High-temperature-resistant and low-temperature-resistant plastic film and preparation method thereof

Abstract

This invention discloses a high-temperature and low-temperature resistant plastic film and its preparation method, relating to the field of polymer materials. In preparing the high-temperature and low-temperature resistant plastic film, bis(4-fluorophenyl)phosphine oxide is reacted sequentially with acrylonitrile, hydroquinone with 4,4'-difluorobenzophenone, 2,4-dihydroxybenzonitrile, N-(2-aminopropyl)maleimide, and furfuryl isocyanate to obtain functionalized polyetheretherketone (PEEK). Glass fibers are then reacted sequentially with N-(3-trimethoxysilylpropyl)pyrrole, 1-allyl-1H-pyrrole with 1-methylpyrrole, N-(furan-2-ylmethyl)ethylamine, and 1,3-propanesulfonic acid lactone to obtain functionalized glass fibers. The functionalized glass fibers and functionalized PEEK are mixed, coated onto a polytetrafluoroethylene (PTFE) plate, and scraped off to obtain the high-temperature and low-temperature resistant plastic film. The high-temperature and low-temperature resistant plastic film prepared by this invention possesses durability, antibacterial properties, self-healing properties, antistatic properties, and flame retardant properties.

Description

Technical Field

[0001] This invention relates to the field of polymer materials, specifically to a high-temperature and low-temperature resistant plastic film and its preparation method. Background Technology

[0002] Plastics refer to materials whose basic components are polymer compounds. These materials can be polymerized in situ, flowed into shape, or solidified at a certain stage of processing or manufacturing. The finished product is a rigid or flexible solid. Based on their application fields, plastics can be divided into general-purpose plastics and engineering plastics. Engineering plastics can be used as structural materials and have excellent comprehensive performance. Polyetheretherketone (PEEK) is a superior engineering plastic with excellent high-temperature and low-temperature resistance and is widely used.

[0003] Living environment and physical health have become two major issues of concern to people. As we all know, harmful bacteria have always been a major factor affecting human health and lifespan. With the increase of carbon dioxide in the atmosphere, global warming and increasingly serious air pollution, various bacteria have begun to proliferate excessively, polluting people's daily living environment and leading to a gradual increase in the infection rate and incidence of infectious diseases. Therefore, this article introduces a high-temperature and low-temperature resistant plastic film with antibacterial properties and its preparation method. Summary of the Invention

[0004] The purpose of this invention is to provide a high-temperature and low-temperature resistant plastic film and its preparation method, so as to solve the problems existing in the prior art.

[0005] A high-temperature and low-temperature resistant plastic film is prepared by mixing functionalized glass fiber and functionalized polyether ether ketone, coating it onto a polytetrafluoroethylene plate, and scraping it off.

[0006] The functionalized glass fiber is prepared by reacting glass fiber sequentially with N-(3-trimethoxysilylpropyl)pyrrole, 1-allyl-1H-pyrrole and 1-methylpyrrole, N-(furan-2-ylmethyl)ethylamine and 1,3-propanesulfonic acid lactone.

[0007] The functionalized polyether ether ketone is prepared by reacting bis(4-fluorophenyl)phosphine oxide with acrylonitrile, hydroquinone with 4,4'-difluorobenzophenone, 2,4-dihydroxybenzonitrile, N-(2-aminopropyl)maleimide and furfuryl isocyanate in sequence.

[0008] A method for preparing a high-temperature and low-temperature resistant plastic film, the method mainly includes the following preparation steps:

[0009] (1) Pre-modified polyether ether ketone, 2,4-dihydroxybenzonitrile and zinc chloride are mixed in a mass ratio of 24-26:4-6:1, ground to 8-10 mesh, reacted at 290-310℃ for 46-50h, ground to 8-10 mesh, washed with ethanol 5-7 times, and vacuum dried at -10-0℃ for 22-26h to obtain modified polyether ether ketone;

[0010] (2) The functionalized polyether ether ketone precursor, furfuryl isocyanate, ethanol and catalyst are mixed at a mass ratio of 1:0.14-0.16:18-22:0.02-0.03, stirred at 200-300 r / min and 63-67℃ for 5.5-6.5 h, filtered, washed with ethanol 3-5 times, and vacuum dried at -10-0℃ for 22-26 h to obtain the functionalized polyether ether ketone;

[0011] (3) Immerse the pre-modified glass fiber in the pyrrole mixture for 3-5 minutes, remove it, and dry it at 55-65℃ for 11-13 hours to obtain the modified glass fiber.

[0012] (4) The modified glass fiber, N-(furan-2-ylmethyl)ethylamine and methanol were mixed at a mass ratio of 1:0.13-0.17:10-14 and stirred for 3.5-4.5 h at 45-55 °C and 200-300 r / min under argon protection. The mixture was then filtered, washed with ethanol 3-5 times, and dried to obtain the functionalized glass fiber precursor.

