CN116622172B - Corrosion-resistant ultraviolet-resistant film and preparation method and application thereof - Google Patents
Corrosion-resistant ultraviolet-resistant film and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of film materials, and discloses a corrosion-resistant ultraviolet-resistant film, a preparation method and application thereof, wherein polyvinyl chloride, polyurethane elastomer, ultraviolet-resistant modified zinc oxide grafted polymethyl methacrylate, polypropylene, flatting agent and antioxidant are uniformly mixed, the corrosion-resistant ultraviolet-resistant film is obtained by utilizing the synergistic effect of all components through melt blending and tape casting, electrons on a nano zinc oxide valence band in the ultraviolet-resistant modified zinc oxide grafted polymethyl methacrylate can absorb ultraviolet rays, meanwhile, the ultraviolet-resistant film has scattering capability, and introduced 2- (2, 4-dihydroxyphenyl) -2H-benzotriazole can destroy hydrogen bonds in molecules after absorbing ultraviolet light and can convert high-energy ultraviolet light into heat energy to release, and meanwhile, polypropylene and polymethyl methacrylate have excellent corrosion resistance and aging resistance.
Description
Technical Field
The invention relates to the technical field of film materials, in particular to a corrosion-resistant ultraviolet-resistant film, a preparation method and application thereof.
Background
With the rapid development of economy, the living standard of people is gradually improved, and an automobile is taken as a walking tool for more and more people, so that people travel is greatly facilitated, but the automobile is exposed to sunlight for a long time, so that the temperature of a seat and a steering wheel in the automobile is suddenly increased, meanwhile, the automobile glass can not completely block the penetration of ultraviolet rays in the running process of the automobile, the human body basically keeps a sitting state, the skin of the human body can be sunburned, and in order to reduce the ultraviolet ray invasion of the skin in the automobile, proper measures are required to be taken to reduce the ultraviolet ray from penetrating the automobile glass, so that the ultraviolet ray injury to the skin of the personnel in the automobile is reduced.
The automobile film is used as a functional film, can improve the optical performance of automobile glass to a great extent, is mainly used on side window glass and sunroof of an automobile, and has the effects of sun protection, ultraviolet isolation and private space building. Along with the serious environmental pollution, the acid-base pollution in the environment can cause the easy damage of the automobile film, and the corrosion resistance treatment of the automobile film is particularly important, so that the service life of the film can be effectively prolonged.
Chinese patent application CN104130553A discloses an ultraviolet-proof solar film and a preparation method thereof, wherein the solar film comprises PET polyester chips, inorganic ultraviolet absorbers, scratch-proof agents, anti-blocking agents and beta-1 # decomposition anti-reflection agents. The invention improves the compatibility of the inorganic ultraviolet absorbent and the PET polyester chip, but has poor heat insulation, sun protection and sun protection effects.
Chinese patent CN104842608B discloses an ultraviolet resistant polyester film for window film and its preparation method, comprising a core layer of crystalline PET homopolymer and benzotriazole modified crystalline PET copolymer, and upper and lower surface layers of crystalline PET copolymer and crystalline PET homopolymer modified with nano inorganic substance as main components. The invention has excellent ultraviolet blocking rate and high visible light transmittance, but has poor weather resistance and narrow ultraviolet absorption frequency.
Disclosure of Invention
In order to solve the technical problems, the invention provides a corrosion-resistant ultraviolet-resistant film, a preparation method and application thereof, and solves the problems of poor ultraviolet resistance, corrosion resistance and weather resistance of an automobile film.
In order to achieve the above purpose, the invention discloses a preparation method of a corrosion-resistant ultraviolet-resistant film, which comprises the following steps:
uniformly mixing dichloromethane and 3,3' - (ethylene-1, 2-diyl) dibenzoyl chloride, adding nano zinc oxide (ZnO) and Triethylamine (TEA), uniformly mixing, reacting, filtering after the reaction is finished, washing filter residues by using dichloromethane, and drying the filter residues in a vacuum drying oven at 45-55 ℃ for 3-5 hours to obtain zinc oxychloride;
step (2) evenly mixing tetrahydrofuran and acyl zinc oxide, adding 2- (2, 4-dihydroxyphenyl) -2H-benzotriazole and triethylamine, evenly mixing, reacting, respectively washing with saturated sodium bicarbonate solution and absolute ethyl alcohol after the reaction is finished, carrying out suction filtration, and carrying out vacuum drying at 50-60 ℃ for 6-8 hours to obtain benzotriazole modified zinc oxide;
step (3) mixing absolute ethyl alcohol and deionized water uniformly, adding benzotriazole modified zinc oxide, dispersing uniformly, adding methyl methacrylate and dibenzoyl peroxide, reacting, pouring into a mould after the reaction is finished, and drying in a drying oven at 55-65 ℃ for 36-48h to obtain the ultraviolet-resistant modified zinc oxide grafted polymethyl methacrylate;
and (4) uniformly mixing polyvinyl chloride, polyurethane elastomer, anti-ultraviolet modified zinc oxide grafted polymethyl methacrylate, polypropylene, a leveling agent and an antioxidant, adding into a double-screw extruder for melt blending, extruding, cooling and granulating to obtain film material master batches, and carrying out tape casting molding on the film material master batches by a tape casting machine to obtain the anti-corrosion anti-ultraviolet film.
