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

Abstract

The invention discloses a high-temperature-resistant and low-temperature-resistant plastic film and a preparation method thereof, and relates to the field of high polymer materials. When the high-temperature-resistant and low-temperature-resistant plastic film is prepared, bis (4-fluorophenyl) phosphine oxide sequentially reacts with acrylonitrile, hydroquinone, 4, 4 '-difluorobenzophenone, 2, 4-dihydroxybenzonitrile, N-(2-aminopropyl) maleimide and furfuryl isocyanate, and functional polyether-ether-ketone is prepared; the preparation method comprises the following steps: enabling glass fibers to react with N-(3-trimethoxysilylpropyl) pyrrole, 1-allyl-1H-pyrrole and 1-methylpyrrole, N-(furan-2-yl methyl) ethylamine and 1, 3-propane sultone in sequence, so as to prepare functional glass fibers; and mixing the functionalized glass fiber and the functionalized polyether-ether-ketone, coating a polytetrafluoroethylene plate with the mixture, and scraping the mixture to obtain the high-temperature-resistant and low-temperature-resistant plastic film. The high-temperature-resistant and low-temperature-resistant plastic film prepared by the invention has the capabilities of durability, antibacterial property, self-repairing property, antistatic property and flame retardance.

Description

Technical Field

[0001] The present invention relates to the field of polymer materials, in particular to a high-temperature and low-temperature resistant plastic film and a preparation method thereof. Background Art

[0002] Plastic refers to a material with high molecular compounds as its basic components. It can be polymerized or flow-formed or solidified in situ at a certain stage in the processing or manufacturing process. The finished product is a rigid or flexible solid material. Plastics can be divided into general plastics and engineering plastics based on their application areas. Engineering plastics can be used as structural materials with excellent comprehensive performance. Polyetheretherketone is an excellent engineering plastic with excellent high and low temperature resistance and is widely used.

[0003] Living environment and physical health have become two major topics of concern to people. As we all know, harmful bacteria have always been the main factor affecting human health and life expectancy. With the increase of carbon dioxide in the atmosphere, global warming and the increasing severity of air pollution, various bacteria have begun to over-multiply, polluting people's daily living environment, 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 ability and its preparation method. Summary of the Invention

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

[0005] A high-temperature and low-temperature resistant plastic film, which is prepared by mixing functionalized glass fiber and functionalized polyetheretherketone, coating the mixture on a polytetrafluoroethylene plate, and scraping it off.

[0006] The functionalized glass fiber is prepared by reacting glass fiber with N-(3-trimethoxysilylpropyl)pyrrole, 1-allyl-1H-pyrrole, 1-methylpyrrole, N-(furan-2-ylmethyl)ethylamine and 1,3-propane sultone in sequence;

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

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

[0009] (1) Pre-modified polyetheretherketone, 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°C for 46-50h, ground to 8-10 mesh, washed with ethanol 5-7 times, and vacuum dried at -10-0°C for 22-26h to obtain modified polyetheretherketone;

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

[0011] (3) soaking the pre-modified glass fiber in the pyrrole mixture for 3 to 5 minutes, taking it out until no liquid drops, and drying it at 55 to 65° C. for 11 to 13 hours to obtain the modified glass fiber;

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

[0013] (5) Functionalized glass fiber and functionalized polyetheretherketone are mixed in a mass ratio of 1:9-11, stirred at 336-340°C for 20-30 minutes, evenly coated on a polytetrafluoroethylene plate with a thickness of 30-40 μm, allowed to stand at 70-74°C for 9-11 hours, and scraped off to obtain a plastic film.

[0014] As an optimization, the pre-modified polyetheretherketone in step (1) is prepared by mixing a 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 hours, pouring into deionized water, standing for 8-12 minutes, filtering, washing with deionized water 5-7 times, and vacuum drying at 55-65°C for 23-25 hours.

