A method for preparing anti-corrosion and heat-resistant TPX release film

Abstract

The present invention provides a method for preparing a corrosion-resistant and heat-resistant TPX release film, comprising the following steps: stirring TPX, dimethylamide, and silica polymer powder at high temperature to obtain a mixture A; adding dioctyl terephthalate (a plasticizer) and dolomite-doped cobalt oxide porous nanospheres to the mixture A and stirring uniformly; performing ultrasonic dispersion; allowing the mixture to stand for degassing; and casting the mixture onto a horizontal glass plate for drying to obtain the corrosion-resistant and heat-resistant TPX release film. The silica polymer powder is an environmentally friendly corrosion inhibitor. The addition of the silica polymer powder acts as a cross-linking filler in the molecular chains of TPX, ensuring the corrosion resistance of TPX while improving its heat resistance. Furthermore, the metallic cobalt in the added cobalt nanospheres is a good heat-resistant material. Dolomite is also added to the cobalt nanospheres. The addition of dolomite significantly hinders molecular motion during heating, thereby improving the heat resistance of the release film.

Description

Technical Field

[0001] The present invention relates to the field of polymer materials, and in particular to a method for preparing a corrosion-resistant and heat-resistant TPX release film. Background Art

[0002] Release film, also known as isolating film, peeling film, separating film, or mold release film, refers to a thin film with a separating surface. It exhibits no or slight adhesion to specific materials under limited conditions. Release film is widely used in the processing of various products and in the mobile phone, medical, home appliance manufacturing, anti-counterfeiting materials, semiconductor, automotive, nameplate, ceramic sheet manufacturing, tape production, and die-cutting industries. There are many types of release films. Depending on the substrate, release films can be categorized as PE, PET, TPX, OPP, PC, PS, PMMA, and BOPP. Based on their release force, release films can be classified as light, medium, and heavy release. Based on their color, release films can be categorized as red, yellow, green, blue, milky white, matte, pearlescent, and black.

[0003] Existing release films often suffer from shortcomings such as poor long-term high-temperature resistance, yellowing, and corrosion. Furthermore, release films frequently come into contact with electronic and electrical components during use. When components overheat, the film lacks sufficient heat resistance, potentially causing the film to melt and deform, impacting the proper functioning of the components. Given these challenges, there is an urgent need to develop corrosion-resistant and heat-resistant release films for application in production and processing across various industries. Summary of the Invention

[0004] Technical problem to be solved: The purpose of the present invention is to provide a method for preparing a corrosion-resistant and heat-resistant TPX release film, which improves the heat resistance and mechanical properties of the TPX release film by adding silicate polymer powder and dolomite-doped cobalt oxide porous nanospheres.

[0005] Technical solution: A method for preparing a corrosion-resistant and heat-resistant TPX release film, which comprises the following steps, calculated by weight:

[0006] (1) Take 15 to 30 parts of TPX, add 5 to 10 parts of dimethylamide, heat and stir at 240 to 280°C for 0.5 h, then add 1 to 5 parts of silicate polymer powder and continue heating and stirring for 2 to 3 h to obtain mixture A;

[0007] (2) adding 0.5 to 1 parts of dioctyl terephthalate (a plasticizer) and 1 to 5 parts of dolomite-doped cobalt oxide porous nanospheres to the mixture A obtained in step (1), and stirring at 1500 to 2000 r / min for 1 hour;

[0008] (3) Ultrasonic dispersion for 20 to 30 minutes;

[0009] (4) Let it stand for 24 to 48 hours to degas;

[0010] (5) Casting onto a horizontal glass plate and drying at 120-150° C. for 12-24 hours to obtain a corrosion-resistant and heat-resistant TPX release film. Preferably, the specific preparation steps of the dolomite-doped cobalt oxide porous nanoparticles in step (2) are as follows:

[0011] S1: preparation of dolomite suspension;

[0012] S2: Add zirconium oxychloride, deionized water, and acetylacetone into a round-bottom flask in a certain proportion, add aqueous ammonia while stirring, and stir at 70-85°C for 8-10 hours to obtain a zirconium dioxide aqueous solution.

[0013] S3: adding cobalt nitrate hexahydrate and formaldehyde aqueous solution to a mixed solution of zirconium dioxide aqueous solution and dolomite suspension, stirring at a speed of 4000-5000 r / min for 3-6 hours, adding glutaraldehyde and letting it stand for 15-20 hours, then adding deionized water and stirring at a speed of 2000-3000 r / min for 1 minute, letting it stand for 2-3 hours and discarding the supernatant, filtering the precipitate and calcining it at high temperature to obtain dolomite-doped cobalt oxide porous nanospheres.