Preferably, the mass ratio of the dichloromethane, the 3,3' - (ethylene-1, 2-diyl) dibenzoyl chloride, the nano zinc oxide and the triethylamine in the step (1) is 5200-6000:75-95:100:1-2.
Preferably, the temperature of the reaction in the step (1) is 40-45 ℃, and the reaction time is 2-3h.
Preferably, the mass ratio of tetrahydrofuran, zinc oxychloride, 2- (2, 4-dihydroxyphenyl) -2H-benzotriazole and triethylamine in the step (2) is 1800-2500:100:240-320:95-150.
Preferably, the temperature of the reaction in the step (2) is 0-5 ℃ and the reaction time is 9-12h.
Preferably, the mass ratio of the absolute ethyl alcohol, the deionized water, the benzotriazole modified zinc oxide, the methyl methacrylate and the dibenzoyl peroxide in the step (3) is 1200-1800:500-750:30-50:100:2-5.
Preferably, the temperature of the reaction in the step (3) is 80-90 ℃ and the reaction time is 5-7h.
Preferably, in the step (4), the mass ratio of the polyvinyl chloride, the polyurethane elastomer, the anti-ultraviolet modified zinc oxide grafted polymethyl methacrylate, the polypropylene, the leveling agent and the antioxidant is 100:75-95:20-32:10-20:0.1-0.3:0.5-2.
Preferably, the leveling agent in the step (4) comprises one or more of modified polydimethylsiloxane, polyacrylamide and polyacrylate.
Preferably, the antioxidant in the step (4) comprises one or more of an antioxidant 1076, an antioxidant 1010 and an antioxidant 168.
Preferably, the twin screw extruder in step (4) has five temperature zones, respectively: the temperature of the first section of feeding section is set to 155-170 ℃, the temperature of the second section of mixing section is set to 165-180 ℃, the temperature of the third section of mixing section is set to 175-190 ℃, the temperature of the fourth section of calculating section is set to 175-200 ℃, the temperature of the fifth section of discharging section is set to 185-200 ℃, and the rotating speed of the twin-screw extruder is 35-45r/min; the temperature of the filter screen of the casting machine is set to be 200-220 ℃, the temperature of the elbow is set to be 205-225 ℃, the connection temperature of the die head is set to be 195-220 ℃, and the temperature of the die head is set to be 195-235 ℃.
Preferably, the corrosion-resistant ultraviolet-resistant film is prepared by the preparation method of the corrosion-resistant ultraviolet-resistant film.
Preferably, the corrosion-resistant ultraviolet-resistant film is applied to an automobile film.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, firstly, 3'- (ethylene-1, 2-diyl) dibenzoyl chloride is used for modifying nano zinc oxide, acyl chloride groups on the 3,3' - (ethylene-1, 2-diyl) dibenzoyl chloride react with hydroxyl groups on the surface of nano zinc oxide, unreacted acyl chloride groups and carbon-carbon double bonds are introduced on the surface of nano zinc oxide, so that acyl chloride zinc oxide is obtained, acyl chloride on the surface of acyl chloride zinc oxide reacts with hydroxyl groups on 2- (2, 4-dihydroxyphenyl) -2H-benzotriazole to obtain benzotriazole modified zinc oxide, and agglomeration of nano zinc oxide in a system is effectively improved, and compatibility and dispersibility are improved; under the action of dibenzoyl peroxide as initiator, the carbon-carbon double bond on benzotriazole modified zinc oxide and methyl methacrylate are polymerized to obtain ultraviolet-resistant modified zinc oxide grafted polymethyl methacrylate, and polyvinyl chloride, polyurethane elastomer, ultraviolet-resistant modified zinc oxide grafted polymethyl methacrylate, polypropylene, flatting agent and antioxidant are uniformly mixed, and the corrosion-resistant ultraviolet-resistant film is obtained through melt blending and tape casting by utilizing the synergistic effect of the components.
The nano zinc oxide has the characteristic of bandwidth inhibition, when being irradiated by ultraviolet rays, electrons on a valence band can absorb ultraviolet rays and be excited to a conduction band, so that electron-hole pairs are generated, and due to the nano-size effect, the nano zinc oxide has scattering capacity on the ultraviolet rays and can play a role in resisting ultraviolet rays, and after the introduced 2- (2, 4-dihydroxyphenyl) -2H-benzotriazole absorbs the ultraviolet rays, hydrogen bonds in molecules are destroyed, high-energy ultraviolet light can be converted into heat energy, corresponding energy conversion is carried out, the energy of the ultraviolet light is converted into harmless low-radiation heat energy to be released, and the ultraviolet light are simultaneously added to the film, so that the ultraviolet light absorption range is wider, the absorption efficiency is higher, and the ageing of the film is effectively slowed down. The anti-ultraviolet modified zinc oxide grafted polymethyl methacrylate is mixed with other materials to obtain a film, so that the ultraviolet absorption capacity can be further enhanced, and the skin of a person in the automobile is protected from being damaged by ultraviolet rays.
