CN112126339A - Preparation method of super-hydrophobic TPU material automobile paint surface protective film self-repairing coating - Google Patents
Preparation method of super-hydrophobic TPU material automobile paint surface protective film self-repairing coating Download PDFInfo
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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- C09D175/08—Polyurethanes from polyethers
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
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Abstract
The invention discloses a preparation method of a super-hydrophobic TPU material automobile paint protective film self-repairing coating, which comprises the following raw materials in parts by weight: 80-120 parts of aliphatic diisocyanate, 600 parts of hydroxyl polyether polyol, 20-30 parts of a catalyst, 25-45 parts (preferably 30-40 parts) of a chain extender, 5-10 parts of an anti-ultraviolet auxiliary agent, 250 parts of a solvent 200, 10-20 parts of inert silicone oil, 2-5 parts of sodium citrate modified nanoparticles, 5-10 parts of a dispersing agent and 10-20 parts of a defoaming agent. Has the advantages that: the polyurethane synthesized by the invention belongs to polyether polyurethane, has more soft segment structures, contains a large amount of hydroxyl groups, and can realize the migration motion of molecular chains after film forming, thereby providing conditions for self-repairing of damaged coatings and realizing rapid self-healing of the damaged coatings; the nano particles modified by the sodium citrate can ensure that the protective film has a very high water contact angle, so that the coating is ensured to have super-hydrophobic characteristics.
Description
Technical Field
The invention relates to the technical field of protective films and protective coatings, in particular to a preparation method of a self-repairing coating of a super-hydrophobic TPU material automobile paint surface protective film.
Background
With the continuous promotion of the reform and open business of China, the domestic economy develops rapidly, and the metal industry also develops rapidly. The metal substrate industry relates to the people's life of China and plays a vital role in all fields of people's life.
However, in the actual use process of metal substrates (especially steel substrates), due to the inherent characteristics of the materials, the metal substrates are easily corroded and damaged by corrosive media, so that the use performance of the metal substrates is affected, even serious industrial accidents can be caused, and the lives and properties of people are threatened. At present, corresponding anticorrosive paint is often coated to deal with the damage of a corrosive medium to a metal substrate, and the interface protection of the metal substrate is realized by isolating the contact of the corrosive medium and the metal substrate or by electrochemical action mechanisms such as a galvanic cell and the like.
With the prolonging of the service life, the anticorrosion coating covered on the surface gradually loses its protective effect under the action of corrosive environment or corrosive medium, and the anticorrosion coating is usually cracked due to external force action such as collision, friction, impact and the like, and once the anticorrosion coating is damaged or has microcracks, the anticorrosion coating can rapidly extend and expand, so that the phenomenon of large-area falling occurs. Therefore, the improvement of the anti-damage capability of the anti-corrosion coating is particularly important, and the self-repairing (self-healing) characteristic of the coating is realized, so that the coating can self-heal after being damaged under the action of external force, thereby preventing macroscopic large-area damage and shedding, and becoming an important new direction for the development of the anti-corrosion coating.
The polyurethane material is an important raw material applied in the field of corrosion prevention, in recent years, the self-healing property of the polyurethane material is widely concerned by researchers, and the polyurethane material containing ether bonds has excellent self-healing performance and can realize rapid repair after self damage, so that the polyurethane material has wide application prospect. For the anti-corrosion coating, the corrosion medium adhered to the surface of the coating or the impurities causing scratch damage of the coating are important adverse factors influencing the service life of the anti-corrosion coating, so that how to reduce the adhesion of the related medium or impurities is also an important research direction. The super-hydrophobic coating with a unique lotus leaf microstructure can effectively inhibit the contamination of corrosive media or impurities, thereby ensuring the smoothness of the surface of the material. Therefore, the super-hydrophobic characteristic and the self-healing characteristic of the polyurethane material are combined, the polyurethane self-healing coating with the super-hydrophobic characteristic is researched and developed, important research and development and industrialization significance is achieved in the field of corrosion prevention, and actual development and use of related products at home and abroad are lacked at present.
Disclosure of Invention
The invention aims to solve the problems and provide a preparation method of a self-repairing coating of a super-hydrophobic TPU material automobile paint protective film.