[0015] As an optimization, the functionalized polyetheretherketone precursor in step (2) is N-(2-aminopropyl)maleimide, The product is prepared by mixing molecular sieve, modified polyetheretherketone and toluene in a mass ratio of 1:1.8-2.2:12-14:26-30, stirring at 155-165°C and 200-300r / min for 23-25h, naturally cooling to room temperature, filtering, removing molecular sieve, washing with ethanol 3-5 times, and vacuum drying at 55-65°C for 11-13h.

[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 uniformly 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 isopropyl alcohol 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°C and 200-300 r / min for 5-7 h, filtering, washing with deionized water 3-5 times, and drying at 90-100°C for 2-4 h.

[0019] As an optimization, the specific operation mode of the 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 a functionalized glass fiber precursor, ethanol and 1,3-propane sultone in a mass ratio of 1:8-10:0.13-0.17, stirring at 200-300 r / min and room temperature for 9-11 hours, filtering, washing with ethanol 3-5 times, and vacuum drying at -10-0°C for 22-26 hours.

[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 the mixture in a high-pressure reactor, and reacting the mixture at 115-125° C. for 10-12 hours.

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] When preparing a high-temperature and low-temperature resistant plastic film, the present invention sequentially reacts bis(4-fluorophenyl)phosphine oxide with acrylonitrile, hydroquinone with 4,4'-difluorobenzophenone, 2,4-dihydroxybenzonitrile, N-(2-aminopropyl)maleimide and furfuryl isocyanate to prepare a functionalized polyetheretherketone; sequentially reacts glass fiber with N-(3-trimethoxysilylpropyl)pyrrole, 1-allyl-1H-pyrrole with 1-methylpyrrole, N-(furan-2-ylmethyl)ethylamine and 1,3-propane sultone to prepare a functionalized glass fiber; and the functionalized glass fiber and the functionalized polyetheretherketone are mixed, coated on a polytetrafluoroethylene plate, and scraped off to prepare a high-temperature and low-temperature resistant plastic film.

[0024] First, bis(4-fluorophenyl)phosphine oxide was reacted with acrylonitrile, hydroquinone, 4,4'-difluorobenzophenone, 2,4-dihydroxybenzonitrile, N-(2-aminopropyl)maleimide and furfuryl isocyanate in sequence to prepare functionalized polyetheretherketone; organic phosphorus was introduced by reacting flame retardant monomer with hydroquinone and 4,4'-difluorobenzophenone to further improve the flame retardant effect of the material; and a hydroxyl group with an o-phenolic hydroxyl group was introduced by reacting 2,4-dihydroxybenzonitrile with a functionalized polyetheretherketone precursor. Triazine ring can delay the aging process of the material by reflecting ultraviolet light. The ortho-phenolic hydroxyl group forms a conjugated ring with triazine, making the electron cloud distribution inside the molecule more uniform, thereby improving its stability and improving the aging resistance of the material; through the reaction of N-(2-aminopropyl)maleimide with modified polyetheretherketone, the maleimide group is introduced, and the self-repair effect is achieved through the DA reaction of the maleimide group with the functionalized polyetheretherketone and the furan group on the functionalized glass fiber.

[0025] The glass fiber is reacted with N-(3-trimethoxysilylpropyl)pyrrole, 1-allyl-1H-pyrrole, 1-methylpyrrole, N-(furan-2-ylmethyl)ethylamine and 1,3-propane sultone in sequence to obtain functional glass fiber; the functional glass fiber is mixed with functional polyetheretherketone, coated on a polytetrafluoroethylene plate, and scraped off to obtain a high-temperature and low-temperature resistant plastic film; polypyrrole is formed on the surface of the glass fiber. As a conductive polymer, polypyrrole can form a conductive layer to quickly leak the generated static charge and achieve an antistatic effect; zwitterions are then introduced through the reaction of tertiary amine with 1,3-propane sultone. The quaternary ammonium salt and sulfonic acid group can absorb the environment as hydrophilic groups. The zwitterions absorb water, forming a conductive channel, thereby promoting the dissipation of charge, avoiding the accumulation of static electricity, and achieving an antistatic effect; the anion and cationic groups in the zwitterions can effectively inhibit bacterial adhesion and prevent the formation of biofilm, thereby achieving the purpose of inhibiting bacterial reproduction; and the anions can interfere with the synthesis of bacterial cell walls, causing defects in the bacterial cell walls. Since the bacteria are in a hypertonic state, external water will continue to penetrate, causing the bacteria to swell, deform, and eventually die; and quaternary ammonium salts can change the permeability of microbial cells, causing the bacteria to rupture, thereby destroying the internal structure of the cells; they can also denature proteins, thereby affecting the normal function of the cells and leading to cell death, thereby achieving an antibacterial effect. DETAILED DESCRIPTION