[0013] (5) Mix functionalized glass fiber and functionalized polyether ether ketone at a mass ratio of 1:9-11, stir at 336-340℃ for 20-30 min, coat evenly on polytetrafluoroethylene plate with a thickness of 30-40 μm, let stand at 70-74℃ for 9-11 h, scrape off, and obtain plastic film.

[0014] As an optimization, the pre-modified polyetheretherketone in step (1) is prepared by mixing flame-retardant monomer, hydroquinone, 4,4'-difluorobenzophenone, potassium carbonate and sulfolane in a molar ratio of 1:4-6:3-5:5.5-6.5:51-52, heating to 205-215°C under argon protection, stirring at 200-300 r / min for 10-11 h, pouring into deionized water, letting stand for 8-12 min, filtering, washing with deionized water 5-7 times, and vacuum drying at 55-65°C for 23-25 ​​h.

[0015] As an optimization, the functionalized polyether ether ketone precursor in step (2) is N-(2-aminopropyl)maleimide, The mixture of molecular sieve, modified polyether ether ketone, and toluene in a mass ratio of 1:1.8–2.2:12–14:26–30 was stirred at 155–165 °C and 200–300 r / min for 23–25 h, allowed to cool naturally to room temperature, filtered to remove the molecular sieve, washed 3–5 times with ethanol, and vacuum dried at 55–65 °C for 11–13 h to obtain the final product.

[0016] As an optimization, the catalyst in step (2) is dibutyltin dilaurate.

[0017] As an optimization, the pyrrole mixture in step (3) is prepared by mixing 1-allyl-1H-pyrrole, 1-methylpyrrole, ferric chloride and ethanol in a molar ratio of 1:3-5:4-6:20-30.

[0018] As an optimization, the pre-modified glass fiber in step (3) is prepared by mixing glass fiber with a diameter of 5 μm, N-(3-trimethoxysilylpropyl)pyrrole and isopropanol in a mass ratio of 1:0.14-0.16:10-12, adjusting the pH to 3.8-4.2 with 0.1 mol / L acetic acid solution, stirring at 85-95℃ and 200-300 r / min for 5-7 h, filtering, washing with deionized water 3-5 times, and drying at 90-100℃ for 2-4 h.

[0019] As an optimization, the specific operation method of drying in step (4) is vacuum drying at -10 to 0°C for 22 to 26 hours.

[0020] As an optimization, the functionalized glass fiber in step (5) is prepared by mixing functionalized glass fiber precursor, ethanol and 1,3-propanesulfonic acid lactone in a mass ratio of 1:8-10:0.13-0.17, stirring at 200-300 r / min at room temperature for 9-11 h, filtering, washing with ethanol 3-5 times, and vacuum drying at -10-0℃ for 22-26 h.

[0021] As an optimization, the flame-retardant monomer is prepared by mixing acrylonitrile and bis(4-fluorophenyl)phosphine oxide in a molar ratio of 1:1, placing them in a high-pressure reactor, and reacting them at 115–125°C for 10–12 h.

[0022] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0023] In preparing a high-temperature and low-temperature resistant plastic film, this invention involves reacting bis(4-fluorophenyl)phosphine oxide sequentially with acrylonitrile, hydroquinone with 4,4'-difluorobenzophenone, 2,4-dihydroxybenzonitrile, N-(2-aminopropyl)maleimide, and furfuryl isocyanate to obtain functionalized polyetheretherketone (PEEK). Glass fibers are then reacted sequentially with N-(3-trimethoxysilylpropyl)pyrrole, 1-allyl-1H-pyrrole with 1-methylpyrrole, N-(furan-2-ylmethyl)ethylamine, and 1,3-propanesulfonic acid lactone to obtain functionalized glass fibers. The functionalized glass fibers and PEEK are then mixed, coated onto a polytetrafluoroethylene (PTFE) plate, and scraped off to obtain the high-temperature and low-temperature resistant plastic film.

[0024] First, bis(4-fluorophenyl)phosphine oxide was reacted sequentially with acrylonitrile, hydroquinone with 4,4'-difluorobenzophenone, 2,4-dihydroxybenzonitrile, N-(2-aminopropyl)maleimide, and furfuryl isocyanate to prepare functionalized polyetheretherketone (PEEK). Then, organophosphorus compounds were introduced by reacting the flame-retardant monomer with hydroquinone and 4,4'-difluorobenzophenone, further enhancing the flame-retardant effect of the material. Finally, 2,4-dihydroxybenzonitrile was reacted with the functionalized PEEK precursor to introduce compounds with ortho- and phenolic hydroxyl groups. Triazine rings can slow down the aging process of materials by reflecting ultraviolet light. The phenolic hydroxyl group at the ortho position forms a conjugated ring with the triazine, making the electron cloud distribution inside the molecule more uniform, thereby improving its stability and the aging resistance of the material. Maleimide groups are introduced by reacting N-(2-aminopropyl)maleimide with modified polyether ether ketone. The self-healing effect is achieved through the DA reaction of maleimide groups with functionalized polyether ether ketone and furan groups on functionalized glass fibers.