The invention realizes the purpose through the following technical scheme:
a preparation method of a super-hydrophobic TPU material self-repairing coating for an automobile paint protective film comprises the following raw materials in parts by weight: 80-120 parts of aliphatic diisocyanate, 600 parts of hydroxyl polyether polyol, 20-30 parts of a catalyst, 25-45 parts (preferably 30-40 parts) of a chain extender, 5-10 parts of an anti-ultraviolet auxiliary agent, 250 parts of a solvent 200, 10-20 parts of inert silicone oil, 2-5 parts of sodium citrate modified nanoparticles, 5-10 parts of a dispersing agent and 10-20 parts of a defoaming agent.
Further, the aliphatic diisocyanate is selected from at least one of hexamethylene diisocyanate and isophorone diisocyanate.
Further, the hydroxyl polyether polyol is selected from any two or three of hydroxyl-terminated polyether polyol, trihydroxy polyether polyol and tetrahydroxy polyether polyol.
Further, the catalyst is a metal organic catalyst and comprises at least one of dibutyltin dilaurate, bismuth neodecanoate and bismuth naphthenate.
Further, the chain extender is selected from at least one of 1, 3-butanediol and 1, 4-butanediol.
Further, the ultraviolet resistance auxiliary agent is selected from at least one of benzotriazole and benzophenone.
Further, the solvent is mixed by xylene, butanone, ethyl acetate and tetrahydrofuran according to the mass ratio of 4:1:4: 1.
Further, the inert silicone oil is at least one of 201-20, 201-50, 201-100 of Shandong Daihu chemical engineering methyl silicone oil, 250-30, 255, 275 of Shanghai Hualing resin methyl phenyl silicone oil.
Further, the sodium citrate modified nano particles are at least one of nano ferroferric oxide, nano zinc oxide and hydrophobic fumed silica; the dispersant is selected from at least one of sodium oleate and sodium dodecyl benzene sulfonate.
The preparation method of the self-repairing coating of the automobile paint surface protective film comprises the following steps:
(1) preparing 0.5mol/150mL disodium citrate solution in at least 500mL beaker, adding nanoparticles into the disodium citrate solution, carrying out ultrasonic treatment on the mixed solution for 15-30 minutes at 80-90 ℃ by using a cell crusher, and circulating the ultrasonic process: the ultrasonic time is 20 seconds, the interval time is 20 seconds, after the ultrasonic solution is cleaned by using excessive acetone, the mixture is easily put into a vacuum drying oven, and vacuum drying is carried out for 24 hours at the temperature of 100 ℃ for standby application;
(2) continuously introducing nitrogen into a reaction kettle of at least 5L for 10min, adding no more than 50 weight percent of aliphatic diisocyanate, hydroxyl polyether polyol and no more than 50 weight percent of solvent into the reaction kettle, and dispersing at the rotating speed of 800-1000rpm at 60-70 ℃ for 5-10 min;
(3) then reducing the temperature to 45-50 ℃, adding the rest aliphatic diisocyanate, the catalyst and the chain extender into the reaction kettle, then increasing the temperature to 65-75 ℃ again, and dispersing at the rotating speed of 800-1000rpm, wherein the whole constant-temperature reaction process lasts for 3-5 h;
(4) adding inert silicon oil and the nano particles modified by the sodium citrate into at least 500mL of beaker while the process (3) is carried out, then putting the beaker into an ultrasonic cleaning agent for ultrasonic treatment for 30-50 min, and taking out for standby;
(5) reducing the temperature to 45-50 ℃, adding the residual solvent into the reaction kettle, and dispersing for 5-15min at the rotating speed of 500 plus materials and 800 rpm;
(6) adding the mixed solution of the inert silicon oil and the nano particles after the ultrasonic treatment into a reaction kettle at the temperature of 45-50 ℃, and dispersing for 30-60min at the rotating speed of 200-300 rpm;
(7) adding the anti-ultraviolet auxiliary agent, the dispersing agent and the defoaming agent into a reaction kettle, and dispersing for 30-60min at the rotating speed of 200-300 rpm;
(8) the prepared mixed solution can be constructed by brushing, spraying, rolling or coating by a coating machine and the like, in order to accelerate the curing speed, the environmental humidity can be properly increased to not more than 80%, and the super-hydrophobic TPU self-repairing coating is formed after the mixed solution is cured to form a film.
