CN110591590B - Preparation process of low-viscosity high-temperature-resistant protective film - Google Patents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3893—Low-molecular-weight compounds having heteroatoms other than oxygen containing silicon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/255—Polyesters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2467/00—Presence of polyester
- C09J2467/006—Presence of polyester in the substrate
Abstract
The invention discloses a preparation process of a low-viscosity high-temperature-resistant protective film, which comprises the following steps: s1, preparing a PET film; s2, preparing adhesive liquid, comprising the following steps: s21, preparing silicon-containing diphenol; s22, preparing a catalyst; s23, dehydrating the macromolecular polyalcohol at the temperature of 100-120 ℃ in vacuum for 1-5h, and cooling to 60-80 ℃; then adding organic solvents acetone and silicon-containing diphenol, stirring and mixing uniformly, adding isocyanate and a catalyst, and stirring at constant temperature for reacting for 5-6 h; cooling to 30-50 ℃, finally adding an emulsifier and deionized water, and carrying out high-speed shearing and dispersion for 2h to obtain a low-viscosity high-temperature-resistant adhesive liquid; s3, coating the adhesive liquid on the PET film subjected to corona treatment, drying in an oven at the temperature of 100-110 ℃, cooling, and attaching a protective layer to the surface coated with the adhesive liquid to obtain the PET protective film. The PET protective film prepared by the preparation process disclosed by the invention has excellent performances of high temperature resistance, low viscosity, easiness in tearing, no adhesive residue, good laminating property and the like, and is particularly suitable for being used as a foaming material.
Description
Technical Field
The invention relates to the technical field of protective films, in particular to a preparation process of a low-viscosity high-temperature-resistant protective film for a foaming material.
Background
With the development of society and the promotion of people's demand, protective films have penetrated into various industries, such as instruments, electronics, machinery, building, automobile manufacturing, and labels, and the application of the protective films not only improves the appearance quality of products, facilitates material processing, but also improves the utilization rate of materials and reduces the production cost of the products.
The foam material is a microporous material having numerous cells in the interior thereof based on a polymer such as plastic, rubber, elastomer, natural polymer material, etc., and can also be considered as a composite material having a gas as a filler. The foam material has the advantages of sound insulation, heat preservation, operation cost reduction, energy conservation, environmental protection and the like, and is widely applied to the fields of sports goods, electronics, precise instruments, household appliances, automobiles and the like. With the development of society and the increase of people's demand, the demand of foam materials for protective films is gradually increasing. Polyethylene terephthalate (PET) is a highly crystalline polymer having excellent properties of abrasion resistance, electrical insulation, flame retardancy, thermal aging resistance, and low water absorption, and a protective film made therefrom is called a PET protective film. However, the PET protective films on the market generally have problems such as poor high temperature resistance, difficulty in tearing, residual glue, poor fitting performance, unstable viscosity and the like. Therefore, the preparation of the low-viscosity PET protective film for the foaming material, which is low in viscosity, easy to tear, free of adhesive residue, good in laminating property, good in high temperature resistance and excellent in mechanical property, has important significance for the protective film industry.
Disclosure of Invention
The invention aims to provide a preparation process of a low-viscosity high-temperature-resistant protective film for a foaming material, and the obtained protective film has the excellent performances of low viscosity, easiness in tearing, no adhesive residue, good adhesiveness, good high temperature resistance and the like.