[0014] Preferably, the specific steps for preparing the dolomite suspension in S1 are as follows:

[0015] S11: using a grinder to grind the human fiber pulp to obtain a flocculent and uniform cellulose pulp, and drying it at 60-80°C;

[0016] S12: Weigh a certain amount of cellulose pulp and add it to a 10% NaOH solution. Freeze it at -20 to -30°C for 12 hours and then thaw it. After thawing, add hydrochloric acid dropwise to adjust the solution to neutrality. Centrifuge it at 8,000 to 10,000 rpm for 3 to 5 times, discard the supernatant, and retain the precipitate.

[0017] S13: dissolving the precipitate with deionized water, and obtaining a nanocellulose solution with a fiber diameter of less than 10 nm after shearing, ultrasonication, and centrifugation;

[0018] S14: adding ultrafine dolomite to the nanocellulose solution in a mass ratio of (2-3):5 to obtain a dolomite suspension.

[0019] Preferably, the particle size of the dolomite-doped cobalt oxide porous nanospheres in step (2) is 3 to 5 μm.

[0020] Preferably, the mass ratio of zirconium oxychloride, deionized water, acetylacetone and ammonia water in S2 is 7:20:1:2, and the concentration of ammonia water is 25%.

[0021] Preferably, the volume ratio of the zirconium dioxide aqueous solution to the dolomite suspension in S3 is 1:1, and the cobalt nitrate hexahydrate and the formaldehyde aqueous solution account for 20-30% of the total solution volume, wherein the volume ratio of the cobalt nitrate hexahydrate to the formaldehyde aqueous solution is 2:(3-4). Preferably, the heating rate of the high-temperature calcination in S3 is 2.5-4°C, and the final temperature is raised to 650-700°C, and the holding time is 3 hours. Preferably, the volume ratio of the cellulose pulp to the NaOH solution in S12 is 1:(3-5).

[0022] Preferably, in S13, the shearing speed is 12000-15000 r / min, the time is 1 hour, the ultrasonic time is 2-3 hours, and the centrifugal speed is 6000-8000 r / min, and the time is 4-5 hours.

[0023] Beneficial effects:

[0024] 1. The silicate polymer powder in the present invention is an environmentally friendly corrosion inhibitor. The addition of silicate polymer powder plays a cross-linking and filling role in the molecular chain of TPX, ensuring the anti-corrosion performance of TPX while improving its heat resistance.

[0025] 2. The metallic cobalt in the cobalt oxide porous nano-microspheres added in the present invention is a good heat-resistant material. Dolomite is also added to the cobalt porous nano-microspheres. The addition of dolomite significantly hinders the movement of molecules during heating, thereby improving the heat resistance of the release film.

[0026] 3. The cobalt oxide in the present invention has a porous structure, which improves the adhesion of dolomite. At the same time, the porous structure promotes the formation of a meshing structure between TPX material molecules, improves the binding force between dolomite-doped cobalt oxide porous nano-microspheres and TPX, and significantly improves the mechanical properties of the release film. DETAILED DESCRIPTION

[0027] The present invention will be further described below in conjunction with examples, which are provided to explain the present invention and are not limited to the following examples:

[0028] Example 1

[0029] A method for preparing a corrosion-resistant and heat-resistant TPX release film comprises the following steps, measured in parts by weight:

[0030] (1) Take 15 parts of TPX, add 5 parts of dimethyl amide, heat and stir at 240°C for 0.5 h, then add 1 part of silicate polymer powder and continue heating and stirring for 2 h to obtain mixture A;

[0031] (2) adding 0.5 parts of dioctyl terephthalate (a plasticizer) and 1 part of dolomite-doped cobalt oxide porous nanospheres to the mixture A prepared in step (1), and stirring at 1500 r / min for 1 hour;

[0032] (3) Ultrasonic dispersion for 20 min;

[0033] (4) Let it stand for 24 hours to degas;

[0034] (5) Cast onto a horizontal glass plate and dry at 120°C for 12 hours to obtain the corrosion-resistant and heat-resistant TPX release film.