The invention has the beneficial effects that:
1. according to the invention, the modified nanoparticles and the TPU pre-resin are effectively mixed by mixing the inert silicone oil with the nanoparticles modified by the sodium citrate, so that the surface of the cured coating is ensured to have a super-hydrophobic lotus leaf shape;
2. the polyurethane synthesized by the invention belongs to polyether polyurethane, has more soft segment structures, and simultaneously contains a large amount of hydroxyl groups, and can realize the migration motion of molecular chains after film forming, thereby providing conditions for self-repairing of damaged coatings and realizing the rapid self-healing of the damaged coatings;
3. the TPU self-repairing coating contains a certain amount of ultraviolet-resistant auxiliary agent, so that the yellowing tendency of polyurethane can be effectively inhibited, and the service cycle of the coating is prolonged;
4. the TPU self-repairing coating surface provided by the invention has a super-hydrophobic characteristic, and can effectively reduce contamination of water, impurities and the like, so that the retention time of scratch impurities on the coating surface is reduced, and the self-repairing service cycle of the coating is further prolonged.
Drawings
FIG. 1 is a water contact angle picture of example 1 in the preparation method of the self-repairing coating of the super-hydrophobic TPU material automobile paint surface protective film.
Detailed Description
The present invention will be described below by way of examples, but the present invention is not limited to the following examples, and various changes can be made within the scope conforming to the spirit of the present invention and the scope of the present invention.
The hydroxyl polyether polyol selected by the invention is purchased from HSH series of the Haian petrochemical plant of Jiangsu province, and has the following molecular weight: 1000-5000, hydroxyl polyether polyols with different molecular weights can be selected according to requirements, and the hydroxyl polyether polyol with the molecular weight of 1000 and the trihydroxy polyether polyol with the molecular weight of 3000 are mainly used in the embodiment of the invention, but the hydroxyl polyether polyol selected in the implementation of the invention is not limited by manufacturers and specific performance parameters thereof.
Example 1: specifically, the super-hydrophobic TPU self-repairing coating comprises the following raw materials in parts by weight: 100 parts of aliphatic diisocyanate, 500 parts of hydroxyl polyether polyol, 20 parts of catalyst, 30 parts of chain extender, 5 parts of ultraviolet-resistant auxiliary agent, 200 parts of solvent, 10 parts of inert silicone oil, 3 parts of sodium citrate modified nano particles, 5 parts of dispersing agent and 10 parts of defoaming agent.
Wherein the aliphatic diisocyanate is hexamethylene diisocyanate; the hydroxyl polyether polyol is prepared by mixing hydroxyl polyether polyol with the molecular weight of 1000 and trihydroxy polyether polyol with the molecular weight of 3000 according to the weight ratio of 40: 10, mixing; selecting dibutyltin dilaurate as a catalyst; the chain extender is 1, 4-butanediol; benzotriazole is selected as the anti-ultraviolet auxiliary agent; the solvent is selected from dimethylbenzene, butanone, ethyl acetate and tetrahydrofuran according to the ratio of 4:1:4:1, mixing; the inert silicone oil is selected from 201-20 methyl silicone oil which is easy to be chemically processed in Shandong; the nano-particles modified by the sodium citrate are nano ferroferric oxide with the particle size of less than 30 nm; the dispersing agent is sodium dodecyl benzene sulfonate; BYK028 from Picker is selected as the defoaming agent.
A preparation method of a super-hydrophobic TPU self-repairing coating comprises the following steps:
(1) preparing 0.5mol/150mL disodium citrate solution in at least 500mL beaker, adding 3 parts of nano ferroferric oxide (<30nm) into the disodium citrate solution, carrying out ultrasonic treatment on the mixed solution for 15 minutes at 80 ℃ by using a cell crusher, and circulating the ultrasonic process: the ultrasonic time is 20 seconds, the interval time is 20 seconds, after the ultrasonic solution is cleaned by using excessive acetone, the mixture is easily put into a vacuum drying oven, and vacuum drying is carried out for 24 hours at the temperature of 100 ℃ for standby.