[0025] Functionalized glass fibers were prepared by reacting glass fibers sequentially with N-(3-trimethoxysilylpropyl)pyrrole, 1-allyl-1H-pyrrole and 1-methylpyrrole, N-(furan-2-ylmethyl)ethylamine and 1,3-propanesulfonic acid lactone. The functionalized glass fibers were then mixed with functionalized polyetheretherketone (PEEK) and coated onto a polytetrafluoroethylene (PTFE) sheet. The mixture was scraped off to obtain a high-temperature and low-temperature resistant plastic film. Polypyrrole was formed on the surface of the glass fibers. As a conductive polymer, polypyrrole can form a conductive layer, allowing existing static charges to dissipate rapidly, achieving an antistatic effect. Furthermore, zwitterions were introduced through the reaction of a tertiary amine with 1,3-propanesulfonic acid lactone. The quaternary ammonium salt and sulfonic acid groups, as hydrophilic groups, can absorb environmental ions. The water in the amphoteric ions forms conductive channels, thereby promoting the dissipation of charge and preventing the accumulation of static electricity, thus achieving an antistatic effect. The anions and cations in the zwitterions can effectively inhibit bacterial adhesion and prevent the formation of biofilms, thereby inhibiting bacterial reproduction. Furthermore, anions can interfere with the synthesis of bacterial cell walls, causing defects in the bacterial cell walls. Since the bacterial cell is in a hypertonic state, external water will continuously seep in, causing the bacterial cell to swell, deform, and eventually die. Quaternary ammonium salts can change the permeability of microbial cells, causing the bacterial cell to rupture and thus destroying the internal structure of the cell. They can also denature proteins, thereby affecting the normal function of the cell and causing cell death, thus achieving an antibacterial effect. Detailed Implementation

[0026] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0027] Example 1:

[0028] A method for preparing a high-temperature and low-temperature resistant plastic film mainly includes the following preparation steps:

[0029] (1) Acrylonitrile and bis(4-fluorophenyl)phosphine oxide were mixed in a molar ratio of 1:1 and placed in a high-pressure reactor. The mixture was reacted at 115°C for 10 h and then removed to obtain a flame-retardant monomer. The flame-retardant monomer, hydroquinone, 4,4'-difluorobenzophenone, potassium carbonate and sulfolane were mixed in a molar ratio of 1:4:3:5.5:51 and heated to 205°C under argon protection. The mixture was stirred at 200 r / min for 10 h, poured into deionized water, allowed to stand for 8 min, filtered, washed 5 times with deionized water, and vacuum dried at 55°C for 23 h to obtain a pre-modified polyether ether ketone. The pre-modified polyether ether ketone, 2,4-dihydroxybenzonitrile and zinc chloride were mixed in a mass ratio of 24:4:1, ground to 8 mesh, reacted at 290°C for 46 h, ground to 8 mesh, washed 5 times with ethanol, and vacuum dried at -10°C for 22 h to obtain a modified polyether ether ketone.

[0030] (2) N-(2-aminopropyl)maleimide, A molecular sieve, modified polyether ether ketone (PEEK) and toluene were mixed at a mass ratio of 1:1.8:12:26 and stirred at 155℃ and 200 r / min for 23 h. After naturally cooling to room temperature, the mixture was filtered to remove the molecular sieve, washed three times with ethanol, and vacuum dried at 55℃ for 11 h to obtain a functionalized PEEK precursor. The functionalized PEEK precursor, furfuryl isocyanate, ethanol and dibutyltin dilaurate were mixed at a mass ratio of 1:0.14:18:0.02 and stirred at 200 r / min and 63℃ for 5.5 h. After filtration, the mixture was washed three times with ethanol and vacuum dried at -10℃ for 22 h to obtain a functionalized PEEK.

[0031] (3) 1-Allyl-1H-pyrrole, 1-methylpyrrole, ferric chloride and ethanol were mixed evenly in a molar ratio of 1:3:4:20 to prepare a pyrrole mixture; glass fibers with a diameter of 5 μm, N-(3-trimethoxysilylpropyl)pyrrole and isopropanol were mixed in a mass ratio of 1:0.14:10, the pH was adjusted to 3.8 with 0.1 mol / L acetic acid solution, stirred at 85℃ and 200 r / min for 5 h, filtered, washed 3 times with deionized water, and dried at 90℃ for 2 h to obtain pre-modified glass fibers; the pre-modified glass fibers were immersed in the pyrrole mixture for 3 min, removed, and dried at 55℃ for 11 h to obtain modified glass fibers;

[0032] (4) Modified glass fiber, N-(furan-2-ylmethyl)ethylamine and methanol were mixed in a mass ratio of 1:0.13:10 and stirred for 3.5 h at 45 °C, 200 r / min and argon protection. The mixture was filtered, washed three times with ethanol, and vacuum dried at -10 °C for 22 h to obtain the functionalized glass fiber precursor. The functionalized glass fiber precursor, ethanol and 1,3-propanesulfonic acid lactone were mixed in a mass ratio of 1:8:0.13 and stirred for 9 h at 200 r / min and room temperature. The mixture was filtered, washed three times with ethanol, and vacuum dried at -10 °C for 22 h to obtain the functionalized glass fiber.