The polyvinyl chloride used in the invention has the characteristics of good transparency and glossiness, and good mechanical properties, the polyurethane elastomer has excellent elasticity, ageing resistance, weather resistance and high and low temperature resistance, the toughness and ageing resistance of the film can be improved to a great extent, the polypropylene material has excellent mechanical properties, is not easy to break, has good chemical stability and corrosion resistance, the polymethyl methacrylate has excellent chemical stability and weather resistance, and meanwhile, the used nanoscale material can reduce the surface tension of the film material, so that pollutants and water are not easy to adhere to a car film, and the obtained film has excellent light transmittance, excellent mechanical properties, good oxidation resistance, prolonged service life of the film, and has good ultraviolet resistance and corrosion resistance.
Drawings
FIG. 1 is a flow chart of the process for preparing the corrosion-resistant UV-resistant film of the present invention.
FIG. 2 is a schematic diagram of the structure of the preparation of acid chloride zinc oxide according to the present invention.
FIG. 3 is a schematic diagram of the structure of benzotriazole modified zinc oxide prepared in accordance with the present invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and all other embodiments obtained by those skilled in the art without making any inventive effort based on the embodiments of the present invention are within the scope of protection of the present invention.
Example 1A method for preparing the anti-corrosion and anti-ultraviolet film of the embodiment comprises the following steps:
(1) Uniformly mixing dichloromethane and 3,3'- (ethylene-1, 2-diyl) dibenzoyl chloride, adding nano zinc oxide and triethylamine, uniformly mixing, wherein the mass ratio of the dichloromethane to the 3,3' - (ethylene-1, 2-diyl) dibenzoyl chloride to the nano zinc oxide to the triethylamine is 5200:75:100:1, reacting at 40 ℃ for 3 hours, filtering after the reaction is finished, washing filter residues by using the dichloromethane, and drying the filter residues in a vacuum drying oven at 45 ℃ for 5 hours to obtain chlorinated zinc oxide;
(2) Evenly mixing tetrahydrofuran and acyl zinc oxide, adding 2- (2, 4-dihydroxyphenyl) -2H-benzotriazole and triethylamine, evenly mixing, wherein the mass ratio of the added tetrahydrofuran to the acyl zinc oxide to the added 2- (2, 4-dihydroxyphenyl) -2H-benzotriazole to the added triethylamine is 1800:100:240:95, reacting at 0 ℃ for 12 hours, washing with saturated sodium bicarbonate solution and absolute ethyl alcohol respectively after the reaction is finished, filtering, and drying in vacuum at 50 ℃ for 8 hours to obtain benzotriazole modified zinc oxide;
(3) Uniformly mixing absolute ethyl alcohol and deionized water, adding benzotriazole modified zinc oxide, uniformly dispersing, adding methyl methacrylate and dibenzoyl peroxide, reacting at 80 ℃ for 7 hours, wherein the mass ratio of the absolute ethyl alcohol to the deionized water to the benzotriazole modified zinc oxide to the methyl methacrylate to the dibenzoyl peroxide is 1200:500:30:100:2, pouring the mixture into a mould after the reaction is finished, and drying the mixture in a drying box at 55 ℃ for 48 hours to obtain the ultraviolet-resistant modified zinc oxide grafted polymethyl methacrylate;
(4) Uniformly mixing polyvinyl chloride, polyurethane elastomer, ultraviolet-resistant modified zinc oxide grafted polymethyl methacrylate, polypropylene, leveling agent polydimethylsiloxane and antioxidant 1076 in a mass ratio of 100:75:20:10:0.1:0.5, adding into a double-screw extruder for melt blending, extruding, cooling and granulating to obtain film material master batches, wherein the double-screw extruder has five sections of temperature areas, namely: the temperature of the first section of feeding section is set at 155 ℃, the temperature of the second section of mixing section is set at 165 ℃, the temperature of the third section of mixing section is set at 175 ℃, the temperature of the fourth section of calculating section is set at 175 ℃, the temperature of the fifth section of discharging section is set at 185 ℃, the rotating speed of the twin-screw extruder is 45r/min, the film material master batch is formed by casting through a casting machine, the temperature of a casting machine filter screen is set at 200 ℃, the temperature of an elbow is set at 205 ℃, the die head connection temperature is set at 195 ℃, and the die head temperature is set at 195 ℃, so that the corrosion-resistant ultraviolet-resistant film is obtained.