(2) Continuously introducing nitrogen into a reaction kettle of at least 5L for 10min, adding 50 parts of hexamethylene diisocyanate, 400 parts of hydroxyl polyether polyol with the molecular weight of 1000, 100 parts of trihydroxy polyether polyol with the molecular weight of 3000, 40 parts of xylene, 10 parts of butanone, 40 parts of ethyl acetate and 10 parts of tetrahydrofuran into the reaction kettle, and dispersing at the rotating speed of 1000rpm for 10min at 60 ℃;
(3) then, reducing the temperature to 45 ℃, adding the rest 50 parts of hexamethylene diisocyanate, 20 parts of dibutyltin dilaurate and 30 parts of 1, 4-butanediol into a reaction kettle, then raising the temperature to 65 ℃ again, dispersing at the rotating speed of 1000rpm, and continuing the whole constant-temperature reaction process for 5 hours;
(4) while the process (3) is carried out, adding 10 parts of 201-20 parts of methyl silicone oil and sodium citrate modified nano ferroferric oxide into at least 500mL of beaker, then putting the beaker into an ultrasonic cleaning agent for ultrasonic treatment for 30min, and taking out for later use;
(5) reducing the temperature to 45 ℃, adding the rest 40 parts of dimethylbenzene, 10 parts of butanone, 40 parts of ethyl acetate and 10 parts of tetrahydrofuran into a reaction kettle, and dispersing for 15min at the rotating speed of 800 rpm;
(6) adding the mixed liquid of 201-20 methylsilicone oil and nano ferroferric oxide after ultrasonic treatment into a reaction kettle at the temperature of 45 ℃, and dispersing for 60min at the rotating speed of 300 rpm;
(7) adding 5 parts of benzotriazole, 5 parts of sodium dodecyl benzene sulfonate and 10 parts of BYK028 into a reaction kettle, and dispersing for 30min at the rotating speed of 300 rpm;
(8) the prepared mixed solution can be constructed by brushing, spraying, rolling or coating by a coating machine and the like, in order to accelerate the curing speed, the environmental humidity can be properly increased to not more than 80%, and the super-hydrophobic TPU self-repairing coating is formed after the mixed solution is cured to form a film.
Example 2: the implementation provides a preparation method of a super-hydrophobic TPU self-repairing coating, which is basically consistent with that of the embodiment 1 and is different from that of the embodiment 1 in that:
the super-hydrophobic TPU self-repairing coating comprises the following raw materials in parts by weight: 120 parts of aliphatic diisocyanate, 600 parts of hydroxyl polyether polyol, 30 parts of catalyst, 45 parts of chain extender, 10 parts of ultraviolet-resistant auxiliary agent, 200 parts of solvent, 20 parts of inert silicone oil, 5 parts of sodium citrate modified nano particles, 5 parts of dispersing agent and 15 parts of defoaming agent.
Wherein the aliphatic diisocyanate is isophorone diisocyanate; the hydroxyl polyether polyol is prepared by mixing hydroxyl polyether polyol with the molecular weight of 1000 and trihydroxy polyether polyol with the molecular weight of 3000 according to the weight ratio of 45: 5, mixing in proportion; selecting bismuth neodecanoate as a catalyst; the chain extender is 1, 3-butanediol; selecting benzophenone as the anti-ultraviolet auxiliary agent; the solvent is selected from dimethylbenzene, butanone, ethyl acetate and tetrahydrofuran according to the ratio of 4:1:4:1, mixing; the inert silicone oil is prepared from 201-100 methyl silicone oil which is easy to be processed by Shandong chemical engineering; the nano particles modified by the sodium citrate are selected from nano zinc oxide, and the particle size is less than 30 nm; selecting sodium oleate as the dispersing agent; BYK-W961 from Pick company is selected as the defoaming agent.
A preparation method of a super-hydrophobic TPU self-repairing coating comprises the following steps:
(1) preparing 0.5mol/150mL disodium citrate solution in at least 500mL beaker, then adding 5 parts of nano zinc oxide (<30nm) into the disodium citrate solution, and carrying out ultrasonic treatment on the mixed solution for 30 minutes at 90 ℃ by using a cell crusher, and circulating the ultrasonic process: the ultrasonic time is 20 seconds, the interval time is 20 seconds, after the ultrasonic solution is cleaned by using excessive acetone, the mixture is easily put into a vacuum drying oven, and vacuum drying is carried out for 24 hours at the temperature of 100 ℃ for standby.