[0026] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts 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 comprises the following preparation steps:

[0029] (1) Acrylonitrile and bis(4-fluorophenyl)phosphine oxide were mixed in a molar ratio of 1:1, placed in a high-pressure reactor, reacted at 115°C for 10 hours, and taken out to obtain a flame retardant monomer; the flame retardant monomer, hydroquinone, 4,4'-difluorobenzophenone, potassium carbonate and cyclopentane sulfone were mixed in a molar ratio of 1:4:3:5.5:51, heated to 205°C under argon protection, stirred at 200r / min for 10 hours, poured into deionized water, allowed to stand for 8 minutes, filtered, washed with deionized water 5 times, and vacuum dried at 55°C for 23 hours to obtain pre-modified polyetheretherketone; the pre-modified polyetheretherketone, 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 hours, ground to 8 mesh, washed with ethanol 5 times, and vacuum dried at -10°C for 22 hours to obtain modified polyetheretherketone;

[0030] (2) N-(2-aminopropyl)maleimide, The functionalized polyetheretherketone precursor was prepared by mixing the molecular sieve, modified polyetheretherketone and toluene in a mass ratio of 1:1.8:12:26, stirring at 155°C and 200 r / min for 23 h, naturally cooling to room temperature, filtering, removing the molecular sieve, washing with ethanol three times, and vacuum drying at 55°C for 11 h. The functionalized polyetheretherketone precursor, furfuryl isocyanate, ethanol and dibutyltin dilaurate were mixed in a mass ratio of 1:0.14:18:0.02, stirring at 200 r / min and 63°C for 5.5 h, filtering, washing with ethanol three times, and vacuum drying at -10°C for 22 h to prepare the functionalized polyetheretherketone.

[0031] (3) 1-allyl-1H-pyrrole, 1-methylpyrrole, ferric chloride and ethanol were mixed uniformly in a molar ratio of 1:3:4:20 to prepare a pyrrole mixture; glass fiber 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 ° C and 200 r / min for 5 h, filtered, washed with deionized water 3 times, and dried at 90 ° C for 2 h to prepare pre-modified glass fiber; the pre-modified glass fiber was immersed in the pyrrole mixture for 3 min, taken out, no liquid dripped, and dried at 55 ° C for 11 h to prepare modified glass fiber;

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

[0033] (5) Functionalized glass fiber and functionalized polyetheretherketone were mixed in a mass ratio of 1:9, stirred at 336°C for 20 min, evenly coated on a polytetrafluoroethylene plate with a thickness of 30 μm, allowed to stand at 70°C for 9 h, and 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 comprises the following preparation steps:

[0036] (1) Acrylonitrile and bis(4-fluorophenyl)phosphine oxide were mixed in a molar ratio of 1:1, placed in a high-pressure reactor, reacted at 120°C for 11 hours, and taken out to obtain a flame retardant monomer; the flame retardant monomer, hydroquinone, 4,4'-difluorobenzophenone, potassium carbonate and cyclopentane sulfone were mixed in a molar ratio of 1:5:4:6:51.5, heated to 210°C under argon protection, stirred at 250r / min for 10.5 hours, poured into deionized water, allowed to stand for 10 minutes, filtered, washed with deionized water 6 times, and vacuum dried at 60°C for 24 hours to obtain pre-modified polyetheretherketone; the pre-modified polyetheretherketone, 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 hours, ground to 9 mesh, washed with ethanol 6 times, and vacuum dried at -5°C for 24 hours to obtain modified polyetheretherketone;