In order to achieve the purpose, the preparation process of the low-viscosity high-temperature-resistant protective film provided by the invention mainly comprises the steps of coating adhesive liquid on a PET film subjected to corona treatment, drying the PET film in an oven at the temperature of 100-110 ℃, cooling, and attaching a protective layer to one surface coated with the adhesive liquid to obtain the PET protective film; the adhesive liquid consists of 20-40 parts by weight of macromolecular polyol, 10-15 parts by weight of silicon-containing diphenol, 5-10 parts by weight of isocyanate, 0.5-2 parts by weight of emulsifier, 4-10 parts by weight of catalyst, 10-30 parts by weight of acetone and 100-150 parts by weight of deionized water. The method specifically comprises the following steps:
s1, pretreating a PET film;
s2, preparing adhesive liquid, comprising the following steps:
s21, reacting p-chlorophenol and trimethylchlorosilane in a solvent toluene to obtain an intermediate a; reacting the intermediate a with dichlorosilane to obtain an intermediate b; hydrolyzing the intermediate b under an acidic condition to prepare silicon-containing diphenol;
s22, mixing methylimidazole and bromoethane with the molar ratio of 1:1, stirring, heating to 80 ℃, reacting for 5 hours, and washing with ethyl acetate for multiple times to obtain a catalyst;
s23, dehydrating the macromolecular polyalcohol at the temperature of 100-120 ℃ in vacuum for 1-5h, and cooling to 60-80 ℃; then adding organic solvents acetone and silicon-containing diphenol, stirring and mixing uniformly, adding isocyanate and a catalyst, and stirring at constant temperature for reacting for 5-6 h; cooling to 30-50 ℃, finally adding an emulsifier and deionized water, and carrying out high-speed shearing and dispersion for 2h to obtain a low-viscosity high-temperature-resistant adhesive liquid;
s3, coating the adhesive liquid on the PET film subjected to corona treatment, drying in an oven at the temperature of 100-110 ℃, cooling, and attaching a protective layer to the surface coated with the adhesive liquid to obtain the PET protective film.
Preferably, the step S21 is specifically: (1) adding p-chlorophenol, pyridine and anhydrous toluene into a reaction flask, dropwise adding trimethylchlorosilane under stirring in an ice bath, heating to room temperature after dropwise adding, stirring for reacting for 8 hours, evaporating and concentrating the filtered solution, and drying in vacuum to obtain a liquid intermediate product a; (2) adding metal sodium and anhydrous toluene into a three-neck flask, stirring, adding a dropping funnel with constant pressure, a thermometer and a condenser, and continuously introducing nitrogen for protection; heating to 110 ℃, vigorously stirring to disperse the metal sodium in toluene to form metal microspheres, then cooling to 80 ℃, dissolving the intermediate product a and dichlorosilane in toluene to prepare a solution, dropwise adding the solution into a flask, carrying out reflux reaction for 4 hours, and cooling to room temperature; evaporating and concentrating the solution to half volume to obtain a concentrated solution containing an intermediate product b; (3) dropwise adding a hydrochloric acid solution into the concentrated solution obtained in the step (2), and stirring for 30min after dropwise adding; the organic phase is washed with pure water and dried over magnesium sulfate, the solvent is removed by evaporation, and the concentrate is cooled to 0 ℃ for crystallization to give the product silicon-containing diphenol. Recrystallizing the silicon-containing diphenol with toluene to obtain the pure silicon-containing diphenol.
The structural formula of the silicon-containing diphenol is as follows:
in the formula, R1And R2Respectively methyl or phenyl.
The reaction equation for preparing the silicon-containing diphenol is as follows:
preferably, the macromolecular polyol is a polyether polyol or a polyester polyol. The emulsifier is one of Sodium Dodecyl Sulfate (SDS), Sodium Dodecyl Benzene Sulfonate (SDBS) and OP-10. The thickness of the PET film is 50-200 μm.
The invention has the advantages that:
silicon-containing diphenol is added into the adhesive liquid for preparing the PET protective film, and long-chain alkyl chains do not exist in the molecular structure of the silicon-containing diphenol, so that the PET protective film has excellent thermal stability and mechanical property. The catalyst is a mild acidic ionic liquid, the catalytic activity of the catalyst is low, and the nucleophilic attack of the catalyst on isocyanate is effectively inhibited, so that the activity of the reaction of the isocyanate and the hydroxyl of macromolecular dihydric alcohol is reduced, the isocyanate also reacts with the phenolic hydroxyl of silicon-containing diphenol, and has a good synergistic effect with an emulsifier, and the viscosity of the product is reduced; and simultaneously controls the viscosity of the reaction system. Therefore, the PET protective film provided by the invention has the characteristics of low viscosity, easiness in tearing, no adhesive residue, good bonding property, good high-temperature resistance and excellent mechanical property. In addition, the preparation process is simple, easy to operate and suitable for industrial production.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and description, and is in no way intended to limit the invention.