(2) Continuously introducing nitrogen into a reaction kettle of at least 5L for 10min, adding 60 parts of isophorone diisocyanate, 540 parts of hydroxyl polyether polyol with the molecular weight of 1000, 60 parts of trihydroxy polyether polyol with the molecular weight of 3000, 40 parts of xylene, 10 parts of butanone, 40 parts of ethyl acetate and 10 parts of tetrahydrofuran into the reaction kettle, and dispersing at the rotating speed of 800rpm for 10min at 70 ℃;
(3) then, reducing the temperature to 50 ℃, adding the rest 60 parts of isophorone diisocyanate, 30 parts of bismuth neodecanoate and 45 parts of 1, 3-butanediol into a reaction kettle, then raising the temperature to 70 ℃ again, dispersing at the rotating speed of 800rpm, and continuing the whole constant-temperature reaction process for 3 hours;
(4) while the process (3) is carried out, 20 parts of 201-100 methylsilicone oil and sodium citrate modified nano-zinc oxide are added into at least 500mL of beaker, and then the beaker is put into an ultrasonic cleaning agent for ultrasonic treatment for 60min and taken out for standby;
(5) reducing the temperature to 50 ℃, adding the rest 40 parts of dimethylbenzene, 10 parts of butanone, 40 parts of ethyl acetate and 10 parts of tetrahydrofuran into a reaction kettle, and dispersing for 10min at the rotating speed of 800 rpm;
(6) adding the mixed solution of the 201-100 methylsilicone oil and the nano-zinc oxide which are subjected to the ultrasonic treatment into a reaction kettle at the temperature of 50 ℃, and dispersing for 60min at the rotating speed of 200 rpm;
(7) adding 10 parts of benzophenone, 5 parts of sodium oleate and 15 parts of BYK-W961 into a reaction kettle, and dispersing for 30min at the rotating speed of 300 rpm;
(8) the prepared mixed solution can be constructed by brushing, spraying, rolling or coating by a coating machine and the like, in order to accelerate the curing speed, the environmental humidity can be properly increased to not more than 80%, and the super-hydrophobic TPU self-repairing coating is formed after the mixed solution is cured to form a film.
Example 3: the implementation provides a preparation method of a super-hydrophobic TPU self-repairing coating, which is basically consistent with that of the embodiment 1 and is different from that of the embodiment 1 in that:
the super-hydrophobic TPU self-repairing coating comprises the following raw materials in parts by weight: 110 parts of aliphatic diisocyanate, 500 parts of hydroxyl polyether polyol, 250 parts of catalyst, 40 parts of chain extender, 8 parts of ultraviolet-resistant auxiliary agent, 250 parts of solvent, 15 parts of inert silicone oil, 4 parts of sodium citrate modified nano particles, 10 parts of dispersing agent and 20 parts of defoaming agent.
Wherein the aliphatic diisocyanate is isophorone diisocyanate; the hydroxyl polyether polyol is prepared by mixing hydroxyl polyether polyol with the molecular weight of 1000 and trihydroxy polyether polyol with the molecular weight of 3000 according to the weight ratio of 45: 5, mixing in proportion; selecting bismuth naphthenate as a catalyst; the chain extender is 1, 3-butanediol; selecting benzophenone as the anti-ultraviolet auxiliary agent; the solvent is selected from dimethylbenzene, butanone, ethyl acetate and tetrahydrofuran according to the ratio of 4:1:4:1, mixing; the inert silicone oil is 255 methyl phenyl silicone oil of Shanghai Hualing resin; the sodium citrate modified nano particles are hydrophobic fumed silica with the particle size of less than 50 nm; selecting sodium oleate as the dispersing agent; the defoaming agent is DF-691 of Rodia company.
A preparation method of a super-hydrophobic TPU self-repairing coating comprises the following steps:
(1) preparing a 0.5mol/150mL disodium citrate solution in at least a 500mL beaker, subsequently adding 4 parts of hydrophobic fumed silica (<50nm) to the disodium citrate solution, sonicating the mixed solution using a cell disruptor at 85 ℃ for 50 minutes, cycling the sonication process: the ultrasonic time is 20 seconds, the interval time is 20 seconds, after the ultrasonic solution is cleaned by using excessive acetone, the mixture is easily put into a vacuum drying oven, and vacuum drying is carried out for 24 hours at the temperature of 100 ℃ for standby.