[0037] (2) N-(2-aminopropyl)maleimide, The functionalized polyetheretherketone precursor was prepared by mixing a type molecular sieve, modified polyetheretherketone and toluene in a mass ratio of 1:2:13:28, stirring at 160°C and 250r / min for 24h, naturally cooling to room temperature, filtering, removing the molecular sieve, washing with ethanol 4 times, and vacuum drying at 60°C for 12h. The functionalized polyetheretherketone precursor, furfuryl isocyanate, ethanol and dibutyltin dilaurate were mixed in a mass ratio of 1:0.15:20:0.025, stirring at 250r / min and 65°C for 6h, filtering, washing with ethanol 4 times, and vacuum drying at -5°C for 24h to prepare the functionalized polyetheretherketone.

[0038] (3) 1-allyl-1H-pyrrole, 1-methylpyrrole, ferric chloride and ethanol were mixed uniformly in a molar ratio of 1:4:5:25 to prepare a pyrrole mixture; glass fiber 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 ° C and 250 r / min for 6 h, filtered, washed with deionized water 4 times, and dried at 95 ° C for 3 h to prepare pre-modified glass fiber; the pre-modified glass fiber was immersed in the pyrrole mixture for 4 min, taken out, no liquid dripped, and dried at 60 ° C for 12 h to prepare modified glass fiber;

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

[0040] (5) Functionalized glass fiber and functionalized polyetheretherketone were mixed in a mass ratio of 1:10, stirred at 338°C for 25 min, evenly 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 a plastic film.

[0041] Example 3:

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

[0043] (1) Acrylonitrile and bis(4-fluorophenyl)phosphine oxide were mixed in a molar ratio of 1:1, placed in a high-pressure reactor, reacted at 125°C for 12 hours, and taken out to obtain a flame retardant monomer; the flame retardant monomer, hydroquinone, 4,4'-difluorobenzophenone, potassium carbonate and cyclopentane sulfone were mixed in a molar ratio of 1:6:5:6.5:52, heated to 215°C under argon protection, stirred at 300r / min for 11 hours, poured into deionized water, allowed to stand for 12 minutes, filtered, washed with deionized water 7 times, and vacuum dried at 65°C for 25 hours to obtain pre-modified polyetheretherketone; the pre-modified polyetheretherketone, 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 hours, ground to 10 mesh, washed with ethanol 7 times, and vacuum dried at 0°C for 26 hours to obtain modified polyetheretherketone;

[0044] (2) N-(2-aminopropyl)maleimide, The functionalized polyetheretherketone precursor was prepared by mixing the molecular sieve, modified polyetheretherketone and toluene in a mass ratio of 1:2.2:14:30, stirring at 165°C and 300 r / min for 25 h, naturally cooling to room temperature, filtering, removing the molecular sieve, washing with ethanol 5 times, and vacuum drying at 65°C for 13 h. The functionalized polyetheretherketone precursor, furfuryl isocyanate, ethanol and dibutyltin dilaurate were mixed in a mass ratio of 1:0.16:22:0.03, stirring at 300 r / min and 67°C for 6.5 h, filtering, washing with ethanol 5 times, and vacuum drying at 0°C for 26 h to prepare the functionalized polyetheretherketone.

[0045] (3) 1-allyl-1H-pyrrole, 1-methylpyrrole, ferric chloride and ethanol were mixed uniformly in a molar ratio of 1:5:6:30 to prepare a pyrrole mixture; glass fiber 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 ° C and 300 r / min for 7 h, filtered, washed with deionized water 5 times, and dried at 100 ° C for 4 h to prepare pre-modified glass fiber; the pre-modified glass fiber was immersed in the pyrrole mixture for 5 min, taken out, no liquid dripped, and dried at 65 ° C for 13 h to prepare modified glass fiber;

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

[0047] (5) Functionalized glass fiber and functionalized polyetheretherketone were mixed in a mass ratio of 1:11, stirred at 340°C for 30 min, evenly coated on a polytetrafluoroethylene plate with a thickness of 40 μm, allowed to stand at 74°C for 11 h, and 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 of Comparative Example 1 and Example 2 lies in the difference in step (2). Step (2) is modified as follows: N-(2-aminopropyl)maleimide, Functionalized polyetheretherketone (PEEK) was prepared by mixing molecular sieves, modified polyetheretherketone (PEEK) and toluene in a mass ratio of 1:2:13:28, stirring at 160°C and 250 rpm for 24 hours, cooling naturally to room temperature, filtering, removing the molecular sieves, washing with ethanol four times, and vacuum drying at 60°C for 12 hours. The remaining steps were the same as in Example 2.