[0035] The specific preparation steps of the dolomite-doped cobalt oxide porous nanospheres in step (2) are as follows:

[0036] S1: preparing a dolomite suspension, wherein the dolomite suspension is prepared by the following steps:

[0037] S11: using a grinder to grind the human fiber pulp to obtain a flocculent and uniform cellulose pulp, and drying it at 60°C;

[0038] S12: Weigh 1 kg of cellulose pulp and add it to 3 kg of 10% NaOH solution. Freeze the solution at -20°C for 12 hours and then freeze it. After thawing, add hydrochloric acid dropwise to adjust the solution to neutrality. Centrifuge at 8000 rpm for 3 times, discard the supernatant, and retain the precipitate.

[0039] S13: The precipitate was dissolved in deionized water, and treated with shearing at 12000 rpm for 1 h, ultrasonication at 2 h, and centrifugation at 6000 rpm for 4 h to obtain a nanocellulose solution with a fiber diameter of less than 10 nm;

[0040] S14: Weigh 0.6 kg of ultrafine dolomite and 1.8 kg of nanocellulose solution, add the ultrafine dolomite to the nanocellulose solution to obtain a dolomite suspension.

[0041] S2: Add 70 g of zirconium oxychloride, 200 g of deionized water, and 10 g of acetylacetone into a round-bottom flask, add 140 g of ammonia water while stirring, and stir at 70°C for 8 h to obtain a zirconium dioxide aqueous solution;

[0042] S3: Add 75mL of cobalt nitrate hexahydrate and 150mL of formaldehyde aqueous solution to a mixed solution of zirconium dioxide aqueous solution and dolomite suspension, the volume of the zirconium dioxide aqueous solution and the dolomite suspension are both 300mL, stir at 4000r / min for 4h, add glutaraldehyde and let it stand for 15h, then add deionized water and stir at 2500r / min for 1min, let it stand for 2h and discard the supernatant, filter the precipitate and calcine it at high temperature, the high temperature calcination heating rate is 2.5℃, and finally the temperature is raised to 680℃ and kept warm for 3h to obtain dolomite-doped cobalt oxide porous nanospheres.

[0043] Example 2

[0044] A method for preparing a corrosion-resistant and heat-resistant TPX release film comprises the following steps, measured in parts by weight:

[0045] (1) 17 parts of TPX were added with 6 parts of dimethylamide and heated and stirred at 250°C for 0.5 h. Then, 2 parts of silicate polymer powder were added and heated and stirred for 2.5 h to obtain a mixture A.

[0046] (2) adding 0.6 parts of dioctyl terephthalate (a plasticizer) and 2 parts of dolomite-doped cobalt oxide porous nanospheres to the mixture A prepared in step (1), and stirring at 1600 r / min for 1 hour;

[0047] (3) Ultrasonic dispersion for 25 min;

[0048] (4) Let it stand for 30 hours to degas;

[0049] (5) Cast onto a horizontal glass plate and dry at 125°C for 15 hours to obtain the corrosion-resistant and heat-resistant TPX release film.

[0050] The specific preparation steps of the dolomite-doped cobalt oxide porous nanospheres in step (2) are as follows:

[0051] S1: preparing a dolomite suspension, wherein the dolomite suspension is prepared by the following steps:

[0052] S11: using a grinder to grind the human fiber pulp to obtain a flocculent and uniform cellulose pulp, and drying it at 65°C;

[0053] S12: Weigh 1 kg of cellulose pulp and add it to 3 kg of 10% NaOH solution. Freeze the solution at -25°C for 12 hours and then freeze it. After thawing, add hydrochloric acid dropwise to adjust the solution to neutrality. Centrifuge at 8000 rpm for 3 times, discard the supernatant, and retain the precipitate.

[0054] S13: The precipitate was dissolved in deionized water, and treated with shearing at 13,000 rpm for 1 h, ultrasonication at 6,500 rpm for 2.5 h, and centrifugation at 6,500 rpm for 4 h to obtain a nanocellulose solution with a fiber diameter of less than 10 nm;

[0055] S14: Weigh 0.6 kg of ultrafine dolomite and 2.4 kg of nanocellulose solution, and add the ultrafine dolomite to the nanocellulose solution to obtain a dolomite suspension.

[0056] S2: Add 70 g of zirconium oxychloride, 200 g of deionized water, and 10 g of acetylacetone into a round-bottom flask, add 140 g of ammonia water while stirring, and stir at 70°C for 8 h to obtain a zirconium dioxide aqueous solution;

[0057] S3: Add 16 mL of cobalt nitrate hexahydrate and 24 mL of formaldehyde aqueous solution to a mixed solution of zirconium dioxide aqueous solution and dolomite suspension, the volume of each of the zirconium dioxide aqueous solution and the dolomite suspension is 200 mL, stir at 4000 r / min for 3 hours, add glutaraldehyde and let it stand for 15 hours, then add deionized water and stir at 2000 r / min for 1 minute, let it stand for 2 hours and discard the supernatant, filter the precipitate and calcine it at high temperature, the high temperature calcination heating rate is 2.5°C, and finally the temperature is raised to 650°C and kept warm for 3 hours to obtain dolomite-doped cobalt oxide porous nanospheres.