(2) Continuously introducing nitrogen into a reaction kettle of at least 5L for 10min, adding 55 parts of isophorone diisocyanate, 450 parts of hydroxyl polyether polyol with the molecular weight of 1000, 50 parts of trihydroxy polyether polyol with the molecular weight of 3000, 50 parts of xylene, 12.5 parts of butanone, 50 parts of ethyl acetate and 12.5 parts of tetrahydrofuran into the reaction kettle, and dispersing at the rotating speed of 1000rpm at 65 ℃ for 10 min;
(3) then, reducing the temperature to 45 ℃, adding the rest 55 parts of isophorone diisocyanate, 25 parts of bismuth naphthenate and 40 parts of 1, 3-butanediol into a reaction kettle, then increasing the temperature to 75 ℃ again, dispersing at the rotating speed of 1000rpm, and continuing the whole constant-temperature reaction process for 4 hours;
(4) while the process (3) is carried out, adding 15 parts of 255 phenyl methyl silicone oil and the hydrophobic fumed silica modified by sodium citrate into at least 500mL of beaker, then putting the beaker into an ultrasonic cleaning agent for ultrasonic treatment for 50min, and taking out for later use;
(5) reducing the temperature to 45 ℃, adding the rest 50 parts of dimethylbenzene, 12.5 parts of butanone, 50 parts of ethyl acetate and 12.5 parts of tetrahydrofuran into a reaction kettle, and dispersing for 5min at the rotating speed of 1000 rpm;
(6) adding the 255 phenyl methyl silicone oil and hydrophobic gas-phase silicon dioxide mixed solution after ultrasonic treatment into a reaction kettle at the temperature of 45 ℃, and dispersing for 50min at the rotating speed of 250 rpm;
(7) adding 8 parts of benzophenone, 10 parts of sodium oleate and 20 parts of DF-691 into a reaction kettle, and dispersing for 30min at the rotating speed of 300 rpm;
(8) the prepared mixed solution can be constructed by brushing, spraying, rolling or coating by a coating machine and the like, in order to accelerate the curing speed, the environmental humidity can be properly increased to not more than 80%, and the super-hydrophobic TPU self-repairing coating is formed after the mixed solution is cured to form a film.
COMPARATIVE EXAMPLE 1 (common TPU self-repairing coating)
The room temperature curing self-repairing TPU invisible film coating comprises the following raw materials in parts by weight: 100 parts of aromatic diisocyanate substance, 400 parts of hydroxyl polyether polyol, 10 parts of catalyst, 20 parts of chain extender and 260 parts of solvent.
2, 4-toluene diisocyanate is selected as the aromatic diisocyanate; the hydroxyl polyether polyol is trihydroxy polyether polyol; the catalyst was dibutyltin dilaurate; the chain extender is 1, 4-butanediol; the solvent is selected from dimethylbenzene and cyclohexanone which are mixed according to the proportion of 1: 1.
The preparation method of the room temperature curing self-repairing TPU invisible film coating comprises the following steps:
(1) continuously introducing nitrogen into a reaction kettle of at least 5L for 10min, adding 100 parts of 2, 4-toluene diisocyanate, 400 parts of trihydroxy polyether polyol, 65 parts of xylene and 65 parts of cyclohexanone into the reaction kettle, and dispersing at 75 ℃ at the rotating speed of 800rpm for 3 h;
(2) then, the temperature is reduced to 50 ℃, 10 parts of dibutyltin dilaurate and 20 parts of 1, 4-butanediol are added into a reaction kettle, the temperature is increased to 75 ℃ again, the mixture is dispersed at the rotating speed of 800rpm, and the whole constant-temperature reaction process lasts for 3.5 hours;
(3) reducing the temperature to 40 ℃, adding 65 parts of dimethylbenzene and 65 parts of ethyl acetate into a reaction kettle, and dispersing for 5min at the rotating speed of 800 rpm;
(4) the prepared mixed solution can be hung and coated through a coating machine, the environment humidity is kept at 80%, and the TPU self-repairing coating is formed after the mixed solution is solidified into a film.
COMPARATIVE EXAMPLE 2 (common TPU self-repairing coating)
The room temperature curing self-repairing TPU invisible film coating comprises the following raw materials in parts by weight: 100 parts of aromatic diisocyanate substance, 400 parts of hydroxyl polyol, 10 parts of catalyst, 20 parts of chain extender and 200 parts of solvent.
2, 4-toluene diisocyanate is selected as the aromatic diisocyanate; the hydroxyl polyalcohol is polypropylene glycol; the catalyst was dibutyltin dilaurate; the chain extender is 1, 4-butanediol; the solvent is selected from dimethylbenzene.
