical lenses.

[0022] Example 5 This embodiment discloses a method for preparing a residue-free weather-resistant composite PE protective film for an optical lens, comprising the following steps: Step 1: Mix 30 parts of low-density polyethylene, 40 parts of linear low-density polyethylene, 0.3 parts of lubricant, 10 parts of composite antioxidant, and 0.3 parts of zinc stearate by weight to obtain a base material; extrude and granulate the base material at a temperature of 210° C. and a screw speed of 400 rpm, and then extrude and blow film at a temperature of 210° C., a screw speed of 25 rpm, and a pulling speed of 25 m / min to obtain a PE base film with a thickness of 68 μm; Step 2: Add 1.5 g of ethyl isocyanate acrylate and 0.02 g of Grubbs second-generation catalyst to 25 g of tetrahydrofuran and mix until uniform to obtain a modified solution; add 12.5 g of methyl vinyl silicone rubber to 150 g of tetrahydrofuran and stir for 4 h, then add the modified solution dropwise at a rate of 1 mL / min, and stir at room temperature in a nitrogen atmosphere for 6 h. After the reaction is completed, the product is washed 4 times with dimethyl sulfoxide and dried to obtain a functionalized methyl vinyl silicone rubber; add 12.5 g of functionalized methyl vinyl silicone rubber to 150 g of tetrahydrofuran and stir for 4 h, then add 4 g of the terpolymer and react at 55 ° C. in a nitrogen atmosphere for 9 h. After the reaction is completed, the product is washed 4 times with N, N-dimethylformamide and dried to obtain a modified methyl vinyl silicone rubber; Step 3: 12.5 mL of 3-mercaptopropyltrimethoxysilane, 285 mL of methanol and 25 mL of 30% hydrochloric acid were mixed, stirred at 600 r / min, and refluxed at 90 ° C for 24 h. The solvent was removed under reduced pressure. The obtained white sticky precipitate was washed three times with methanol, dissolved in 6.5 mL of tetrahydrofuran, and then 250 mL of acetonitrile was added and crystallized at 20 ° C for 12.5 h. The obtained crystalline product was washed with acetone and vacuum dried to obtain POSS-SH; 3.5 g of POSS-SH was added to 40 g of tetrahydrofuran and ultrasonically treated for 30 minutes to obtain a POSS-SH dispersion; 12.5 g of modified methyl vinyl silicone rubber was added to 125 g of tetrahydrofuran, heated to 55°C, and then mixed with the above POSS-SH dispersion and stirred for 30 minutes. 0.2 g of azobisisobutyronitrile was then added and stirred for 5 hours. After the reaction was completed, the product was washed four times with N,N-dimethylformamide and dried to obtain high-performance methyl vinyl silicone rubber; Step 4: Take 80 parts of high molecular weight polyisobutylene OPPANOL B50 by weight, and knead them at a temperature of 170°C and a speed of 65r / min for 10 minutes. Then add 30 parts of high-performance methyl vinyl silicone rubber, and knead them at a temperature of 180°C and a speed of 65r / min for 25 minutes. Then, press them into a sheet on a flat vulcanizer to obtain a base sheet for later use; mix 30 parts of low molecular weight polyisobutylene PB1300 and 50 parts of cyclohexane oil N4010, stir them at 160°C in a nitrogen atmosphere, add the above-mentioned base sheet and continue stirring until the system becomes a uniform viscous liquid to obtain an adhesive; apply the above-mentioned adhesive on the PE base film, and the thickness of the adhesive layer after drying is 15μm to obtain a residue-free weather-resistant composite PE protective film for optical lenses.

[0023] The composite antioxidant and terpolymer used in Examples 3-5 are the composite antioxidant prepared in Example 1 and the terpolymer prepared in Example 2.

[0024] Comparative Example 1 Compared with Example 1, in the process of preparing the composite nanomaterial in Comparative Example 1, no doped modified carbon dots were added, and other conditions remained unchanged.