Example 2A method for preparing the anti-corrosion and anti-ultraviolet film of the embodiment comprises the following steps:
(1) Uniformly mixing dichloromethane and 3,3'- (ethylene-1, 2-diyl) dibenzoyl chloride, adding nano zinc oxide and triethylamine, uniformly mixing, wherein the mass ratio of the dichloromethane to the 3,3' - (ethylene-1, 2-diyl) dibenzoyl chloride to the nano zinc oxide to the triethylamine is 5500:82:100:1.4, reacting at 42 ℃ for 2.5 hours, filtering after the reaction is finished, washing filter residues by using the dichloromethane, and drying the filter residues in a vacuum drying oven at 50 ℃ for 4 hours to obtain acyl zinc oxide chloride;
(2) Evenly mixing tetrahydrofuran and acyl zinc oxide, adding 2- (2, 4-dihydroxyphenyl) -2H-benzotriazole and triethylamine, evenly mixing, wherein the mass ratio of the added tetrahydrofuran to the acyl zinc oxide to the added 2- (2, 4-dihydroxyphenyl) -2H-benzotriazole to the added triethylamine is 2100:100:270:115, reacting at 2 ℃ for 10 hours, washing with saturated sodium bicarbonate solution and absolute ethyl alcohol respectively after the reaction is finished, filtering, and vacuum drying at 55 ℃ for 7 hours to obtain benzotriazole modified zinc oxide;
(3) Uniformly mixing absolute ethyl alcohol and deionized water, adding benzotriazole modified zinc oxide, uniformly dispersing, adding methyl methacrylate and dibenzoyl peroxide, reacting at 85 ℃ for 6 hours, wherein the mass ratio of the absolute ethyl alcohol to the deionized water to the benzotriazole modified zinc oxide to the methyl methacrylate to the dibenzoyl peroxide is 1400:600:38:100:3, pouring the mixture into a mould after the reaction is finished, and drying the mixture in a drying box at 60 ℃ for 42 hours to obtain the ultraviolet-resistant modified zinc oxide grafted polymethyl methacrylate;
(4) Uniformly mixing polyvinyl chloride, polyurethane elastomer, ultraviolet-resistant modified zinc oxide grafted polymethyl methacrylate, polypropylene, leveling agent polydimethylsiloxane and antioxidant 1076 in a mass ratio of 100:82:25:14:0.15:1, adding into a double-screw extruder for melt blending, extruding, cooling and granulating to obtain film material master batches, wherein the double-screw extruder is provided with five sections of temperature areas, and the five sections of temperature areas are respectively: the temperature of the first section of feeding section is set at 160 ℃, the temperature of the second section of mixing section is set at 170 ℃, the temperature of the third section of mixing section is set at 180 ℃, the temperature of the fourth section of calculating section is set at 180 ℃, the temperature of the fifth section of discharging section is set at 190 ℃, the rotating speed of the twin-screw extruder is 40r/min, the film material master batch is formed by casting through a casting machine, the temperature of a casting machine filter screen is set at 210 ℃, the temperature of an elbow is set at 215 ℃, the die head connection temperature is set at 205 ℃, and the die head temperature is set at 210 ℃, so that the corrosion-resistant ultraviolet-resistant film is obtained.
Example 3A method for preparing the anti-corrosion and anti-ultraviolet film of the embodiment comprises the following steps:
(1) Uniformly mixing dichloromethane and 3,3'- (ethylene-1, 2-diyl) dibenzoyl chloride, adding nano zinc oxide and triethylamine, uniformly mixing, wherein the mass ratio of the dichloromethane to the 3,3' - (ethylene-1, 2-diyl) dibenzoyl chloride to the nano zinc oxide to the triethylamine is 5800:90:100:1.8, reacting at 42 ℃ for 2.5 hours, filtering after the reaction is finished, washing filter residues by using the dichloromethane, and drying the filter residues in a vacuum drying oven at 50 ℃ for 4 hours to obtain acyl zinc oxide chloride;
(2) Evenly mixing tetrahydrofuran and acyl zinc oxide, adding 2- (2, 4-dihydroxyphenyl) -2H-benzotriazole and triethylamine, evenly mixing, wherein the mass ratio of the added tetrahydrofuran to the acyl zinc oxide to the added 2- (2, 4-dihydroxyphenyl) -2H-benzotriazole to the added triethylamine is 2400:100:300:135, reacting at 2 ℃ for 11 hours, washing with saturated sodium bicarbonate solution and absolute ethyl alcohol respectively after the reaction is finished, filtering, and vacuum drying at 55 ℃ for 7 hours to obtain benzotriazole modified zinc oxide;
(3) Uniformly mixing absolute ethyl alcohol and deionized water, adding benzotriazole modified zinc oxide, uniformly dispersing, adding methyl methacrylate and dibenzoyl peroxide, reacting at 85 ℃ for 6 hours, wherein the mass ratio of the absolute ethyl alcohol to the deionized water to the benzotriazole modified zinc oxide to the methyl methacrylate to the dibenzoyl peroxide is 1600:700:45:100:4, pouring the mixture into a mould after the reaction is finished, and drying the mixture in a drying box at 60 ℃ for 42 hours to obtain the ultraviolet-resistant modified zinc oxide grafted polymethyl methacrylate;
(4) Uniformly mixing polyvinyl chloride, polyurethane elastomer, ultraviolet-resistant modified zinc oxide grafted polymethyl methacrylate, polypropylene, leveling agent polydimethylsiloxane and antioxidant 1076 in a mass ratio of 100:90:30:18:0.25:1.5, adding into a double-screw extruder for melt blending, extruding, cooling and granulating to obtain film material master batches, wherein the double-screw extruder has five temperature zones: the temperature of the first section of feeding section is set at 165 ℃, the temperature of the second section of mixing section is set at 175 ℃, the temperature of the third section of mixing section is set at 185 ℃, the temperature of the fourth section of calculating section is set at 190 ℃, the temperature of the fifth section of discharging section is set at 195 ℃, the rotating speed of the twin-screw extruder is 40r/min, the film material master batch is formed by casting through a casting machine, the temperature of a casting machine filter screen is set at 215 ℃, the temperature of an elbow is set at 220 ℃, the die head connection temperature is set at 215 ℃, and the die head temperature is set at 225 ℃ to obtain the corrosion-resistant ultraviolet-resistant film.