Example 1
A preparation process of a low-viscosity high-temperature-resistant protective film specifically comprises the following steps:
s1, pretreatment of the PET film: carrying out corona treatment on the PET film, washing the PET film by acetone and alcohol in sequence, and then drying the PET film in a vacuum oven at 70 ℃ for 12 hours for later use;
s2, preparing adhesive liquid, comprising the following steps:
s21, preparing the silicon-containing diphenol, and the specific steps are as follows: (1) adding 0.11mol of p-chlorophenol, 0.2mol of pyridine and 100mL of anhydrous toluene into a reaction flask, dropwise adding 0.12mol of trimethylchlorosilane under stirring in an ice bath, heating to room temperature after dropwise adding, stirring for reacting for 8 hours, evaporating and concentrating the filtered solution, and drying in vacuum to obtain a liquid intermediate product a; (2) adding 0.2mol of metal sodium and 100mL of anhydrous toluene into a three-neck flask, stirring, adding a dropping funnel at constant pressure, a thermometer and a condenser, and continuously introducing nitrogen for protection; heating to 110 ℃, vigorously stirring to disperse the metal sodium in toluene to form metal microspheres, cooling to 80 ℃, dissolving the intermediate product a and 50mmol of dimethyldichlorosilane in 20mL of toluene to prepare a solution, dropwise adding the solution into a flask, carrying out reflux reaction for 4 hours, and cooling to room temperature; adding 10mL of anhydrous methanol into a reaction flask to consume excessive metal sodium, and evaporating and concentrating the solution to half volume to obtain a concentrated solution containing an intermediate product b; (3) dropwise adding a hydrochloric acid solution (1mol, 15mL) into the concentrated solution obtained in the step (2), and stirring for 30min after dropwise adding; the organic phase is washed with pure water and dried over magnesium sulfate, the solvent is removed by evaporation, and the concentrate is cooled to 0 ℃ for crystallization to give the product silicon-containing diphenol. Recrystallizing the silicon-containing diphenol with toluene to obtain the pure silicon-containing diphenol.
S22, mixing methylimidazole and bromoethane with the molar ratio of 1:1, stirring, heating to 80 ℃, reacting for 5 hours, and washing with ethyl acetate for multiple times to obtain the catalyst.
S23, weighing the components of the adhesive liquid: 20 parts by weight of polyether polyol, 15 parts by weight of silicon-containing diphenol, 10 parts by weight of isocyanate, 0.5 part by weight of emulsifier, 4 parts by weight of catalyst, 10 parts by weight of acetone and 100 parts by weight of deionized water; dehydrating polyether polyol at the temperature of 100-120 ℃ for 1h in vacuum, and cooling to 60 ℃; then adding organic solvents acetone and silicon-containing diphenol, stirring and mixing uniformly, adding isocyanate and a catalyst, and stirring at constant temperature for reacting for 6 hours; cooling to 30 ℃, finally adding an emulsifier OP-10 and deionized water, and carrying out high-speed shearing and dispersion for 2h to obtain the low-viscosity high-temperature-resistant adhesive liquid.
S3, coating (spin coating) the adhesive liquid on the PET film subjected to corona treatment, drying in an oven at the temperature of 100-110 ℃, cooling, and attaching a protective layer to the surface coated with the adhesive liquid to obtain the PET protective film.
Example 2
A preparation process of a low-viscosity high-temperature-resistant protective film specifically comprises the following steps:
s1, pretreatment of the PET film: the PET film was corona treated, then washed with acetone and alcohol in sequence, and then dried in a vacuum oven at 70 ℃ for 12 hours for further use.