[0025] Specifically, 6.3 g of 3-mercaptopropionic acid, 43.2 g of ethanol, and 0.5 g of sodium hydroxide were mixed and stirred for 30 minutes to form a mixed solution A; 9.9 g of calcium nitrate and 110 g of deionized water were mixed and stirred for 30 minutes to obtain a mixed solution B; under stirring conditions, the mixed solution A, the mixed solution B, and a 0.8 mol / L sodium fluoride aqueous solution were mixed in a volume ratio of 40:15:17.5, stirred for 60 minutes, and then hydrothermally treated at 160° C. for 25 hours. The mixture was cooled to room temperature, and the solid product was collected by centrifugation, washed four times with deionized water and ethanol, respectively, and vacuum dried at 55° C. to obtain a composite nanomaterial.

[0026] Comparative Example 2 Compared with Example 2, in the process of preparing the terpolymer in Comparative Example 2, the intermediate product A was not added, that is, a binary copolymer was obtained in Comparative Example 2, and other conditions remained unchanged.

[0027] Specifically, 9 g of intermediate product B, 1 g of 2-methylallylamine, 0.25 g of azobisisobutyronitrile, and 175 g of N,N-dimethylformamide were mixed, stirred at room temperature for 1.5 h, then reacted at 80 ° C for 24 h in a nitrogen atmosphere, cooled to room temperature, and the reaction mixture was precipitated in methanol at 0 ° C, filtered, and dried at 55 ° C to obtain a binary copolymer.

[0028] Comparative Example 3 Compared with Example 5, in the process of preparing the PE base film in Comparative Example 3, the composite antioxidant prepared in Comparative Example 1 was used, and other conditions remained unchanged.

[0029] Comparative Example 4 Compared with Example 5, in Comparative Example 4, during the preparation of the PE base film, the composite nanomaterial was used instead of the composite antioxidant, while other conditions remained unchanged.

[0030] The composite nanomaterial is specifically as follows: 3g of citric acid, 3.5g of 3-fluoroaniline, and 50g of dimethyl sulfoxide are mixed, ultrasonically treated for 15 minutes, and reacted at 180°C for 6 hours. After the reaction, 150g of ethanol is added to the mixed system, and the mixture is centrifuged at a speed of 12000r / min for 15 minutes. The above washing and centrifugation operations are repeated until the supernatant becomes clear and transparent. Finally, the obtained solid product is vacuum dried at 45°C to obtain doped modified carbon dots; 6.3g of 3-Mercaptopropionic acid, 43.2 g ethanol, and 0.5 g sodium hydroxide were mixed and stirred for 30 minutes to form a mixed solution A; 1.1 g doped modified carbon dots, 9.9 g calcium nitrate, and 110 g deionized water were mixed and stirred for 30 minutes to obtain a mixed solution B; under stirring conditions, the mixed solution A, the mixed solution B, and a 0.8 mol / L sodium fluoride aqueous solution were mixed in a volume ratio of 40:15:17.5, stirred for 60 minutes, and then hydrothermally treated at 160°C for 25 hours. The mixture was cooled to room temperature, and the solid product was collected by centrifugation, washed four times with deionized water and ethanol, respectively, and dried in vacuo at 55°C to obtain a composite nanomaterial.

[0031] Comparative Example 5 Compared with Example 5, in the process of preparing the modified methyl vinyl silicone rubber in Comparative Example 5, the binary copolymer prepared in Comparative Example 2 was used instead of the ternary copolymer, and other conditions remained unchanged.

[0032] Comparative Example 6 Compared with Example 5, in Comparative Example 6, during the preparation of the PE base film, no composite antioxidant was added, and other conditions remained unchanged.

[0033] Specifically, based on weight, 30 parts of low-density polyethylene, 40 parts of linear low-density polyethylene, 0.3 parts of lubricant, and 0.3 parts of zinc stearate are mixed to obtain a base material.