[0058] Example 3

[0059] A method for preparing a corrosion-resistant and heat-resistant TPX release film comprises the following steps, measured in parts by weight:

[0060] (1) Take 20 parts of TPX, add 6 parts of dimethylamide, heat and stir at 250°C for 0.5 h, then add 3 parts of silicate polymer powder and continue heating and stirring for 3 h to obtain mixture A;

[0061] (2) adding 0.7 parts of dioctyl terephthalate (a plasticizer) and 3 parts of dolomite-doped cobalt oxide porous nanospheres to the mixture A prepared in step (1), and stirring at 1700 r / min for 1 hour;

[0062] (3) Ultrasonic dispersion for 20 min;

[0063] (4) Let it stand for 48 hours to degas;

[0064] (5) Cast onto a horizontal glass plate and dry at 130°C for 24 hours to obtain the corrosion-resistant and heat-resistant TPX release film.

[0065] The specific preparation steps of the dolomite-doped cobalt oxide porous nanospheres in step (2) are as follows:

[0066] S1: preparing a dolomite suspension, wherein the dolomite suspension is prepared by the following steps:

[0067] S11: using a grinder to grind the human fiber pulp to obtain a flocculent and uniform cellulose pulp, and drying it at 70°C;

[0068] S12: Weigh 1 kg of cellulose pulp and add it to 3 kg of 10% NaOH solution. Freeze at -25°C for 12 hours and then thaw. After thawing, add hydrochloric acid dropwise to adjust the solution to neutrality. Centrifuge at 9000 rpm for 4 times, discard the supernatant, and retain the precipitate.

[0069] S13: The precipitate was dissolved in deionized water, and treated with shearing at 14,000 rpm for 1 hour, ultrasonic treatment at 7,000 rpm for 2.5 hours, and centrifugation at 7,000 rpm for 4 hours to obtain a nanocellulose solution with a fiber diameter of less than 10 nm;

[0070] S14: Weigh 0.6 kg of ultrafine dolomite and 3 kg of nanocellulose solution, and add the ultrafine dolomite to the nanocellulose solution to obtain a dolomite suspension.

[0071] S2: 70 g of zirconium oxychloride, 200 g of deionized water, and 10 g of acetylacetone were added to a round-bottom flask, and 140 g of ammonia water was added while stirring. The mixture was stirred at 75°C for 9 h to obtain a zirconium dioxide aqueous solution.

[0072] S3: Add 40 mL of cobalt nitrate hexahydrate and 80 mL of formaldehyde aqueous solution to a mixed solution of zirconium dioxide aqueous solution and dolomite suspension, the volume of each of the zirconium dioxide aqueous solution and the dolomite suspension is 200 mL, stir at 4500 r / min for 4 hours, add glutaraldehyde and let it stand for 15 hours, then add deionized water and stir at 3000 r / min for 1 minute, let it stand for 2 hours and discard the supernatant, filter the precipitate and calcine it at high temperature, the high temperature calcination heating rate is 3°C, and finally the temperature is raised to 650°C and kept warm for 3 hours to obtain dolomite-doped cobalt oxide porous nanospheres.

[0073] Example 4

[0074] A method for preparing a corrosion-resistant and heat-resistant TPX release film comprises the following steps, measured in parts by weight:

[0075] (1) 24 parts of TPX were added with 8 parts of dimethylamide and heated and stirred at 260°C for 0.5 h, and then 4 parts of silicate polymer powder were added and heated and stirred for 3 h to obtain mixture A;

[0076] (2) adding 0.8 parts of dioctyl terephthalate (a plasticizer) and 4 parts of dolomite-doped cobalt oxide porous nanospheres to the mixture A prepared in step (1), and stirring at 1800 r / min for 1 hour;

[0077] (3) Ultrasonic dispersion for 25 min;

[0078] (4) Let it stand for 35 hours to degas;

[0079] (5) Cast onto a horizontal glass plate and dry at 140°C for 20 hours to obtain the corrosion-resistant and heat-resistant TPX release film.