[0033] (5) Functionalized glass fiber and functionalized polyether ether ketone are mixed at a mass ratio of 1:9, stirred at 336°C for 20 min, and uniformly coated on a polytetrafluoroethylene plate with a thickness of 30 μm. After standing at 70°C for 9 h, the mixture is scraped off to obtain a plastic film.

[0034] Example 2:

[0035] A method for preparing a high-temperature and low-temperature resistant plastic film mainly includes the following preparation steps:

[0036] (1) Acrylonitrile and bis(4-fluorophenyl)phosphine oxide were mixed in a molar ratio of 1:1 and placed in a high-pressure reactor. The mixture was reacted at 120°C for 11 h and then removed to obtain a flame-retardant monomer. The flame-retardant monomer, hydroquinone, 4,4'-difluorobenzophenone, potassium carbonate and sulfolane were mixed in a molar ratio of 1:5:4:6:51.5. Under argon protection, the mixture was heated to 210°C and stirred at 250 r / min for 10.5 h. The mixture was poured into deionized water, allowed to stand for 10 min, filtered, washed 6 times with deionized water, and vacuum dried at 60°C for 24 h to obtain a pre-modified polyether ether ketone. The pre-modified polyether ether ketone, 2,4-dihydroxybenzonitrile and zinc chloride were mixed in a mass ratio of 25:5:1, ground to 9 mesh, reacted at 300°C for 48 h, ground to 9 mesh, washed 6 times with ethanol, and vacuum dried at -5°C for 24 h to obtain a modified polyether ether ketone.

[0037] (2) N-(2-aminopropyl)maleimide, A molecular sieve, modified polyether ether ketone (PEEK) and toluene were mixed in a mass ratio of 1:2:13:28 and stirred at 160℃ and 250 r / min for 24 h. After naturally cooling to room temperature, the mixture was filtered to remove the molecular sieve, washed four times with ethanol, and vacuum dried at 60℃ for 12 h to obtain the functionalized PEEK precursor. The functionalized PEEK precursor, furfuryl isocyanate, ethanol and dibutyltin dilaurate were mixed in a mass ratio of 1:0.15:20:0.025 and stirred at 250 r / min and 65℃ for 6 h. After filtration, the mixture was washed four times with ethanol and vacuum dried at -5℃ for 24 h to obtain the functionalized PEEK.

[0038] (3) 1-Allyl-1H-pyrrole, 1-methylpyrrole, ferric chloride and ethanol were mixed evenly in a molar ratio of 1:4:5:25 to prepare a pyrrole mixture; glass fibers with a diameter of 5 μm, N-(3-trimethoxysilylpropyl)pyrrole and isopropanol were mixed in a mass ratio of 1:0.15:11, the pH was adjusted to 4 with 0.1 mol / L acetic acid solution, stirred at 90℃ and 250 r / min for 6 h, filtered, washed 4 times with deionized water, and dried at 95℃ for 3 h to obtain pre-modified glass fibers; the pre-modified glass fibers were immersed in the pyrrole mixture for 4 min, removed, and dried at 60℃ for 12 h without dripping to obtain modified glass fibers;

[0039] (4) Modified glass fiber, N-(furan-2-ylmethyl)ethylamine and methanol were mixed in a mass ratio of 1:0.15:12, stirred for 4 h at 50 °C and 250 r / min under argon protection, filtered, washed 4 times with ethanol, and vacuum dried at -5 °C for 24 h to obtain functionalized glass fiber precursor; functionalized glass fiber precursor, ethanol and 1,3-propanesulfonic acid lactone were mixed in a mass ratio of 1:9:0.15, stirred for 10 h at 250 r / min and room temperature, filtered, washed 4 times with ethanol, and vacuum dried at -5 °C for 24 h to obtain functionalized glass fiber;

[0040] (5) Functionalized glass fiber and functionalized polyether ether ketone are mixed at a mass ratio of 1:10, stirred at 338°C for 25 min, and uniformly coated on a polytetrafluoroethylene plate with a thickness of 35 μm. After standing at 72°C for 10 h, the mixture is scraped off to obtain a plastic film.