Example 4A method for preparing the anti-corrosion and anti-ultraviolet film of the embodiment comprises the following steps:
(1) Uniformly mixing dichloromethane and 3,3'- (ethylene-1, 2-diyl) dibenzoyl chloride, adding nano zinc oxide and triethylamine, uniformly mixing, wherein the mass ratio of the dichloromethane to the 3,3' - (ethylene-1, 2-diyl) dibenzoyl chloride to the nano zinc oxide to the triethylamine is 6000:95:100:2, reacting at 45 ℃ for 2 hours, filtering after the reaction is finished, washing filter residues by using dichloromethane, and drying the filter residues in a vacuum drying oven at 55 ℃ for 3 hours to obtain chlorinated zinc oxide;
(2) Uniformly mixing tetrahydrofuran and acyl zinc oxide, adding 2- (2, 4-dihydroxyphenyl) -2H-benzotriazole and triethylamine, uniformly mixing, wherein the mass ratio of the added tetrahydrofuran to the acyl zinc oxide to the added 2- (2, 4-dihydroxyphenyl) -2H-benzotriazole to the added triethylamine is 2500:100:320:150, reacting at 5 ℃ for 9 hours, washing with saturated sodium bicarbonate solution and absolute ethyl alcohol respectively after the reaction is finished, filtering, and vacuum drying at 60 ℃ for 6 hours to obtain benzotriazole modified zinc oxide;
(3) Uniformly mixing absolute ethyl alcohol and deionized water, adding benzotriazole modified zinc oxide, uniformly dispersing, adding methyl methacrylate and dibenzoyl peroxide, reacting at 90 ℃ for 5 hours, wherein the mass ratio of the absolute ethyl alcohol to the deionized water to the benzotriazole modified zinc oxide to the methyl methacrylate to the dibenzoyl peroxide is 1800:750:50:100:5, pouring the mixture into a mould after the reaction is finished, and drying the mixture in a drying oven at 65 ℃ for 36 hours to obtain the ultraviolet-resistant modified zinc oxide grafted polymethyl methacrylate;
(4) Uniformly mixing polyvinyl chloride, polyurethane elastomer, ultraviolet-resistant modified zinc oxide grafted polymethyl methacrylate, polypropylene, leveling agent polydimethylsiloxane and antioxidant 1076 in a mass ratio of 100:95:32:20:0.3:2, adding into a double-screw extruder for melt blending, extruding, cooling and granulating to obtain film material master batches, wherein the double-screw extruder is provided with five sections of temperature areas, and the five sections of temperature areas are respectively: the temperature of the first section of feeding section is set at 170 ℃, the temperature of the second section of mixing section is set at 180 ℃, the temperature of the third section of mixing section is set at 190 ℃, the temperature of the fourth section of calculating section is set at 200 ℃, the temperature of the fifth section of discharging section is set at 200 ℃, the rotating speed of the twin-screw extruder is 35r/min, the master batch of the film material is formed by casting through a casting machine, the temperature of a filter screen of the casting machine is set at 220 ℃, the temperature of an elbow is set at 225 ℃, the die head connection temperature is set at 220 ℃, and the die head temperature is set at 235 ℃, so that the corrosion-resistant ultraviolet-resistant film is obtained.