[0080] The specific preparation steps of the dolomite-doped cobalt oxide porous nanospheres in step (2) are as follows:

[0081] S1: preparing a dolomite suspension, wherein the dolomite suspension is prepared by the following steps:

[0082] S11: using a grinder to grind the human fiber pulp to obtain a flocculent and uniform cellulose pulp, and drying it at 70°C;

[0083] S12: Weigh 1 kg of cellulose pulp and add it to 3 kg of 10% NaOH solution. Freeze at -30°C for 12 hours and then thaw. After thawing, add hydrochloric acid dropwise to adjust the solution to neutrality. Centrifuge at 10,000 rpm for 5 times, discard the supernatant, and retain the precipitate.

[0084] S13: The precipitate was dissolved in deionized water, and treated with shearing at 14,000 rpm for 1 hour, ultrasonic treatment at 8,000 rpm for 2.5 hours, and centrifugation at 8,000 rpm for 4 hours to obtain a nanocellulose solution with a fiber diameter of less than 10 nm.

[0085] S14: Weigh 0.5 kg of ultrafine dolomite and 2 kg of nanocellulose solution, and add the ultrafine dolomite to the nanocellulose solution to obtain a dolomite suspension.

[0086] S2: 70 g of zirconium oxychloride, 200 g of deionized water, and 10 g of acetylacetone were added to a round-bottom flask, and 140 g of ammonia water was added while stirring. The mixture was stirred at 80°C for 9 h to obtain a zirconium dioxide aqueous solution.

[0087] S3: Add 40 mL of cobalt nitrate hexahydrate and 60 mL of formaldehyde aqueous solution to a mixed solution of zirconium dioxide aqueous solution and dolomite suspension, the volume of each of the zirconium dioxide aqueous solution and the dolomite suspension is 200 mL, stir at 4500 r / min for 5 hours, add glutaraldehyde and let stand for 15 hours, then add deionized water and stir at 3000 r / min for 1 minute, let stand for 3 hours and discard the supernatant, filter the precipitate and calcine at high temperature, the high temperature calcination heating rate is 3°C, and finally the temperature is raised to 680°C and kept warm for 3 hours to obtain dolomite-doped cobalt oxide porous nanospheres.

[0088] Example 5

[0089] A method for preparing a corrosion-resistant and heat-resistant TPX release film comprises the following steps, measured in parts by weight:

[0090] (1) 28 parts of TPX were added to 9 parts of dimethylamide and heated and stirred at 270°C for 0.5 h. 5 parts of silicate polymer powder were then added and heated and stirred for 3 h to obtain a mixture A.

[0091] (2) adding 0.8 parts of dioctyl terephthalate (a plasticizer) and 4 parts of dolomite-doped cobalt oxide porous nanospheres to the mixture A prepared in step (1), and stirring at 2000 r / min for 1 hour;

[0092] (3) Ultrasonic dispersion for 30 min;

[0093] (4) Let it stand for 30 hours to degas;

[0094] (5) Cast onto a horizontal glass plate and dry at 145°C for 20 hours to obtain the corrosion-resistant and heat-resistant TPX release film.

[0095] The specific preparation steps of the dolomite-doped cobalt oxide porous nanospheres in step (2) are as follows:

[0096] S1: preparing a dolomite suspension, wherein the dolomite suspension is prepared by the following steps:

[0097] S11: using a grinder to grind the human fiber pulp to obtain a flocculent and uniform cellulose pulp, and drying it at 80°C;

[0098] S12: Weigh 1 kg of cellulose pulp and add it to 3 kg of 10% NaOH solution. Freeze at -30°C for 12 hours and then thaw. After thawing, add hydrochloric acid dropwise to adjust the solution to neutrality. Centrifuge at 10,000 rpm for 5 times, discard the supernatant, and retain the precipitate.

[0099] S13: dissolving the precipitate with deionized water, and subjecting the precipitate to shearing at 15,000 rpm for 1 h, ultrasonic treatment at 8,000 rpm for 3 h, and centrifugation at 8,000 rpm for 5 h to obtain a nanocellulose solution with a fiber diameter of less than 10 nm;

[0100] S14: Weigh 0.5 kg of ultrafine dolomite and 2.25 kg of nanocellulose solution, and add the ultrafine dolomite to the nanocellulose solution to obtain a dolomite suspension.

[0101] S2: 70 g of zirconium oxychloride, 200 g of deionized water, and 10 g of acetylacetone were added to a round-bottom flask, and 140 g of ammonia water was added while stirring. The mixture was stirred at 85°C for 10 h to obtain a zirconium dioxide aqueous solution.