[0034] Comparative Example 7 Compared with Example 5, in Comparative Example 6, during the preparation of high-performance methyl vinyl silicone rubber, functionalized methyl vinyl silicone rubber was used instead of modified methyl vinyl silicone rubber, while other conditions remained unchanged.

[0035] The functionalized methyl vinyl silicone rubber is specifically prepared as follows: 1.5 g of ethyl isocyanate acrylate and 0.02 g of Grubbs second-generation catalyst are added to 25 g of tetrahydrofuran and mixed until uniform to obtain a modified liquid; 12.5 g of methyl vinyl silicone rubber is added to 150 g of tetrahydrofuran and stirred for 4 hours, and then the above-mentioned modified liquid is added dropwise at a rate of 1 mL / min. The reaction is stirred at room temperature in a nitrogen atmosphere for 6 hours. After the reaction is completed, the obtained product is washed 4 times with dimethyl sulfoxide and dried to obtain functionalized methyl vinyl silicone rubber.

[0036] In the above embodiments and comparative examples, the lubricant is ethylene bisstearamide, model EBS-FF, pH value 4.0-5.0, brand Kao of Japan, from Dongguan Zhenming Chemical Co., Ltd.; low-density polyethylene (LDPE), brand LD200GH, density 0.922 g / mL, melt flow index 2.0 g / 10 min, purchased from Sinopec Beijing Yanshan Branch; linear low-density polyethylene, brand Daqing Petrochemical, density 0.926 g / mL, melt flow index 20 g / 10 min, purchased from Anhui Suchuang Chemical Co., Ltd.; methyl vinyl silicone rubber (MVSR, Mn≈25000, vinyl content of about 4%) from Dongjue Silicone Group Co., Ltd.; Grubbs second-generation catalyst, CAS No. 246047-72-3, model PA69761,, from Guangdong Wengjiang Chemical Reagent Co., Ltd.; high molecular weight polyisobutylene OPPANOL B50, number average molecular weight 120,000, glass transition temperature -64°C, ash content (PPM) <200, from Guangzhou Jinkai Chemical Co., Ltd.; low molecular weight polyisobutylene PB1300, density 0.92 g / cm³, transparent color, fluid shape, brand is Platinum, from Platinum (Hangzhou) New Materials Co., Ltd.; cyclohexane oil N4010, appearance is colorless and transparent oily liquid, density is 904.5 kg / m³, flash point is 216°C, from Shandong Taichang Petrochemical Technology Co., Ltd.

[0037] Experimental example Performance tests were performed on the samples of the residue-free weather-resistant composite PE protective film for optical lenses prepared in Examples 3-5 and Comparative Examples 3-7.

[0038] 1. Anti-residue performance test: Refer to the 180° peel strength test method in accordance with standard GB2792-2014. Remove the protective film and observe the steel plate for any residual adhesive. Record the residual adhesive area as a percentage of the total sample area (where: × represents a residual adhesive area greater than 40%; □ represents a residual adhesive area between 15% and 40%; ○ represents a residual adhesive area less than 15%; √ represents no residual adhesive).

[0039] 2. Weather resistance test: 1. UV aging resistance test: The test standard is GBT16422.3-2022. Test condition 1 is the UV band of 280nm-400nm, and the aging time is 100 hours; test condition 2 is the UV band of 254nm, the UV lamp power is 15W, the irradiation distance is 15cm, and the aging time is 72 hours; 2. High temperature and high humidity resistance test: Test for 7 days at a temperature of 65°C and a relative humidity of 95% (i.e., each group of samples is tested after being placed under these conditions for 7 days).

[0040] 3. Light transmittance test: Tested in accordance with the test standard GB / T 2410-2008.