Comparative example 1. A method for preparing the anti-corrosion and anti-ultraviolet film of the comparative example comprises the following steps:
(1) Uniformly mixing absolute ethyl alcohol and deionized water, adding methyl methacrylate and dibenzoyl peroxide, reacting at 85 ℃ for 6 hours, wherein the mass ratio of the absolute ethyl alcohol to the deionized water to the methyl methacrylate to the dibenzoyl peroxide is 1600:700:145:4, pouring the mixture into a mould after the reaction is finished, and drying the mixture in a drying box at 60 ℃ for 42 hours to obtain polymethyl methacrylate;
(2) Uniformly mixing polyvinyl chloride, polyurethane elastomer, nano zinc oxide, 2- (2, 4-dihydroxyphenyl) -2H-benzotriazole, polymethyl methacrylate, polypropylene, leveling agent polydimethylsiloxane and antioxidant 1076 in a mass ratio of 100:90:2.5:6.5:21:18:0.25:1.5, adding into a double-screw extruder for melt blending, extruding, cooling and granulating to obtain film material master batches, wherein the double-screw extruder has five sections of temperature areas, namely: the temperature of the first section of feeding section is set at 165 ℃, the temperature of the second section of mixing section is set at 175 ℃, the temperature of the third section of mixing section is set at 185 ℃, the temperature of the fourth section of calculating section is set at 190 ℃, the temperature of the fifth section of discharging section is set at 195 ℃, the rotating speed of the twin-screw extruder is 40r/min, the film material master batch is formed by casting through a casting machine, the temperature of a casting machine filter screen is set at 215 ℃, the temperature of an elbow is set at 220 ℃, the die head connection temperature is set at 215 ℃, and the die head temperature is set at 225 ℃ to obtain the corrosion-resistant ultraviolet-resistant film.
Comparative example 2. A method for preparing the anti-corrosion and anti-ultraviolet film of the comparative example comprises the following steps:
(1) Uniformly mixing dichloromethane and 3,3'- (ethylene-1, 2-diyl) dibenzoyl chloride, adding nano zinc oxide and triethylamine, uniformly mixing, wherein the mass ratio of the dichloromethane to the 3,3' - (ethylene-1, 2-diyl) dibenzoyl chloride to the nano zinc oxide to the triethylamine is 5800:90:100:1.8, reacting at 42 ℃ for 2.5 hours, filtering after the reaction is finished, washing filter residues by using the dichloromethane, and drying the filter residues in a vacuum drying oven at 50 ℃ for 4 hours to obtain acyl zinc oxide chloride;
(2) Uniformly mixing absolute ethyl alcohol and deionized water, adding zinc oxychloride, dispersing uniformly, adding methyl methacrylate and dibenzoyl peroxide, reacting at 85 ℃ for 6 hours, wherein the mass ratio of the absolute ethyl alcohol to the deionized water to the zinc oxychloride to the methyl methacrylate to the dibenzoyl peroxide is 1600:700:45:100:4, pouring the mixture into a mould after the reaction is finished, and drying the mixture in a drying oven at 60 ℃ for 42 hours to obtain zinc oxide grafted polymethyl methacrylate;
(3) Uniformly mixing polyvinyl chloride, polyurethane elastomer, zinc oxide grafted polymethyl methacrylate, polypropylene, leveling agent polydimethylsiloxane and antioxidant 1076 in a mass ratio of 100:90:30:18:0.25:1.5, adding into a double-screw extruder for melt blending, extruding, cooling and granulating to obtain film material master batches, wherein the double-screw extruder has five sections of temperature areas, namely: the temperature of the first section of feeding section is set at 165 ℃, the temperature of the second section of mixing section is set at 175 ℃, the temperature of the third section of mixing section is set at 185 ℃, the temperature of the fourth section of calculating section is set at 190 ℃, the temperature of the fifth section of discharging section is set at 195 ℃, the rotating speed of the twin-screw extruder is 40r/min, the film material master batch is formed by casting through a casting machine, the temperature of a casting machine filter screen is set at 215 ℃, the temperature of an elbow is set at 220 ℃, the die head connection temperature is set at 215 ℃, and the die head temperature is set at 225 ℃ to obtain the corrosion-resistant ultraviolet-resistant film.
Comparative example 3. A method for preparing the anti-corrosion and anti-ultraviolet film of the comparative example comprises the following steps:
(1) Uniformly mixing absolute ethyl alcohol and deionized water, adding methyl methacrylate and dibenzoyl peroxide, reacting at 85 ℃ for 6 hours, wherein the mass ratio of the absolute ethyl alcohol to the deionized water to the methyl methacrylate to the dibenzoyl peroxide is 1600:700:145:4, pouring the mixture into a mould after the reaction is finished, and drying the mixture in a drying box at 60 ℃ for 42 hours to obtain polymethyl methacrylate;
(2) Uniformly mixing polyvinyl chloride, polyurethane elastomer, 2- (2, 4-dihydroxyphenyl) -2H-benzotriazole, polymethyl methacrylate, polypropylene, leveling agent polydimethylsiloxane and antioxidant 1076 in a mass ratio of 100:90:6.5:23.5:18:0.25:1.5, adding into a double-screw extruder for melt blending, extruding, cooling and granulating to obtain film material master batches, wherein the double-screw extruder has five temperature zones, namely: the temperature of the first section of feeding section is set at 165 ℃, the temperature of the second section of mixing section is set at 175 ℃, the temperature of the third section of mixing section is set at 185 ℃, the temperature of the fourth section of calculating section is set at 190 ℃, the temperature of the fifth section of discharging section is set at 195 ℃, the rotating speed of the twin-screw extruder is 40r/min, the film material master batch is formed by casting through a casting machine, the temperature of a casting machine filter screen is set at 215 ℃, the temperature of an elbow is set at 220 ℃, the die head connection temperature is set at 215 ℃, and the die head temperature is set at 225 ℃ to obtain the corrosion-resistant ultraviolet-resistant film.