[0050] Comparative Example 2:

[0051] The preparation method of the high-temperature and low-temperature resistant plastic film of Comparative Example 2 differs from that of Comparative Example 1 in that 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, reacted at 120°C for 11 hours, and taken out to prepare a flame retardant monomer; the flame retardant monomer, hydroquinone, 4,4'-difluorobenzophenone, potassium carbonate, and cyclopentane 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 hours, poured into deionized water, allowed to stand for 10 minutes, filtered, washed with deionized water 6 times, and vacuum dried at 60°C for 24 hours to prepare modified polyetheretherketone. The remaining steps are the same as those of Comparative Example 1.

[0052] Comparative Example 3:

[0053] The method for preparing a high-temperature and low-temperature resistant plastic film of Comparative Example 3 differs from that of Comparative Example 1 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°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 with deionized water 6 times, and vacuum dried at 60°C for 24 h to obtain modified polyetheretherketone. The remaining steps are the same as those of Comparative Example 1.

[0054] Comparative Example 4:

[0055] The method for preparing a high-temperature and low-temperature resistant plastic film of Comparative Example 4 differs from that of Example 2 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 with ethanol five times, and vacuum dried at 0°C for 26 h to obtain functionalized polyetheretherketone. The remaining steps are the same as those of Example 2.

[0056] Comparative Example 5:

[0057] The method for preparing a high-temperature-resistant and low-temperature-resistant plastic film in Comparative Example 5 differs from that in Example 2 in step (4). Step (4) is modified as follows: modified glass fiber, N-(furan-2-ylmethyl)ethylamine, and methanol are mixed in a mass ratio of 1:0.15:12, stirred at 50°C, 250 rpm, under argon protection for 4 hours, filtered, washed four 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 method for preparing the high-temperature and low-temperature resistant plastic film of Comparative Example 6 differs from that of Example 2 in that steps (3), (4), and (5) are different. Steps (3) and (4) are deleted, and step (5) is modified as follows: glass fiber with a diameter of 5 μm and functionalized polyetheretherketone are mixed in a mass ratio of 1:10, stirred at 338°C for 25 minutes, and evenly coated on a polytetrafluoroethylene plate to a thickness of 35 μm. The mixture is allowed to stand at 72°C for 10 hours and scraped off to obtain a plastic film. The remaining steps are the same as those of Example 2.

[0060] Test Example 1:

[0061] Flame retardancy test

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

[0063] Table 1

[0064]

[0065]

[0066] From the comparison of the experimental data in Table 1, it can be found that the high-temperature and low-temperature resistant plastic film prepared by the present invention has good flame retardancy.

[0067] From the comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 3 in Table 1, it can be found that the limiting oxygen index of Examples 1, 2, and 3 is larger than that of Comparative Example 3. The difference between Comparative Example 3 and the Examples is that the polyetheretherketone is not modified by organic phosphorus, which shows that the introduction of organic phosphorus enhances the flame retardant effect of the material.

[0068] Test Example 2:

[0069] Antibacterial testing

[0070] The high-temperature and low-temperature resistant plastic films prepared in each example and comparative example were crushed to 30 mesh, and 1 g was taken for testing according to GB / T31402-2015 standard, wherein the selected bacterial species were Staphylococcus aureus and Escherichia coli. The results are shown in Table 2.

[0071] Table 2

[0072]

[0073]

[0074] From the comparison of the experimental data in Table 2, it can be found that the high-temperature and low-temperature resistant plastic film prepared by the present invention has good antibacterial ability.