[0041] The test results are shown in Table 1:

[0042] From the test results in Table 1, it can be seen that the non-residue weather-resistant composite PE protective films for optical lenses prepared in Examples 3-5 of the present invention have excellent weather resistance and transparency, and no residue is left during use. From the comparison between Comparative Example 3 and Example 5, it can be seen that due to the unique ultraviolet absorption characteristics of carbon dots, they can be used as anti-ultraviolet absorbers, and the n→π* transition of heteroatoms fluorine, nitrogen, and sulfur enhances the ultraviolet absorption intensity of the doped modified carbon dots, giving the PE base film excellent anti-ultraviolet aging performance; from the comparison between Comparative Example 4 and Example 5, it can be seen that by attaching eugenol having a benzene ring and a phenolic hydroxyl structure to the composite nanomaterial, while improving the anti-ultraviolet performance of the composite nanomaterial, it also improves the compatibility of the composite nanomaterial with the PE matrix, thereby making the PE base film have excellent heat resistance, anti-ultraviolet performance, toughness and transparency. Brightness; From the comparison of Comparative Example 5 and Comparative Example 7 with Example 5, it can be seen that the high-performance methyl vinyl silicone rubber contains a ternary copolymer chain, and the ternary copolymer chain contains a quadruple hydrogen bond structure and a long fluorine-containing chain, which work together to enhance the mechanical properties, adhesion, and high temperature and high humidity resistance of the methyl vinyl silicone rubber, and improve the cohesive strength of the adhesive to avoid adhesive residue; From the comparison of Comparative Example 6 and Example 5, it can be seen that the PE base film contains a composite antioxidant, and the components in the composite antioxidant work together to give the PE base film excellent heat resistance and UV resistance, and enable the PE base film to maintain high transparency.

[0043] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a residue-free weather-resistant composite PE protective film for an optical lens, characterized in that: The following steps are involved: Step 1: low-density polyethylene, linear low-density polyethylene, lubricant, composite antioxidant, and zinc stearate are mixed to obtain a base material; The base material is extruded into granules and then blown into film to obtain a PE base film; Step 2: Modifying the methyl vinyl silicone rubber with methyl vinyl silicone rubber and a terpolymer in sequence to obtain a modified methyl vinyl silicone rubber; wherein the preparation method of the terpolymer comprises: reacting 2-amino-4-hydroxy-6-methylpyrimidine with isocyanoethyl methacrylate to obtain an intermediate product A; reacting magnolol with 1H,1H,2H,2H-perfluorododecanethiol to obtain an intermediate product B; and copolymerizing the intermediate product A, the intermediate product B, and 2-methylallylamine to obtain a terpolymer; Step 3, preparing POSS-SH using 3-mercaptopropyltrimethoxysilane as a raw material; reacting the modified methyl vinyl silicone rubber with POSS-SH to obtain high-performance methyl vinyl silicone rubber; Step 4: Prepare an adhesive using high molecular weight polyisobutylene, high performance methyl vinyl silicone rubber, low molecular weight polyisobutylene, and plasticizer as raw materials; apply the above adhesive on the PE base film to obtain a residue-free weather-resistant composite PE protective film for optical lenses.

2. The method for preparing a residue-free weather-resistant composite PE protective film for an optical lens according to claim 1, characterized in that: In the step 1, the contents of the components in the base material are, by weight, 20-40 parts of low-density polyethylene, 30-50 parts of linear low-density polyethylene, 0.2-0.3 parts of lubricant, 6-14 parts of composite antioxidant, and 0.2-0.3 parts of zinc stearate.

3. The method for preparing a residue-free weather-resistant composite PE protective film for an optical lens according to claim 1, characterized in that: In the step 1, the preparation method of the PE base film is as follows: the base material is extruded and granulated at a temperature of 200-220°C and a screw speed of 300-500rpm, and then extruded and blown at a temperature of 200-220°C, a screw speed of 20-30rpm, and a traction speed of 20-30m / min to obtain a PE base film with a thickness of 60-75μm.