[0041] Example 3:

[0042] A method for preparing a high-temperature and low-temperature resistant plastic film mainly includes the following preparation steps:

[0043] (1) Acrylonitrile and bis(4-fluorophenyl)phosphine oxide were mixed in a molar ratio of 1:1 and placed in a high-pressure reactor. The mixture was reacted at 125°C for 12 h and then removed to obtain a flame-retardant monomer. The flame-retardant monomer, hydroquinone, 4,4'-difluorobenzophenone, potassium carbonate and sulfolane were mixed in a molar ratio of 1:6:5:6.5:52 and heated to 215°C under argon protection. The mixture was stirred at 300 r / min for 11 h and then poured into deionized water. The mixture was allowed to stand for 12 min, filtered, washed 7 times with deionized water, and vacuum dried at 65°C for 25 h to obtain a pre-modified polyether ether ketone. The pre-modified polyether ether ketone, 2,4-dihydroxybenzonitrile and zinc chloride were mixed in a mass ratio of 26:6:1, ground to 10 mesh, reacted at 310°C for 50 h, ground to 10 mesh, washed 7 times with ethanol, and vacuum dried at 0°C for 26 h to obtain a modified polyether ether ketone.

[0044] (2) N-(2-aminopropyl)maleimide, A molecular sieve, modified polyether ether ketone (PEEK) and toluene were mixed at a mass ratio of 1:2.2:14:30 and stirred at 165℃ and 300 r / min for 25 h. After naturally cooling to room temperature, the mixture was filtered to remove the molecular sieve, washed five times with ethanol, and vacuum dried at 65℃ for 13 h to obtain a functionalized PEEK precursor. The functionalized PEEK precursor, furfuryl isocyanate, ethanol, and dibutyltin dilaurate were mixed at a mass ratio of 1:0.16:22:0.03 and stirred at 300 r / min and 67℃ for 6.5 h. After filtration, the mixture was washed five times with ethanol and vacuum dried at 0℃ for 26 h to obtain a functionalized PEEK.

[0045] (3) 1-Allyl-1H-pyrrole, 1-methylpyrrole, ferric chloride and ethanol were mixed evenly in a molar ratio of 1:5:6:30 to prepare a pyrrole mixture; glass fibers with a diameter of 5 μm, N-(3-trimethoxysilylpropyl)pyrrole and isopropanol were mixed in a mass ratio of 1:0.16:12, the pH was adjusted to 4.2 with 0.1 mol / L acetic acid solution, stirred at 95℃ and 300 r / min for 7 h, filtered, washed 5 times with deionized water, and dried at 100℃ for 4 h to obtain pre-modified glass fibers; the pre-modified glass fibers were immersed in the pyrrole mixture for 5 min, removed, and dried at 65℃ for 13 h to obtain modified glass fibers;

[0046] (4) Modified glass fiber, N-(furan-2-ylmethyl)ethylamine and methanol were mixed at a mass ratio of 1:0.17:14 and stirred at 55℃, 300r / min and argon protection for 4.5h. The mixture was filtered, washed 5 times with ethanol, and dried under vacuum at 0℃ for 26h to obtain the functionalized glass fiber precursor. The functionalized glass fiber precursor, ethanol and 1,3-propanesulfonic acid lactone were mixed at a mass ratio of 1:10:0.17 and stirred at 300r / min and room temperature for 11h. The mixture was filtered, washed 5 times with ethanol, and dried under vacuum at 0℃ for 26h to obtain the functionalized glass fiber.

[0047] (5) Functionalized glass fiber and functionalized polyether ether ketone are mixed at a mass ratio of 1:11, stirred at 340°C for 30 min, and uniformly coated on a polytetrafluoroethylene plate with a thickness of 40 μm. After standing at 74°C for 11 h, the mixture is scraped off to obtain a plastic film.

[0048] Comparative Example 1:

[0049] The difference between the preparation method of the high-temperature and low-temperature resistant plastic film in Comparative Example 1 and that in Example 2 lies in step (2). Step (2) is modified as follows: N-(2-aminopropyl)maleimide, Molecular sieve, modified polyether ether ketone, and toluene were mixed in a mass ratio of 1:2:13:28 and stirred at 160°C and 250 r / min for 24 h. After naturally cooling to room temperature, the mixture was filtered to remove the molecular sieve, washed four times with ethanol, and vacuum dried at 60°C for 12 h to obtain functionalized polyether ether ketone. The remaining steps were the same as in Example 2.

[0050] Comparative Example 2:

[0051] The difference between the preparation method of the high-temperature and low-temperature resistant plastic film of Comparative Example 2 and Comparative Example 1 lies in step (1). Step (1) is modified as follows: Acrylonitrile and bis(4-fluorophenyl)phosphine oxide are mixed in a molar ratio of 1:1, placed in a high-pressure reactor, and reacted at 120°C for 11 h. The mixture is then removed to obtain the flame-retardant monomer. The flame-retardant monomer, hydroquinone, 4,4'-difluorobenzophenone, potassium carbonate, and sulfolane are mixed in a molar ratio of 1:5:4:6:51.5, heated to 210°C under argon protection, stirred at 250 r / min for 10.5 h, poured into deionized water, allowed to stand for 10 min, filtered, washed 6 times with deionized water, and vacuum dried at 60°C for 24 h to obtain the modified polyetheretherketone. The remaining steps are the same as in Comparative Example 1.