The preparation method of the room temperature curing self-repairing TPU invisible film coating comprises the following steps:
(1) continuously introducing nitrogen into a reaction kettle of at least 5L for 10min, adding 100 parts of 2, 4-toluene diisocyanate, 400 parts of polypropylene glycol and 100 parts of xylene into the reaction kettle, and dispersing at 75 ℃ at the rotating speed of 800rpm for 3 h;
(2) then, the temperature is reduced to 50 ℃, 10 parts of dibutyltin dilaurate and 20 parts of 1, 4-butanediol are added into a reaction kettle, the temperature is increased to 75 ℃ again, the mixture is dispersed at the rotating speed of 800rpm, and the whole constant-temperature reaction process lasts for 3 hours;
(3) reducing the temperature to 40 ℃, adding 100 parts of dimethylbenzene into the reaction kettle, and dispersing for 15min at the rotating speed of 800 rpm;
(4) the prepared mixed solution can be hung and coated through a coating machine, the environment humidity is kept at 80%, and the TPU self-repairing coating is formed after the mixed solution is solidified into a film.
The comparative example, example TPU self-healing coatings have the following water contact angle and rolling contact angle comparison table at the same room temperature:
TABLE 1
| Name (R) | Comparative example 1 | Comparative example 2 | Example 1 | Example 2 | Example 3 |
| Water contact angle | 92.5° | 94.3° | 154.1° | 151.7° | 156.0° |
| Rolling contact angle | 13.3° | 9.1° | 6.5° | 4.8° | 5.7° |
As can be seen from Table 1, under the same room temperature condition, the water contact angle of the TPU coating prepared by the invention is more than 150 degrees, and the rolling contact angle is less than 10 degrees, so that the TPU coating meets the definition of the super-hydrophobic coating, and the coating shows obvious super-hydrophobic characteristic
The self-repair time comparison table of the super-hydrophobic TPU self-repair coating prepared by the embodiment of the invention and the comparative example at the same temperature is as follows:
TABLE 2
As can be seen from Table 2, under the same temperature, the super-hydrophobic TPU self-repairing coating disclosed by the embodiment of the invention has self-repairing capability under a scratch self-repairing experimental test, and the self-repairing time is close to that of a comparative example.
Variations and modifications to the above-described embodiments may also occur to those skilled in the art, which are disclosed and guided by the above description. Therefore, the present invention is not limited to the above-described embodiments, and modifications to the present invention are also intended to fall within the scope of the appended claims.
Claims (10)
1. A preparation method of a super-hydrophobic TPU material automobile paint protective film self-repairing coating is characterized by comprising the following steps: the self-repairing coating of the automobile paint surface protective film comprises the following raw materials in parts by weight: 80-120 parts of aliphatic diisocyanate, 600 parts of hydroxyl polyether polyol, 20-30 parts of a catalyst, 25-45 parts (preferably 30-40 parts) of a chain extender, 5-10 parts of an anti-ultraviolet auxiliary agent, 250 parts of a solvent 200, 10-20 parts of inert silicone oil, 2-5 parts of sodium citrate modified nanoparticles, 5-10 parts of a dispersing agent and 10-20 parts of a defoaming agent.
2. The preparation method of the super-hydrophobic TPU material automobile paint protective film self-repairing coating according to claim 1, characterized in that: the aliphatic diisocyanate is at least one selected from hexamethylene diisocyanate and isophorone diisocyanate.
3. The preparation method of the super-hydrophobic TPU material automobile paint protective film self-repairing coating according to claim 1, characterized in that: the hydroxyl polyether polyol is selected from any two or three of hydroxyl-terminated polyether polyol, trihydroxy polyether polyol and tetrahydroxy polyether polyol.
4. The preparation method of the super-hydrophobic TPU material automobile paint protective film self-repairing coating according to claim 1, characterized in that: the catalyst is a metal organic catalyst and comprises at least one of dibutyltin dilaurate, bismuth neodecanoate and bismuth naphthenate.
5. The preparation method of the super-hydrophobic TPU material automobile paint protective film self-repairing coating according to claim 1, characterized in that: the chain extender is selected from at least one of 1, 3-butanediol and 1, 4-butanediol.
6. The preparation method of the super-hydrophobic TPU material automobile paint protective film self-repairing coating according to claim 1, characterized in that: the ultraviolet resistance auxiliary agent is at least one of benzotriazole and benzophenone.
7. The preparation method of the super-hydrophobic TPU material automobile paint protective film self-repairing coating according to claim 1, characterized in that: the solvent is prepared by mixing xylene, butanone, ethyl acetate and tetrahydrofuran in a mass ratio of 4:1:4: 1.