4. The method for preparing a residue-free weather-resistant composite PE protective film for an optical lens according to claim 1, characterized in that: In the step 1, the preparation method of the composite antioxidant specifically includes: mixing citric acid, 3-fluoroaniline, and dimethyl sulfoxide, ultrasonically treating, reacting at 175-185° C. for 5-7 hours, centrifuging, washing, and drying after the reaction to obtain doped modified carbon dots; wherein the mass ratio of citric acid, 3-fluoroaniline, and dimethyl sulfoxide is (2-4):(2.3-4.6):(40-60); mixing 3-mercaptopropionic acid, ethanol, and sodium hydroxide in a mass ratio of (4.2-8.4):(28.8-57.6):(0.3-0.6) and stirring to form a mixed solution A; mixing doped modified carbon dots, calcium nitrate, and deionized water in a mass ratio of (0.8-1.5):(6.6-13.2):(100-120) and stirring, The method comprises the steps of: obtaining a mixed solution B; mixing the mixed solution A, the mixed solution B, and a sodium fluoride aqueous solution with a concentration of 0.8 mol / L in a volume ratio of 40:15:(15-20) under stirring conditions, stirring, hydrothermally treating at 155-165° C. for 20-30 hours, cooling to room temperature, centrifuging, and drying to obtain a composite nanomaterial; adding the composite nanomaterial to ethanol, heating to 50-70° C., adding a eugenol / ethanol solution with a concentration of 0.2 g / mL, and then adding an azobisisobutyronitrile / ethanol solution, stirring for reaction for 3-5 hours, centrifuging, washing, and drying to obtain a composite antioxidant; wherein the mass ratio of the composite nanomaterial, the eugenol / ethanol solution, and the azobisisobutyronitrile / ethanol solution is (1-2):(20-40):(4-8).

5. The method for preparing a residue-free weather-resistant composite PE protective film for an optical lens according to claim 1, characterized in that: In the step 2, the preparation method of the modified methyl vinyl silicone rubber specifically comprises: adding ethyl isocyanate acrylate and Grubbs second generation catalyst to tetrahydrofuran, mixing until uniform, and obtaining a modified liquid; adding methyl vinyl silicone rubber to tetrahydrofuran, stirring, and then dropwise adding the modified liquid, stirring and reacting at room temperature in a nitrogen atmosphere for 5.5-6.5 hours, washing and drying after the reaction is completed to obtain functionalized methyl vinyl silicone rubber; wherein, ethyl isocyanate acrylate, Grubbs second generation catalyst, The mass ratio of methyl vinyl silicone rubber is (1-2):(0.01-0.02):(10-15); the functionalized methyl vinyl silicone rubber is added to tetrahydrofuran, stirred, and then the terpolymer is added, and the reaction is carried out at 50-60°C in a nitrogen atmosphere for 8-10 hours. After the reaction is completed, the modified methyl vinyl silicone rubber is washed and dried to obtain the modified methyl vinyl silicone rubber; wherein the mass ratio of the functionalized methyl vinyl silicone rubber, tetrahydrofuran, and the terpolymer is (10-15):(100-200):(2.5-5.5).