[0052] Comparative Example 3:

[0053] The difference between the preparation method of the high-temperature and low-temperature resistant plastic film of Comparative Example 3 and Comparative Example 1 lies in step (1). Step (1) is modified as follows: Hydroquinone, 4,4'-difluorobenzophenone, potassium carbonate and sulfolane are mixed in a molar ratio of 5:5:6:51.5, heated to 210℃ under argon protection, stirred at 250 r / min for 10.5 h, poured into deionized water, allowed to stand for 10 min, filtered, washed 6 times with deionized water, and vacuum dried at 60℃ for 24 h to obtain modified polyetheretherketone. The remaining steps are the same as in Comparative Example 1.

[0054] Comparative Example 4:

[0055] The difference between the preparation method of the high-temperature and low-temperature resistant plastic film in Comparative Example 4 and Example 2 lies in step (2). Step (2) is modified as follows: modified polyetheretherketone, furfuryl isocyanate, ethanol, and dibutyltin dilaurate are mixed in a mass ratio of 1:0.16:22:0.03, stirred at 300 r / min and 67°C for 6.5 h, filtered, washed 5 times with ethanol, and vacuum dried at 0°C for 26 h to obtain functionalized polyetheretherketone. The remaining steps are the same as in Example 2.

[0056] Comparative Example 5:

[0057] The difference between the preparation method of the high-temperature and low-temperature resistant plastic film of Comparative Example 5 and Example 2 lies in step (4). Step (4) is modified as follows: modified glass fiber, N-(furan-2-ylmethyl)ethylamine and methanol are mixed at a mass ratio of 1:0.15:12, stirred for 4 hours at 50°C and 250 r / min under argon protection, filtered, washed 4 times with ethanol, and vacuum dried at -5°C for 24 hours to obtain functionalized glass fiber. The remaining steps are the same as in Example 2.

[0058] Comparative Example 6:

[0059] The difference between the preparation method of the high-temperature and low-temperature resistant plastic film of Comparative Example 6 and Example 2 lies in the different steps (3), (4), and (5). Steps (3) and (4) are deleted, and step (5) is modified as follows: glass fiber with a diameter of 5 μm and functionalized polyether ether ketone are mixed at a mass ratio of 1:10, stirred at 338°C for 25 min, uniformly coated on a polytetrafluoroethylene plate with a thickness of 35 μm, allowed to stand at 72°C for 10 h, and scraped off to obtain the plastic film. The remaining steps are the same as in Example 2.

[0060] Test Example 1:

[0061] Flame retardancy test

[0062] The limiting oxygen index was tested according to the GBT / 2406 testing standard. The results are shown in Table 1.

[0063] Table 1

[0064]

[0065]

[0066] A comparison of the experimental data in Table 1 shows that the high-temperature and low-temperature resistant plastic film prepared by this invention has good flame retardant properties.

[0067] A comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 3 in Table 1 reveals that Examples 1, 2, and 3 have a larger limiting oxygen index than Comparative Example 3. The difference between Comparative Example 3 and the Examples is that the polyether ether ketone was not modified using organophosphorus compounds, indicating that the introduction of organophosphorus compounds enhances the flame retardant effect of the material.

[0068] Test Example 2:

[0069] Antibacterial test

[0070] The high-temperature and low-temperature resistant plastic films prepared in each example and comparative example were pulverized to 30 mesh. 1 g of the pulverized film was tested according to GB / T31402-2015 standard, with Staphylococcus aureus and Escherichia coli selected as the bacterial strains. The results are shown in Table 2.

[0071] Table 2

[0072]

[0073]

[0074] A comparison of the experimental data in Table 2 shows that the high-temperature and low-temperature resistant plastic film prepared by this invention has good antibacterial properties.

[0075] A comparison of the experimental data from Examples 1, 2, and 3 and Comparative Example 5 in Table 2 reveals that Examples 1, 2, and 3 exhibit higher antibacterial rates compared to Comparative Example 5. The difference between Comparative Example 5 and the Examples lies in the absence of zwitterions forming on the glass fiber surface. This indicates that the anionic and cationic groups in zwitterions can effectively inhibit bacterial adhesion and prevent the formation of biofilms, thereby inhibiting bacterial reproduction. Furthermore, sulfonic acid anions can interfere with bacterial cell wall synthesis, causing defects in the bacterial cell wall. Due to the hypertonic state within the bacterial cell, external water continuously seeps in, causing the bacterial cell to swell, deform, and ultimately die. Quaternary ammonium salts can alter the permeability of microbial cells, leading to cell rupture and thus disrupting the internal structure of the cell. They can also denature proteins, thereby affecting normal cell function and causing cell death, thus achieving an antibacterial effect.

[0076] Test Example 3:

[0077] Aging resistance and self-healing test:

[0078] Self-healing test: The plastics prepared in each example and comparative example were made into strips with a length of 10 mm, a width of 4 mm, and a thickness of 30 μm. The tensile strength was tested and recorded as the initial tensile strength. Then, a small slit with a length of 3 mm and a depth of 15 μm was cut transversely in the middle of the same strip. The strip was placed in a constant temperature oven at 70℃ for 2 hours. The tensile strength of the repaired strip was tested and recorded as the tensile strength after self-healing. The self-healing efficiency was calculated, where the self-healing efficiency = tensile strength after self-healing / initial tensile strength * 100%.