The nano zinc oxide used in the embodiment of the invention is purchased from Nanjing Baoket New Material Co., ltd, and has the model of PZT-30 and the average grain diameter of 30nm;3,3' - (ethylene-1, 2-diyl) dibenzoyl chloride has a CAS number of 97203-72-0; polyvinyl chloride is purchased from Dongguan engineering plastics Co., ltd, and the product number is S-65; the polyurethane elastomer is purchased from Bodhisattva high polymer new material Co., ltd, and the model is E8185; polypropylene is purchased from China petroleum Daqing petrochemical company, and the model is T30S; the polydimethylsiloxane is purchased from Dongguan, a new material Co., ltd, and is BYK-333 and has the chemical components of polyether modified polydimethylsiloxane; the remaining reagents were all commercially available.
The performance test is carried out on the prepared corrosion-resistant ultraviolet-resistant film, and the specific test is as follows:
(1) Transparency test of film: selecting the corresponding corrosion-resistant uvioresistant films in examples 1-4 and comparative examples 1-3 for performance test, wherein the performance test is expressed by haze and light transmittance, and the test refers to national standard GB/T2410-2008, and in the test process, the corresponding films are prepared into a wafer with the diameter of 50mm and a sample with the thickness of 0.1 mm;
(2) Ultraviolet resistance test: the corresponding anti-corrosion and anti-ultraviolet films in examples 1-4 and comparative examples 1-3 are selected for performance test, and a Japanese Shimadzu UV-3600 spectrophotometer is adopted for testing, and the test is referred to the national standard GB/T2680-2021;
the results of the above tests are recorded as shown in table 1:
TABLE 1
As can be seen from the test results in Table 1, the anti-UV films of examples 1 to 4 have excellent transparency and UV absorption properties, the haze of example 1 is as low as 1.24%, the light transmittance is 93.3%, and the UV absorption of example 4 is as high as 98.5%. The polyvinyl chloride has the characteristics of good transparency and glossiness, the polyurethane elastomer has excellent ageing resistance and weather resistance, the anti-ultraviolet performance of the film can be improved to a great extent, the nano zinc oxide has the characteristic of forbidden bandwidth, electrons on the valence band can absorb ultraviolet rays and be excited to a conduction band when being irradiated by ultraviolet rays, so that electron-hole pairs are generated, the nano zinc oxide has scattering capacity on ultraviolet rays due to nano-size effect, the anti-ultraviolet effect can be achieved, and the introduced 2- (2, 4-dihydroxyphenyl) -2H-benzotriazole can break hydrogen bonds in molecules after absorbing ultraviolet rays and convert high-energy ultraviolet light energy into heat energy to perform corresponding energy conversion, release the ultraviolet light energy into harmless low-radiation heat energy, has a wide absorption range and high absorption efficiency, and has excellent ultraviolet absorption performance. The nano zinc oxide is not modified in comparative example 1, the nano zinc oxide is easy to agglomerate, the performance is greatly affected, the performance is reduced, the 2- (2, 4-dihydroxyphenyl) -2H-benzotriazole is not added in comparative example 2, the ultraviolet absorption performance is reduced, the nano zinc oxide is not added in comparative example 3, the transparency of the film is improved, but the ultraviolet absorption performance is greatly reduced.