6. The method for preparing a residue-free weather-resistant composite PE protective film for an optical lens according to claim 1, characterized in that: In the step 2, the preparation method of the terpolymer specifically comprises: adding 2-amino-4-hydroxy-6-methylpyrimidine to dimethyl sulfoxide, stirring at 140-160° C. for 10-20 minutes, cooling to room temperature, adding isocyanoethyl methacrylate, stirring and reacting at room temperature for 12-14 hours, filtering, washing, and drying to obtain an intermediate product A; wherein the mass ratio of 2-amino-4-hydroxy-6-methylpyrimidine, dimethyl sulfoxide, and isocyanoethyl methacrylate is (2-4):(100-180):(2.7-5.4); adding magnolol to methanol, stirring, heating to 50-60° C., adding 1H,1H,2H,2H-perfluorododecanethiol, and then adding azobisisobutyronitrile / methanol solution, stirring and reacting for 5-6 hours, and rotary evaporation to obtain an intermediate product B; The mass ratio of magnolol, 1H,1H,2H,2H-perfluorododecanethiol, azobisisobutyronitrile / methanol solution, and methanol is (2.4-4.8):(4.5-9):(6-10):(120-150); the intermediate product A, the intermediate product B, 2-methylallylamine, azobisisobutyronitrile, and N,N-dimethylformamide are mixed and stirred at room temperature, and then reacted at 75-85°C in a nitrogen atmosphere for 20-28 hours, cooled to room temperature, and the reaction mixture is precipitated in methanol, filtered, and dried to obtain a terpolymer; the mass ratio of the intermediate product A, the intermediate product B, 2-methylallylamine, azobisisobutyronitrile, and N,N-dimethylformamide is (3-5):(8-10):(0.8-1.2):(0.2-0.3):(150-200).

7. The method for preparing a residue-free weather-resistant composite PE protective film for an optical lens according to claim 1, characterized in that: In the step 3, the preparation method of the high-performance methyl vinyl silicone rubber specifically comprises: mixing mercaptopropyltrimethoxysilane, methanol and hydrochloric acid in a volume ratio of (10-15): (240-330): (20-30), stirring, and refluxing at 85-95 ° C for 20-28 hours, removing the solvent under reduced pressure, washing the obtained white sticky precipitate with methanol three times, dissolving it with tetrahydrofuran, and then adding acetonitrile, crystallizing at 18-22 ° C for 10-15 hours, washing the obtained crystalline product with acetone and vacuum drying to obtain POSS-SH; POSS-SH is added to tetrahydrofuran and ultrasonically treated to obtain a POSS-SH dispersion; modified methyl vinyl silicone rubber is added to tetrahydrofuran, heated to 50-60°C, mixed with the above-mentioned POSS-SH dispersion, stirred, and then azobisisobutyronitrile is added and stirred for 4-6 hours. After the reaction is completed, the rubber is washed and dried to obtain a high-performance methyl vinyl silicone rubber; wherein the mass ratio of POSS-SH, modified methyl vinyl silicone rubber, and azobisisobutyronitrile is (2.5-4.5):(10-15):(0.1-0.2).

8. The method for preparing a residue-free weather-resistant composite PE protective film for an optical lens according to claim 1, wherein: In the step 4, the preparation method of the residue-free weather-resistant composite PE protective film for optical lenses specifically includes: taking high molecular weight polyisobutylene and kneading it at a temperature of 160-180°C for 5-15 minutes, then adding high-performance methyl vinyl silicone rubber, kneading it for 20-30 minutes, and then pressing it through a flat vulcanizer to obtain a base sheet for later use; mixing low molecular weight polyisobutylene and plasticizer, stirring at 150-170°C in a nitrogen atmosphere, then adding the above-mentioned base sheet and continuing to stir until the system becomes a uniform viscous liquid to obtain an adhesive; coating the above-mentioned adhesive on the PE base film, and the thickness of the adhesive layer after drying is 10-20 μm, to obtain a residue-free weather-resistant composite PE protective film for optical lenses.

9. The method for preparing a residue-free weather-resistant composite PE protective film for an optical lens according to claim 1, characterized in that: In the step 4, the content of each component in the adhesive is calculated in parts by weight: 60-100 parts of high molecular weight polyisobutylene, 10-50 parts of high performance methyl vinyl silicone rubber, 10-50 parts of low molecular weight polyisobutylene, and 30-70 parts of plasticizer.

10. A residue-free weather-resistant composite PE protective film for an optical lens, prepared by the method for preparing a residue-free weather-resistant composite PE protective film for an optical lens according to any one of claims 1 to 9.

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