[0075] From the comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 5 in Table 2, it can be found that the antibacterial rates of Examples 1, 2, and 3 are higher than those of Comparative Example 5. The difference between Comparative Example 5 and the Examples is that no zwitterions are formed on the surface of the glass fiber, which shows that the anion and cationic groups in the zwitterions can effectively inhibit bacterial adhesion and prevent the formation of biofilms, thereby achieving the purpose of inhibiting bacterial reproduction; and the sulfonic acid anions can interfere with the synthesis of bacterial cell walls, causing defects in the bacterial cell walls. Since the bacteria are in a hypertonic state, external water will continue to infiltrate, causing the bacteria to swell, deform, and eventually die; and quaternary ammonium salts can change the permeability of microbial cells, causing the bacteria to rupture, thereby destroying the internal structure of the cells; they can also denature proteins, thereby affecting the normal function of the cells and causing cell death, thereby achieving an antibacterial effect.

[0076] Test Example 3:

[0077] Aging resistance and self-repair test:

[0078] Self-repair test: The plastics prepared in each embodiment 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. A small cut 3 mm long and 15 μm deep was made in the middle of the same strips. The strips were placed in a constant temperature oven at 70°C for 2 hours. The tensile strength of the repaired strips was tested and recorded as the tensile strength after self-repair. The self-repair efficiency was calculated, where self-repair efficiency = tensile strength after self-repair / initial tensile strength * 100%;

[0079] Aging resistance test: The plastics produced in each example and comparative example were molded into strips 10 mm long, 4 mm wide, and 30 μm thick. The tensile strength was measured, which was recorded as the initial tensile strength. The same strips were then irradiated with a UV-A340 fluorescent lamp for 15 days and the tensile strength was again measured, which was recorded as the post-aging tensile strength. The tensile strength retention rate was calculated as follows: tensile strength retention rate = post-aging tensile strength / initial tensile strength * 100%. The results are shown in Table 3.

[0080] Table 3

[0081]

[0082]

[0083] From the comparison of the experimental data in Table 3, it can be found that the high-temperature and low-temperature resistant plastic film prepared by the present invention has good aging resistance and self-repairing ability.

[0084] From the comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 1 in Table 3, it can be found that the self-repair efficiency of Examples 1, 2, and 3 is greater than that of Comparative Example 1. The difference between Comparative Example 1 and the embodiment is that no furan group is introduced into the polyetheretherketone chain, which shows that the difference between Comparative Example 1 and the embodiment is that the polyetheretherketone is not functionalized with furan, and the maleimide group and the furan group can react in a DA reaction without a catalyst and under relatively mild reaction conditions to achieve a self-repair effect.

[0085] From the comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 2, it can be found that the tensile strength retention rate of Examples 1, 2, and 3 is greater than that of Comparative Example 2. The difference between Comparative Example 2 and the embodiment is that no triazine ring is formed on the polyetheretherketone chain, which shows that the difference between Comparative Example 2 and the embodiment is that no triazine ring is generated on the polyetheretherketone. The triazine ring can delay the aging process of the material by reflecting ultraviolet light, and through the reaction of 2,4-dihydroxybenzonitrile with the polyetheretherketone main chain, a triazine with an ortho-phenolic hydroxyl group can be formed. The ortho-phenolic hydroxyl group forms a conjugated ring with the triazine, which makes the electron cloud distribution inside the molecule more uniform, thereby improving its stability and further improving the aging resistance of the material.

[0086] Test Example 4:

[0087] Antistatic test:

[0088] The surface resistivity test was conducted at 20°C according to GB / T1410-2006. 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] From the comparison of the experimental data in Table 4, it can be found that the high-temperature and low-temperature resistant plastic film prepared by the present invention has good antistatic ability.

[0092] From the comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 5 in Table 4, it can be found that the surface resistivity of Examples 1, 2, and 3 is lower than that of Comparative Example 5. The difference between Comparative Example 5 and the Example is that no zwitterions are formed on the surface of the glass fiber, which shows that the quaternary ammonium salt and the sulfonic acid group as hydrophilic groups can absorb moisture in the environment to form a conductive path, thereby promoting the dissipation of charge, avoiding the accumulation of static electricity, and achieving an antistatic effect.