[0102] S3: Add 50 mL of cobalt nitrate hexahydrate and 100 mL of formaldehyde aqueous solution to a mixed solution of zirconium dioxide aqueous solution and dolomite suspension, the volume of the zirconium dioxide aqueous solution and the dolomite suspension are both 300 mL, stir at 5000 r / min for 6 hours, add glutaraldehyde and let it stand for 20 hours, then add deionized water and stir at 3000 r / min for 1 minute, let it stand for 3 hours and discard the supernatant, filter the precipitate and calcine it at high temperature, the high temperature calcination heating rate is 4°C, and finally the temperature is raised to 700°C and kept warm for 3 hours to obtain dolomite-doped cobalt oxide porous nanospheres.

[0103] Comparative Example 1

[0104] The difference between this embodiment and embodiment 4 is that the embodiment does not contain silicate polymer powder. Specifically:

[0105] A method for preparing a corrosion-resistant and heat-resistant TPX release film comprises the following steps, measured in parts by weight:

[0106] (1) 24 parts of TPX were added with 8 parts of dimethylamide and heated and stirred at 260°C for 0.5 h to obtain a mixture A;

[0107] (2) adding 0.8 parts of dioctyl terephthalate (a plasticizer) and 4 parts of dolomite-doped cobalt oxide porous nanospheres to the mixture A prepared in step (1), and stirring at 1800 r / min for 1 hour;

[0108] (3) Ultrasonic dispersion for 25 min;

[0109] (4) Let it stand for 35 hours to degas;

[0110] (5) Cast onto a horizontal glass plate and dry at 140°C for 20 hours to obtain the corrosion-resistant and heat-resistant TPX release film.

[0111] The specific preparation steps of the dolomite-doped cobalt oxide porous nanospheres in step (2) are as follows:

[0112] S1: preparing a dolomite suspension, wherein the dolomite suspension is prepared by the following steps:

[0113] S11: using a grinder to grind the human fiber pulp to obtain a flocculent and uniform cellulose pulp, and drying it at 70°C;

[0114] S12: Weigh 1 kg of cellulose pulp and add it to 3 kg of 10% NaOH solution. Freeze at -30°C for 12 hours and then thaw. After thawing, add hydrochloric acid dropwise to adjust the solution to neutrality. Centrifuge at 10,000 rpm for 5 times, discard the supernatant, and retain the precipitate.

[0115] S13: The precipitate was dissolved in deionized water, and treated with shearing at 14,000 rpm for 1 hour, ultrasonic treatment at 8,000 rpm for 2.5 hours, and centrifugation at 8,000 rpm for 4 hours to obtain a nanocellulose solution with a fiber diameter of less than 10 nm.

[0116] S14: Weigh 0.5 kg of ultrafine dolomite and 2 kg of nanocellulose solution, and add the ultrafine dolomite to the nanocellulose solution to obtain a dolomite suspension.

[0117] S2: 70 g of zirconium oxychloride, 200 g of deionized water, and 10 g of acetylacetone were added to a round-bottom flask, and 140 g of ammonia water was added while stirring. The mixture was stirred at 80°C for 9 h to obtain a zirconium dioxide aqueous solution.

[0118] S3: Add 40 mL of cobalt nitrate hexahydrate and 60 mL of formaldehyde aqueous solution to a mixed solution of zirconium dioxide aqueous solution and dolomite suspension, the volume of each of the zirconium dioxide aqueous solution and the dolomite suspension is 200 mL, stir at 4500 r / min for 5 hours, add glutaraldehyde and let stand for 15 hours, then add deionized water and stir at 3000 r / min for 1 minute, let stand for 3 hours and discard the supernatant, filter the precipitate and calcine at high temperature, the high temperature calcination heating rate is 3°C, and finally the temperature is raised to 680°C and kept warm for 3 hours to obtain dolomite-doped cobalt oxide porous nanospheres.

[0119] Comparative Example 2

[0120] The difference between this embodiment and embodiment 4 is that the dolomite-doped cobalt oxide porous nano-microspheres are not included. Specifically:

[0121] A method for preparing a corrosion-resistant and heat-resistant TPX release film comprises the following steps, measured in parts by weight:

[0122] (1) 24 parts of TPX were added with 8 parts of dimethylamide and heated and stirred at 260°C for 0.5 h, and then 4 parts of silicate polymer powder were added and heated and stirred for 3 h to obtain mixture A;

[0123] (2) adding 0.8 parts of dioctyl terephthalate (a plasticizer) to the mixture A obtained in step (1) and stirring at 1800 r / min for 1 hour;

[0124] (3) Ultrasonic dispersion for 25 min;

[0125] (4) Let it stand for 35 hours to degas;

[0126] (5) Cast onto a horizontal glass plate and dry at 140°C for 20 hours to obtain the corrosion-resistant and heat-resistant TPX release film.