[0079] Aging resistance test: The plastics prepared in each example and comparative example were made into strips with a length of 10 mm, a width of 4 mm, and a thickness of 30 μm. The tensile strength was tested and recorded as the initial tensile strength. The same strip was then irradiated under a fluorescent ultraviolet lamp UV-A340 for 15 days, and the tensile strength was tested again and recorded as the tensile strength after aging. The tensile strength retention rate was calculated, where the tensile strength retention rate = tensile strength after aging / initial tensile strength * 100%. The results are shown in Table 3.

[0080] Table 3

[0081]

[0082]

[0083] A comparison of the experimental data in Table 3 shows that the high-temperature and low-temperature resistant plastic film prepared by this invention has good aging resistance and self-healing ability.

[0084] A comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 1 in Table 3 shows that Examples 1, 2, and 3 have a higher self-healing efficiency than Comparative Example 1. The difference between Comparative Example 1 and Examples is that furan groups were not introduced into the polyether ether ketone chain. This indicates that the difference between Comparative Example 1 and Examples is that the polyether ether ketone was not modified with furan functionalization. The self-healing effect can be achieved through the DA reaction between maleimide groups and furan groups under relatively mild reaction conditions without the need for a catalyst.

[0085] A comparison of the experimental data from Examples 1, 2, 3 and Comparative Example 2 reveals that Examples 1, 2, and 3 exhibit a higher tensile strength retention rate compared to Comparative Example 2. The difference between Comparative Example 2 and the Examples lies in the absence of a triazine ring formed on the polyetheretherketone (PEEK) chain. This indicates that the triazine ring can slow down the aging process of the material by reflecting ultraviolet light. Furthermore, the reaction between 2,4-dihydroxybenzonitrile and the PEEK backbone can form a triazine with an ortho-phenolic hydroxyl group. The ortho-phenolic hydroxyl group forms a conjugated ring with the triazine, resulting in a more uniform electron cloud distribution within the molecule, thereby improving its stability and further enhancing the material's aging resistance.

[0086] Test Example 4:

[0087] Antistatic test:

[0088] Surface resistivity was tested at 20℃ according to GB / T1410-2006 standard. The results are shown in Table 4.

[0089] Table 4

[0090] Surface resistivity Example 1 5.13*10^8Ω Example 2 5.11*10^8Ω Example 3 5.14*10^8Ω Comparative Example 1 5.18*10^8Ω Comparative Example 2 5.12*10^8Ω Comparative Example 3 5.17*10^8Ω Comparative Example 4 5.19*10^8Ω Comparative Example 5 7.32*10^10Ω Comparative Example 6 8.96*10^14Ω

[0091] A comparison of the experimental data in Table 4 shows that the high-temperature and low-temperature resistant plastic film prepared by this invention has good antistatic properties.

[0092] A comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 5 in Table 4 reveals that Examples 1, 2, and 3 have lower surface resistivity than Comparative Example 5. The difference between Comparative Example 5 and the Examples is that no zwitterions are formed on the glass fiber surface. This indicates that quaternary ammonium salts and sulfonic acid groups, as hydrophilic groups, can absorb moisture from the environment, form conductive channels, thereby promoting charge dissipation, avoiding the accumulation of static electricity, and achieving an antistatic effect.

[0093] A comparison of the experimental data from Examples 1, 2, 3 and Comparative Example 6 reveals that Examples 1, 2, and 3 have lower surface resistivity than Comparative Example 6. The difference between Comparative Example 6 and the Examples is that the glass fiber was not modified. This demonstrates that polypyrrole, as a conductive polymer, can form a conductive layer, allowing the generated static charge to leak out quickly and achieving an antistatic effect.

[0094] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A high-temperature and low-temperature resistant plastic film, characterized in that, The high-temperature and low-temperature resistant plastic film is prepared by mixing functionalized glass fiber and functionalized polyether ether ketone, coating it onto a polytetrafluoroethylene plate, and scraping it off. The functionalized glass fiber is prepared by reacting glass fiber sequentially with N-(3-trimethoxysilylpropyl)pyrrole, 1-allyl-1H-pyrrole and 1-methylpyrrole, N-(furan-2-ylmethyl)ethylamine and 1,3-propanesulfonic acid lactone. The functionalized polyether ether ketone is prepared by reacting bis(4-fluorophenyl)phosphine oxide with acrylonitrile, hydroquinone with 4,4'-difluorobenzophenone, 2,4-dihydroxybenzonitrile, N-(2-aminopropyl)maleimide and furfuryl isocyanate in sequence.