[0093] From the comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 6, it can be found that the surface resistivity of Examples 1, 2, 3 is lower than that of Comparative Example 6. The difference between Comparative Example 6 and the examples is that the glass fiber is not modified, which shows that polypyrrole, as a conductive polymer, can form a conductive layer, so that the static charge that has been generated can be quickly leaked, thereby achieving an antistatic effect.

[0094] The specific implementation methods described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific implementation method 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 in 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 polyetheretherketone, coating the mixture on a polytetrafluoroethylene plate, and scraping it off. The functionalized glass fiber is prepared by reacting glass fiber with N-(3-trimethoxysilylpropyl)pyrrole, 1-allyl-1H-pyrrole, 1-methylpyrrole, N-(furan-2-ylmethyl)ethylamine and 1,3-propane sultone in sequence; The functionalized polyetheretherketone is prepared by sequentially reacting bis(4-fluorophenyl)phosphine oxide with acrylonitrile, hydroquinone, 4,4'-difluorobenzophenone, 2,4-dihydroxybenzonitrile, N-(2-aminopropyl)maleimide and furfuryl isocyanate.

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 polyetheretherketone, 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°C for 46-50h, ground to 8-10 mesh, washed with ethanol 5-7 times, and vacuum dried at -10-0°C for 22-26h to obtain modified polyetheretherketone; (2) functionalized polyetheretherketone precursor, furfuryl isocyanate, ethanol and catalyst are mixed in a mass ratio of 1:0.14-0.16:18-22:0.02-0.03, stirred at 200-300 r / min and 63-67°C for 5.5-6.5 h, filtered, washed with ethanol 3-5 times, and vacuum dried at -10-0°C for 22-26 h to obtain functionalized polyetheretherketone; (3) soaking the pre-modified glass fiber in the pyrrole mixture for 3 to 5 minutes, taking it out until no liquid drops, and drying it at 55 to 65° C. for 11 to 13 hours to obtain the modified glass fiber; (4) Modified glass fiber, N-(furan-2-ylmethyl)ethylamine and methanol are mixed in a mass ratio of 1:0.13-0.17:10-14, stirred at 45-55°C, 200-300 r / min, under argon protection for 3.5-4.5 hours, filtered, washed with ethanol 3-5 times, and dried to obtain a functionalized glass fiber precursor; (5) Functionalized glass fiber and functionalized polyetheretherketone are mixed in a mass ratio of 1:9-11, stirred at 336-340°C for 20-30 minutes, evenly coated on a polytetrafluoroethylene plate with a thickness of 30-40 μm, allowed to stand at 70-74°C for 9-11 hours, and scraped off to obtain a 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 in step (1) is prepared by mixing a 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 the mixture to 205-215°C under argon protection, stirring the mixture at 200-300 r / min for 10-11 hours, pouring the mixture into deionized water, allowing the mixture to stand for 8-12 minutes, filtering the mixture, washing the mixture with deionized water for 5-7 times, and vacuum drying the mixture at 55-65°C for 23-25 hours.

4. The method for preparing a high-temperature and low-temperature resistant plastic film according to claim 2, characterized in that: The functionalized polyetheretherketone precursor in step (2) is N-(2-aminopropyl)maleimide, The product is prepared by mixing molecular sieve, modified polyetheretherketone and toluene in a mass ratio of 1:1.8-2.2:12-14:26-30, stirring at 155-165°C and 200-300r / min for 23-25h, naturally cooling to room temperature, filtering, removing molecular sieve, washing with ethanol 3-5 times, and vacuum drying at 55-65°C for 11-13h.

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 uniformly 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 isopropyl alcohol 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° C. and 200-300 r / min for 5-7 hours, filtering, washing with deionized water for 3-5 times, and drying at 90-100° C. for 2-4 hours.

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

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 the mixture in a high-pressure reactor, and reacting the mixture at 115-125° C. for 10-12 hours.

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