[0127] Comparative Example 3

[0128] The difference between this embodiment and embodiment 4 is that the added cobalt oxide porous nano-microspheres do not contain dolomite. Specifically: A method for preparing an anti-corrosion and heat-resistant TPX release film, in parts by weight, comprises the following steps:

[0129] (1) 24 parts of TPX were added with 8 parts of dimethylamide and heated and stirred at 260°C for 0.5 h, and then 4 parts of silicate polymer powder were added and heated and stirred for 3 h to obtain mixture A;

[0130] (2) adding 0.8 parts of dioctyl terephthalate (a plasticizer) and 4 parts of cobalt oxide porous nanospheres to the mixture A prepared in step (1), and stirring at 1800 r / min for 1 hour;

[0131] (3) Ultrasonic dispersion for 25 min;

[0132] (4) Let it stand for 35 hours to degas;

[0133] (5) Cast onto a horizontal glass plate and dry at 140°C for 20 hours to obtain the corrosion-resistant and heat-resistant TPX release film.

[0134] The specific preparation steps of the cobalt oxide-doped porous nanospheres in step (2) are as follows:

[0135] S1: 70 g zirconium oxychloride, 200 g deionized water, and 10 g acetylacetone were added to a round-bottom flask, and 140 g ammonia solution was added while stirring. The mixture was stirred at 80°C for 9 h to obtain a zirconium dioxide aqueous solution.

[0136] S3: Add 40 mL of cobalt nitrate hexahydrate and 60 mL of formaldehyde aqueous solution to the zirconium dioxide aqueous solution. 400 mL of the zirconium dioxide aqueous solution is stirred at 4500 r / min for 5 hours. After adding glutaraldehyde, it is allowed to stand for 15 hours. Then, deionized water is added and stirred at 3000 r / min for 1 minute. After standing for 3 hours, the supernatant is discarded, the precipitate is filtered and calcined at high temperature. The high-temperature calcination heating rate is 3°C, and the temperature is finally raised to 680°C and kept warm for 3 hours to obtain dolomite-doped cobalt oxide porous nanospheres.

[0137] The performance of the anti-corrosion and heat-resistant TPX release films prepared in Examples 1 to 5 and Comparative Examples 1 to 3 was compared and analyzed. According to GB / T 528-2009, mechanical properties were tested using a universal testing machine at a tensile rate of 100 mm / min. The experimental results are the average of six experimental results, as shown in Table 1.

[0138] Table 1 Performance analysis of different embodiments and comparative examples

[0139] Tensile strength (MPa) Elongation at break (%) Example 1 57.8 136.8 Example 2 54.3 120.3 Example 3 53.5 112.5 Example 4 59.2 145.8 Example 5 54.1 123.9 Comparative Example 1 50.1 109.8 Comparative Example 2 47.9 98.8 Comparative Example 3 48.5 103.8

[0140] The corrosion-resistant and heat-resistant TPX release films prepared in Examples 1 to 5 and Comparative Examples 1 to 3 were placed at high temperatures of 130° C., 150° C., and 170° C. for 1 hour, and the surfaces of the release films were observed for abnormalities such as color spots and yellowing. The test results are shown in Table 2.

[0141] Table 1 Heat resistance test results of different embodiments and comparative examples

[0142] 130℃ 150℃ 170℃ Example 1 pass pass pass Example 2 pass pass pass Example 3 pass pass pass Example 4 pass pass pass Example 5 pass pass pass Comparative Example 1 pass pass Slight yellowing Comparative Example 2 pass Severe yellowing Severe yellowing Comparative Example 3 pass Slight yellowing Severe yellowing

[0143] It can be seen from Tables 1 and 2 that the addition of silicate polymer powder and dolomite-doped cobalt oxide porous nanospheres can significantly improve the heat resistance of the TPX release film, and also has a positive effect on the mechanical properties of the TPX release film.

[0144] Obviously, the above embodiments are merely examples for clarity of explanation and are not intended to limit the implementation methods. Those skilled in the art will readily appreciate that other variations or modifications based on the above descriptions are possible. It is not necessary and impossible to enumerate all implementation methods here. Obvious variations or modifications arising therefrom remain within the scope of protection of the present invention.