S2, preparing adhesive liquid, comprising the following steps:
s21, preparing the silicon-containing diphenol, and the specific steps are as follows: (1) adding 0.11mol of p-chlorophenol, 0.2mol of pyridine and 100mL of anhydrous toluene into a reaction flask, dropwise adding 0.12mol of trimethylchlorosilane under stirring in an ice bath, heating to room temperature after dropwise adding, stirring for reacting for 8 hours, evaporating and concentrating the filtered solution, and drying in vacuum to obtain a liquid intermediate product a; (2) adding 0.2mol of metal sodium and 100mL of anhydrous toluene into a three-neck flask, stirring, adding a dropping funnel at constant pressure, a thermometer and a condenser, and continuously introducing nitrogen for protection; heating to 110 ℃, vigorously stirring to disperse the metal sodium in toluene to form metal microspheres, cooling to 80 ℃, dissolving the intermediate product a and 50mmol of diphenyldichlorosilane in 20mL of toluene to prepare a solution, dropwise adding the solution into a flask, carrying out reflux reaction for 4 hours, and cooling to room temperature; adding 10mL of anhydrous methanol into a reaction flask to consume excessive metal sodium, and evaporating and concentrating the solution to half volume to obtain a concentrated solution containing an intermediate product b; (3) dropwise adding a hydrochloric acid solution (1mol, 15mL) into the concentrated solution obtained in the step (2), and stirring for 30min after dropwise adding; the organic phase is washed with pure water and dried over magnesium sulfate, the solvent is removed by evaporation, and the concentrate is cooled to 0 ℃ for crystallization to give the product silicon-containing diphenol. Recrystallizing the silicon-containing diphenol with toluene to obtain the pure silicon-containing diphenol.
S22, mixing methylimidazole and bromoethane with the molar ratio of 1:1, stirring, heating to 80 ℃, reacting for 5 hours, and washing with ethyl acetate for multiple times to obtain the catalyst.
S23, weighing the components of the adhesive liquid: 40 parts by weight of polyester polyol, 10 parts by weight of silicon-containing diphenol, 5 parts by weight of isocyanate, 2 parts by weight of emulsifier, 10 parts by weight of catalyst, 30 parts by weight of acetone and 150 parts by weight of deionized water; dehydrating polyester polyol at the temperature of 100-120 ℃ for 5h in vacuum, and cooling to 80 ℃; then adding organic solvents acetone and silicon-containing diphenol, stirring and mixing uniformly, adding isocyanate and a catalyst, and stirring at constant temperature for reacting for 6 hours; cooling to 30 ℃, finally adding an emulsifier SDBS and deionized water, and carrying out high-speed shearing and dispersion for 2h to obtain the low-viscosity high-temperature-resistant adhesive liquid.
S3, coating (spin coating) the adhesive liquid on the PET film subjected to corona treatment, drying in an oven at the temperature of 100-110 ℃, cooling, and attaching a protective layer to the surface coated with the adhesive liquid to obtain the PET protective film.
Comparative example 1
The specific steps of the preparation process of the low-viscosity high-temperature-resistant protective film are the same as those of the example 1, and the difference is that the adhesive liquid adopts the low-viscosity adhesive purchased in the market at present.
Comparative example 2
The preparation process of the low-viscosity high-temperature-resistant protective film is the same as that in example 1, except that the adhesive liquid does not contain silicon-containing diphenol.
The protective films obtained in examples 1 and 2 and comparative examples 1 and 2 were subjected to adhesion test (see national standard GB/T2792-1995); the high temperature resistance test is to apply the sample on a 304SUS plate, keep the temperature at 120 ℃ for 60min, and then keep the temperature at 140 ℃ for 60 min; the mechanical property test refers to the national standard GB/T3398.2-2008. The results of the performance tests are shown in table 1.