8. The preparation method of the super-hydrophobic TPU material automobile paint protective film self-repairing coating according to claim 1, characterized in that: the inert silicone oil is at least one of 201-20, 201-50 and 201-100 of Shandong Dayi chemical engineering methyl silicone oil and 250-30, 255 and 275 of Shanghai Hualing resin methyl phenyl silicone oil.
9. The preparation method of the super-hydrophobic TPU material automobile paint protective film self-repairing coating according to claim 1, characterized in that: the nano particles modified by the sodium citrate are at least one of nano ferroferric oxide, nano zinc oxide and hydrophobic fumed silica; the dispersant is selected from at least one of sodium oleate and sodium dodecyl benzene sulfonate.
10. The preparation method of the super-hydrophobic TPU material automobile paint protective film self-repairing coating according to claim 1, characterized in that: the method comprises the following steps:
(1) preparing 0.5mol/150mL disodium citrate solution in at least 500mL beaker, adding nanoparticles into the disodium citrate solution, carrying out ultrasonic treatment on the mixed solution for 15-30 minutes at 80-90 ℃ by using a cell crusher, and circulating the ultrasonic process: the ultrasonic time is 20 seconds, the interval time is 20 seconds, after the ultrasonic solution is cleaned by using excessive acetone, the mixture is easily put into a vacuum drying oven, and vacuum drying is carried out for 24 hours at the temperature of 100 ℃ for standby application;
(2) continuously introducing nitrogen into a reaction kettle of at least 5L for 10min, adding no more than 50 weight percent of aliphatic diisocyanate, hydroxyl polyether polyol and no more than 50 weight percent of solvent into the reaction kettle, and dispersing at the rotating speed of 800-1000rpm at 60-70 ℃ for 5-10 min;
(3) then reducing the temperature to 45-50 ℃, adding the rest aliphatic diisocyanate, the catalyst and the chain extender into the reaction kettle, then increasing the temperature to 65-75 ℃ again, and dispersing at the rotating speed of 800-1000rpm, wherein the whole constant-temperature reaction process lasts for 3-5 h;
(4) adding inert silicon oil and the nano particles modified by the sodium citrate into at least 500mL of beaker while the process (3) is carried out, then putting the beaker into an ultrasonic cleaning agent for ultrasonic treatment for 30-50 min, and taking out for standby;
(5) reducing the temperature to 45-50 ℃, adding the residual solvent into the reaction kettle, and dispersing for 5-15min at the rotating speed of 500 plus materials and 800 rpm;
(6) adding the mixed solution of the inert silicon oil and the nano particles after the ultrasonic treatment into a reaction kettle at the temperature of 45-50 ℃, and dispersing for 30-60min at the rotating speed of 200-300 rpm;
(7) adding the anti-ultraviolet auxiliary agent, the dispersing agent and the defoaming agent into a reaction kettle, and dispersing for 30-60min at the rotating speed of 200-300 rpm;
(8) the prepared mixed solution can be constructed by brushing, spraying, rolling or coating by a coating machine and the like, in order to accelerate the curing speed, the environmental humidity can be properly increased to not more than 80%, and the super-hydrophobic TPU self-repairing coating is formed after the mixed solution is cured to form a film.
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| CN113897121A (en) * | 2021-10-18 | 2022-01-07 | 上海昶瀚科技有限公司 | Yellowing-resistant self-repairing coating composition, automobile paint protective film and preparation method thereof |
| CN113897121B (en) * | 2021-10-18 | 2022-08-09 | 上海昶瀚科技有限公司 | Yellowing-resistant self-repairing coating composition, automobile paint protective film and preparation method thereof |
| CN116285628A (en) * | 2023-03-23 | 2023-06-23 | 山东科技大学 | Preparation method of pipeline steel-based underwater cooperative self-repairing super-hydrophobic coating |
| CN116285628B (en) * | 2023-03-23 | 2024-02-02 | 山东科技大学 | Preparation method of pipeline steel-based underwater cooperative self-repairing super-hydrophobic coating |
| CN117264550A (en) * | 2023-11-23 | 2023-12-22 | 石狮佳南热熔胶有限公司 | Paint protective film and self-repairing coating thereof |
| CN117264550B (en) * | 2023-11-23 | 2024-03-08 | 石狮佳南热熔胶有限公司 | Paint protective film and self-repairing coating thereof |
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