Claims

1. A corrosion-resistant and heat-resistant TPX release film, characterized by: Calculated by weight, comprising the following steps: (1) Take 15-30 parts of TPX, add 5-10 parts of dimethylamide, heat and stir at 240-280°C for 0.5 h, then add 1-5 parts of silicate polymer powder and continue heating and stirring for 2-3 h to obtain mixture A; (2) Add 0.5-1 parts of dioctyl terephthalate (a plasticizer) and 1-5 parts of dolomite-doped cobalt oxide porous microspheres to the mixture A prepared in step (1), and stir at 1500-2000 r / min for 1 hour; (3) Ultrasonic dispersion for 20-30 minutes; (4) Let it stand for 24 to 48 hours to degas; (5) Cast onto a horizontal glass plate and dry at 120-150°C for 12-24 hours to obtain the corrosion-resistant and heat-resistant TPX release film.

2. The corrosion-resistant and heat-resistant TPX release film according to claim 1, characterized in that: The specific preparation steps of dolomite-doped cobalt oxide porous microspheres in step (2) are as follows: S1: preparation of dolomite suspension; S2: Zirconium oxychloride, deionized water, and acetylacetone are added to a round-bottom flask in a certain proportion, and ammonia is added while stirring. Stir at 70-85°C for 8-10 hours to obtain a zirconium dioxide aqueous solution; S3: Add cobalt nitrate hexahydrate and formaldehyde aqueous solution to a mixed solution of zirconium dioxide aqueous solution and dolomite suspension, stir at 4000-5000 r / min for 3-6 hours, add glutaraldehyde and let it stand for 15-20 hours, then add deionized water and stir at 2000-3000 r / min for 1 minute, let it stand for 2-3 hours, discard the supernatant, filter the precipitate and calcine it at high temperature to obtain dolomite-doped cobalt oxide porous microspheres.

3. The corrosion-resistant and heat-resistant TPX release film according to claim 2, characterized in that: The specific preparation steps of the dolomite suspension in S1 are as follows: S11: using a grinder to grind the human fiber pulp to obtain a flocculent and uniform cellulose pulp, and drying it at 60-80°C; S12: Weigh a certain amount of cellulose pulp and add it to a 10% NaOH solution. Freeze at -20-30°C for 12 hours and then thaw. After thawing, add hydrochloric acid dropwise to adjust the solution to neutrality. Centrifuge at 8000-10000 rpm for 3-5 times, discard the supernatant, and retain the precipitate. S13: dissolving the precipitate with deionized water, and obtaining a nanocellulose solution with a fiber diameter of less than 10 nm after shearing, ultrasonication, and centrifugation; S14: adding ultrafine dolomite to the nanocellulose solution in a mass ratio of (3-5):4 to obtain a dolomite suspension.

4. The corrosion-resistant and heat-resistant TPX release film according to claim 1, characterized in that: The particle size of the dolomite-doped cobalt oxide porous microspheres in step (2) is 3-5 μm.

5. The corrosion-resistant and heat-resistant TPX release film according to claim 2, characterized in that: The mass ratio of zirconium oxychloride, deionized water, acetylacetone and ammonia water in S2 is 7:20:1:2, and the concentration of ammonia water is 25%.

6. The corrosion-resistant and heat-resistant TPX release film according to claim 2, characterized in that: The volume ratio of the zirconium dioxide aqueous solution and the dolomite suspension in S3 is 1:1, and the cobalt nitrate hexahydrate and the formaldehyde aqueous solution account for 20-30% of the total solution volume, wherein the volume ratio of the cobalt nitrate hexahydrate and the formaldehyde aqueous solution is 2:(3-4).

7. The corrosion-resistant and heat-resistant TPX release film according to claim 2, characterized in that: The temperature rise rate of the high temperature calcination in S3 is 2.5-4°C, and the temperature is finally raised to 650-700°C, and the holding time is 3 hours.

8. The corrosion-resistant and heat-resistant TPX release film according to claim 3, characterized in that: The volume ratio of the cellulose pulp to the NaOH solution in S12 is 1:(3~5).

9. The corrosion-resistant and heat-resistant TPX release film according to claim 3, characterized in that: In the S13, the shear speed is 12000-15000 r / min, the time is 1 hour, the ultrasonic time is 2-3 hours, and the centrifugal speed is 6000-8000 r / min, and the time is 4-5 hours.