(3) Corrosion resistance test: preparing the corresponding corrosion-resistant ultraviolet-resistant films in examples 1-4 into wafers with the diameter of 50mm and the thickness of 0.05mm, respectively putting the wafers into sodium hydroxide aqueous solution with the mass ratio of 25%, and observing the color change after 15 min; the corrosion-resistant and ultraviolet-resistant films corresponding to examples 1 to 4 are respectively placed into an acetic acid aqueous solution with pH paper of 4, after 15min, whether corrosion phenomenon exists or not is observed, and test results are recorded as shown in Table 2:
TABLE 2
As can be seen from the test results of Table 2, the anti-corrosion and anti-ultraviolet films corresponding to examples 1 to 4 have excellent corrosion resistance. The polypropylene material has good chemical stability and corrosion resistance, polymethyl methacrylate has good chemical stability and weather resistance, nano zinc oxide also has good corrosion resistance, and the obtained film has good corrosion resistance.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made hereto without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A preparation method of a corrosion-resistant ultraviolet-resistant film is characterized by comprising the following steps: the method comprises the following steps:
uniformly mixing dichloromethane and 3,3' - (ethylene-1, 2-diyl) dibenzoyl chloride, adding nano zinc oxide and triethylamine, uniformly mixing, reacting, and performing suction filtration, washing and drying after the reaction is finished to obtain acyl chloride zinc oxide;
step (2) evenly mixing tetrahydrofuran and acyl zinc oxide, adding 2- (2, 4-dihydroxyphenyl) -2H-benzotriazole and triethylamine, evenly mixing, reacting, washing and drying after the reaction is finished to obtain benzotriazole modified zinc oxide;
step (3) mixing absolute ethyl alcohol and deionized water uniformly, adding benzotriazole modified zinc oxide, dispersing uniformly, adding methyl methacrylate and dibenzoyl peroxide, reacting, and drying after the reaction is finished to obtain ultraviolet-resistant modified zinc oxide grafted polymethyl methacrylate;
and (4) uniformly mixing polyvinyl chloride, polyurethane elastomer, anti-ultraviolet modified zinc oxide grafted polymethyl methacrylate, polypropylene, a leveling agent and an antioxidant, adding into a double-screw extruder for melt blending, extruding, cooling and granulating to obtain film material master batches, and carrying out tape casting molding on the film material master batches by a tape casting machine to obtain the anti-corrosion anti-ultraviolet film.
2. The method for preparing the corrosion-resistant ultraviolet-resistant film according to claim 1, wherein the method comprises the following steps: in the step (1), the mass ratio of dichloromethane, 3' - (ethylene-1, 2-diyl) dibenzoyl chloride, nano zinc oxide and triethylamine is 5200-6000:75-95:100:1-2; the reaction temperature is 40-45 ℃, and the reaction time is 2-3h.
3. The method for preparing the corrosion-resistant ultraviolet-resistant film according to claim 1, wherein the method comprises the following steps: in the step (2), the mass ratio of tetrahydrofuran, zinc oxychloride, 2- (2, 4-dihydroxyphenyl) -2H-benzotriazole and triethylamine is 1800-2500:100:240-320:95-150; the reaction temperature is 0-5 ℃, and the reaction time is 9-12h.
4. The method for preparing the corrosion-resistant ultraviolet-resistant film according to claim 1, wherein the method comprises the following steps: in the step (3), the mass ratio of the absolute ethyl alcohol to the deionized water to the benzotriazole modified zinc oxide to the methyl methacrylate to the dibenzoyl peroxide is 1200-1800:500-750:30-50:100:2-5.
5. The method for preparing the corrosion-resistant ultraviolet-resistant film according to claim 1, wherein the method comprises the following steps: the reaction temperature in the step (3) is 80-90 ℃, and the reaction time is 5-7h.
6. The method for preparing the corrosion-resistant ultraviolet-resistant film according to claim 1, wherein the method comprises the following steps: in the step (4), the mass ratio of the polyvinyl chloride to the polyurethane elastomer to the anti-ultraviolet modified zinc oxide grafted polymethyl methacrylate to the polypropylene to the leveling agent to the antioxidant is 100:75-95:20-32:10-20:0.1-0.3:0.5-2.
7. The method for preparing the corrosion-resistant ultraviolet-resistant film according to claim 1, wherein the method comprises the following steps: the leveling agent in the step (4) comprises one or more of modified polydimethylsiloxane, polyacrylamide and polyacrylate; the antioxidant comprises one or more of antioxidant 1076, antioxidant 1010 and antioxidant 168.
8. The method for preparing the corrosion-resistant ultraviolet-resistant film according to claim 1, wherein the method comprises the following steps: the twin-screw extruder in the step (4) has five temperature zones, which are respectively: the temperature of the first section of feeding section is set to 155-170 ℃, the temperature of the second section of mixing section is set to 165-180 ℃, the temperature of the third section of mixing section is set to 175-190 ℃, the temperature of the fourth section of calculating section is set to 175-200 ℃, the temperature of the fifth section of discharging section is set to 185-200 ℃, and the rotating speed of the twin-screw extruder is 35-45r/min; the temperature of the filter screen of the casting machine is set to be 200-220 ℃, the temperature of the elbow is set to be 205-225 ℃, the connection temperature of the die head is set to be 195-220 ℃, and the temperature of the die head is set to be 195-235 ℃.
9. A corrosion-resistant ultraviolet-resistant film prepared by the method for preparing a corrosion-resistant ultraviolet-resistant film according to any one of claims 1 to 8.
10. Use of the corrosion-resistant, uv-resistant film according to claim 9 in automotive film applications.
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| JP2015105325A (en) * | 2013-11-29 | 2015-06-08 | 住友大阪セメント株式会社 | Transparent resin composition, coating film, and heat ray shielding film |
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