2. A method for preparing a high-temperature and low-temperature resistant plastic film, characterized in that, The preparation method of the high-temperature and low-temperature resistant plastic film mainly includes the following preparation steps: (1) Pre-modified polyether ether ketone, 2,4-dihydroxybenzonitrile and zinc chloride are mixed in a mass ratio of 24-26:4-6:1, ground to 8-10 mesh, reacted at 290-310℃ for 46-50h, ground to 8-10 mesh, washed with ethanol 5-7 times, and vacuum dried at -10-0℃ for 22-26h to obtain modified polyether ether ketone; (2) The functionalized polyether ether ketone precursor, furfuryl isocyanate, ethanol and catalyst are mixed at a mass ratio of 1:0.14-0.16:18-22:0.02-0.03, stirred at 200-300 r / min and 63-67℃ for 5.5-6.5 h, filtered, washed with ethanol 3-5 times, and vacuum dried at -10-0℃ for 22-26 h to obtain the functionalized polyether ether ketone; (3) Immerse the pre-modified glass fiber in the pyrrole mixture for 3-5 minutes, remove it, and dry it at 55-65℃ for 11-13 hours to obtain the modified glass fiber. (4) The modified glass fiber, N-(furan-2-ylmethyl)ethylamine and methanol were mixed at a mass ratio of 1:0.13-0.17:10-14 and stirred for 3.5-4.5 h at 45-55 °C and 200-300 r / min under argon protection. The mixture was then filtered, washed with ethanol 3-5 times, and dried to obtain the functionalized glass fiber precursor. (5) Mix functionalized glass fiber and functionalized polyether ether ketone at a mass ratio of 1:9-11, stir at 336-340℃ for 20-30 min, coat evenly on polytetrafluoroethylene plate with a thickness of 30-40 μm, let stand at 70-74℃ for 9-11 h, scrape off, and obtain plastic film.

3. The method for preparing a high-temperature and low-temperature resistant plastic film according to claim 2, characterized in that, The pre-modified polyetheretherketone (PEEK) described in step (1) is prepared by mixing flame-retardant monomers, hydroquinone, 4,4'-difluorobenzophenone, potassium carbonate, and sulfolane in a molar ratio of 1:4-6:3-5:5.5-6.5:51-52, heating to 205-215°C under argon protection, stirring at 200-300 r / min for 10-11 h, pouring into deionized water, letting stand for 8-12 min, filtering, washing with deionized water 5-7 times, and vacuum drying at 55-65°C for 23-25 ​​h.

4. The method for preparing a high-temperature and low-temperature resistant plastic film according to claim 2, characterized in that, The functionalized polyether ether ketone precursor in step (2) is N-(2-aminopropyl)maleimide, The mixture of molecular sieve, modified polyether ether ketone, and toluene in a mass ratio of 1:1.8–2.2:12–14:26–30 was stirred at 155–165 °C and 200–300 r / min for 23–25 h, allowed to cool naturally to room temperature, filtered to remove the molecular sieve, washed 3–5 times with ethanol, and vacuum dried at 55–65 °C for 11–13 h to obtain the final product.

5. The method for preparing a high-temperature and low-temperature resistant plastic film according to claim 2, characterized in that, The catalyst in step (2) is dibutyltin dilaurate.

6. The method for preparing a high-temperature and low-temperature resistant plastic film according to claim 2, characterized in that, The pyrrole mixture in step (3) is prepared by mixing 1-allyl-1H-pyrrole, 1-methylpyrrole, ferric chloride and ethanol in a molar ratio of 1:3-5:4-6:20-30.

7. The method for preparing a high-temperature and low-temperature resistant plastic film according to claim 2, characterized in that, The pre-modified glass fiber in step (3) is prepared by mixing glass fiber with a diameter of 5 μm, N-(3-trimethoxysilylpropyl)pyrrole and isopropanol in a mass ratio of 1:0.14-0.16:10-12, adjusting the pH to 3.8-4.2 with 0.1 mol / L acetic acid solution, stirring at 85-95℃ and 200-300 r / min for 5-7 h, filtering, washing with deionized water 3-5 times, and drying at 90-100℃ for 2-4 h.

8. The method for preparing a high-temperature and low-temperature resistant plastic film according to claim 2, characterized in that, The specific drying operation in step (4) is vacuum drying at -10 to 0°C for 22 to 26 hours.

9. The method for preparing a high-temperature and low-temperature resistant plastic film according to claim 2, characterized in that, The functionalized glass fiber described in step (5) is prepared by mixing functionalized glass fiber precursor, ethanol and 1,3-propanesulfonic acid lactone in a mass ratio of 1:8-10:0.13-0.17, stirring at 200-300 r / min at room temperature for 9-11 h, filtering, washing with ethanol 3-5 times, and vacuum drying at -10-0℃ for 22-26 h.

10. The method for preparing a high-temperature and low-temperature resistant plastic film according to claim 3, characterized in that, The flame-retardant monomer is prepared by mixing acrylonitrile and bis(4-fluorophenyl)phosphine oxide in a molar ratio of 1:1, placing them in a high-pressure reactor, and reacting them at 115–125°C for 10–12 h.

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