Table 1 results of performance test of protective films prepared in examples 1 and 2 and comparative examples 1 and 2
As can be seen from table 1, compared with the commercially available low viscose (comparative example 1), the adhesive solution of the present invention has been developed and innovated, the prepared protective films (examples 1 and 2) have lower adhesion, and the high temperature performance is significantly improved. Compared with the adhesive liquid without silicon-containing diphenol, the protective films (example 1 and example 2) prepared by the process disclosed by the invention are lower in adhesion and better in high temperature resistance, and the protective films of examples 1 and 2 are still cold and hot without degumming at 140 ℃ and show remarkable high temperature resistance. Therefore, the addition of the silicon-containing diphenol improves the high-temperature resistance of the adhesive liquid, further improves the high-temperature resistance of the protective film, and is suitable for being used for foaming materials.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (6)
1. A preparation process of a low-viscosity high-temperature-resistant protective film is characterized in that adhesive liquid is coated on a PET film subjected to corona treatment, the PET film is placed in an oven with the temperature of 100-110 ℃ for drying and cooling, and a protective layer is attached to one surface coated with the adhesive liquid to obtain the PET protective film; the adhesive liquid consists of 20-40 parts by weight of macromolecular polyol, 10-15 parts by weight of silicon-containing diphenol, 5-10 parts by weight of isocyanate, 0.5-2 parts by weight of emulsifier, 4-10 parts by weight of catalyst, 10-30 parts by weight of acetone and 120-150 parts by weight of deionized water; the emulsifier is one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and OP-10; the preparation process comprises the following steps:
s1, pretreating a PET film;
s2, preparing adhesive liquid, comprising the following steps:
s21, reacting p-chlorophenol and trimethylchlorosilane in a solvent toluene to obtain an intermediate a; reacting the intermediate a with dichlorosilane to obtain an intermediate b; hydrolyzing the intermediate b under an acidic condition to prepare silicon-containing diphenol;
s22, mixing methylimidazole and bromoethane with the molar ratio of 1:1, stirring, heating to 80 ℃, reacting for 5 hours, and washing with ethyl acetate for multiple times to obtain a catalyst;
s23, dehydrating the macromolecular polyalcohol at the temperature of 100-120 ℃ in vacuum for 1-5h, and cooling to 60-80 ℃; then adding organic solvents acetone and silicon-containing diphenol, stirring and mixing uniformly, adding isocyanate and a catalyst, and stirring at constant temperature for reacting for 5-6 h; cooling to 30-50 ℃, finally adding an emulsifier and deionized water, and carrying out high-speed shearing and dispersion for 2h to obtain a low-viscosity high-temperature-resistant adhesive liquid;
s3, coating the adhesive liquid on the PET film subjected to corona treatment, drying in an oven at the temperature of 100-110 ℃, cooling, and attaching a protective layer to the surface coated with the adhesive liquid to obtain the PET protective film.
2. The process for preparing a low-viscosity high-temperature-resistant protective film according to claim 1, wherein the step S21 is specifically: (1) adding p-chlorophenol, pyridine and anhydrous toluene into a reaction flask, dropwise adding trimethylchlorosilane under stirring in an ice bath, heating to room temperature after dropwise adding, stirring for reacting for 8 hours, evaporating and concentrating the filtered solution, and drying in vacuum to obtain a liquid intermediate product a; (2) adding metal sodium and anhydrous toluene into a three-neck flask, and continuously introducing nitrogen for protection, wherein the three-neck flask is provided with a stirrer, a constant-pressure dropping funnel, a thermometer and a condenser; heating to 110 ℃, vigorously stirring to disperse the metal sodium in toluene to form metal microspheres, then cooling to 80 ℃, dissolving the intermediate product a and dichlorosilane in toluene to prepare a solution, dropwise adding the solution into a flask, carrying out reflux reaction for 4 hours, and cooling to room temperature; evaporating and concentrating the solution to half volume to obtain a concentrated solution containing an intermediate product b; (3) dropwise adding a hydrochloric acid solution into the concentrated solution obtained in the step (2), and stirring for 30min after dropwise adding; the organic phase is washed with pure water and dried over magnesium sulfate, the solvent is removed by evaporation, and the concentrate is cooled to 0 ℃ for crystallization to give the product silicon-containing diphenol.
3. The process for preparing a low viscosity high temperature resistant protective film according to claim 2, wherein the prepared silicon-containing diphenol is recrystallized with toluene to obtain pure silicon-containing diphenol.
4. The process for preparing a low viscosity high temperature resistant protective film according to claim 3, wherein the structural formula of the silicon-containing diphenol is:
in the formula, R1And R2Respectively methyl or phenyl.
5. The process for preparing a low-viscosity high-temperature-resistant protective film according to claim 1, wherein the macromolecular polyol is polyether polyol or polyester polyol.
6. The process for preparing a low-viscosity high-temperature-resistant protective film according to claim 1, wherein the thickness of the PET film is 50-200 μm.
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