CN116855167A - Impact-resistant self-repairing coating for UTG - Google Patents

Impact-resistant self-repairing coating for UTG Download PDF

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CN116855167A
CN116855167A CN202310958714.2A CN202310958714A CN116855167A CN 116855167 A CN116855167 A CN 116855167A CN 202310958714 A CN202310958714 A CN 202310958714A CN 116855167 A CN116855167 A CN 116855167A
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utg
reaction
coating
intermediate product
impact
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CN116855167B (en
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赵江
李钦
李鹏
李东娥
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Suzhou Yisheng Optical Materials Co ltd
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    • C—CHEMISTRY; METALLURGY
    • 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
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
    • C03C17/009—Mixtures of organic and inorganic materials, e.g. ormosils and ormocers
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Dispersion Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention belongs to the technical field of ultrathin flexible glass for folding screens, and particularly relates to an impact-resistant self-repairing coating for UTG. UTG sheet for foldable cover plates of electronic screens is insufficient in impact resistance and is easy to fracture. Aiming at the problems, the invention provides an impact-resistant self-repairing coating for UTG, which is prepared by adding the self-made functional monomer into a material system, wherein the functional monomer is of a microsphere structure with a hard core and a soft shell, a core layer is of inorganic silica nano particles, and a shell layer is of a polyurethane acrylate structure; the shell layer of the functional monomer can play roles of an isolating layer and a compatilizer, so that the problem that nano-sized particles are easy to agglomerate and difficult to disperse is solved; the shell layer of the functional monomer is of a polyurethane acrylic ester structure, can form a homogeneous structure with the main resin, and has no influence on the transmittance of the film; the functional monomer is of a microsphere structure with a hard core and a soft shell, has excellent impact resistance and energy absorption effects, and is very beneficial to improving the impact resistance of the obtained film material.

Description

Impact-resistant self-repairing coating for UTG
Technical Field
The invention belongs to the technical field of ultrathin flexible glass for folding screens, and particularly relates to an impact-resistant self-repairing coating for UTG.
Background
Currently, the most potential of foldable cover materials for electronic screens such as mobile phones are transparent polyimide (CPI) and ultra-thin flexible glass (UTG). CPI has good flexibility, but its optical properties and scratch resistance are slightly insufficient; UTG has high hardness, but has insufficient impact resistance, and is easily broken by strong impact. Therefore, the comprehensive properties of the foldable cover plate material for electronic screens such as mobile phones and the like in the aspects of scratch resistance, impact resistance, optical properties and the like are required to be further improved.
In general, after a foldable cover plate for an electronic screen is normally used for about two months, many fine wrinkles and pits appear on the surface of the cover plate, which affect the appearance and the use sensitivity.
In addition, the current molding process of UTG is divided into one-step molding and two-step molding, and no matter what molding mode is, the molding process is related to casting molding of molten glass, heating and cooling molding of solution and chemical corrosion molding, and the anisotropy of tension in the molding process can lead to the appearance of extremely fine holes on the surface of the UTG sheet. The presence of very fine micro-voids on the surface of the UTG sheet resulted in poor adhesion between the coating formed after curing of the coating and the UTG sheet, both of which were prone to interfacial delamination.
Disclosure of Invention
The problems in the prior art are: UTG sheet for foldable cover plates of electronic screens is insufficient in impact resistance and is easy to fracture. Aiming at the problems, the invention provides an impact-resistant self-repairing coating for UTG, which comprises the following raw materials in parts by weight:
40-50 parts of polyurethane acrylic ester;
12-20 parts of functional monomer;
15-20 parts of a reactive diluent;
0.5-2 parts of silane coupling agent;
1-3 parts of a photoinitiator;
0.1-0.2 part of defoaming agent;
0.5-1.0 part of leveling agent;
the balance of solvent.
Specifically, the preparation method of the functional monomer comprises the following steps:
(1) Nano SiO 2 Placing the mixture into a four-neck flask filled with 200mL of ethyl acetate, performing ultrasonic dispersion for 1h, adding a silane coupling agent KH550 and deionized water, slowly heating to 60-80 ℃, heating and stirring for reaction for 6-14h, cooling to room temperature after the reaction is finished, filtering, washing with 600mL of ethyl acetate, and performing vacuum drying at 80 ℃ to constant weight to obtain an intermediate product I;
the SiO is 2 The dosage ratio of the silane coupling agent KH550 to the deionized water is as follows: 5.00g:35.00g:3.00g;
(2) Placing the intermediate product I and isophorone diisocyanate into 500mL of N, N-dimethylformamide, stirring at room temperature for reaction for 2-4h, distilling under reduced pressure after the reaction is finished, and vacuum drying at 80 ℃ for 4h to obtain an intermediate product II;
The dosage ratio of the intermediate product I to isophorone diisocyanate is as follows: 33g:0.16 to 0.18mol;
(3)N 2 under the protection, 68g of an intermediate product II, dibutyltin dilaurate and 1000mL of N, N-dimethylformamide are placed in a flask, the temperature of a reaction system is raised to 100-120 ℃, then 800mL of N, N-dimethylformamide solution containing 0.16-0.18mol of polypropylene glycol 600 is dropwise added through a peristaltic pump while stirring, the progress of the reaction system is monitored by adopting FTIR, the absorption peak of NCO-in an infrared spectrum continuously dropwise added into the reaction system disappears, the dropwise addition is stopped, the reaction is ended, the solution is concentrated, 1000mL of dichloromethane is slowly added, the reaction product is filtered, the filtrate is taken, the dichloromethane is removed through reduced pressure distillation, and vacuum drying is carried out for 4 hours at 80 ℃ to obtain an intermediate product III;
the dosage of the dibutyl tin dilaurate is 0.5% of the mass of the intermediate product II;
(4)N 2 under the protection, 164g of intermediate product III and 1000mL of N, N-dimethylformamide are placed in a flask, the temperature of a reaction system is raised to 70-100 ℃, 800mL of N, N-dimethylformamide solution containing 0.16mol of diisocyanate and 2g of dibutyltin dilaurate is dropwise added through a peristaltic pump while stirring, and the mixture is stirred at constant temperature for reaction for 8-12 hours to obtain a solution containing an intermediate product IV;
(5) Raising the temperature of the solution containing the intermediate product IV obtained in the step (4) to 100-120 ℃, then dropwise adding 500mL of N, N-dimethylformamide solution containing 0.16mol of 2,2' -dithiodiethanol by a peristaltic pump while stirring, reacting at constant temperature until the absorption peak of NCO-in a reaction system disappears on an infrared spectrum, stopping dropwise adding, concentrating the solution after the reaction is finished, slowly adding 1000mL of dichloromethane, filtering, taking filtrate, distilling under reduced pressure to remove the dichloromethane, and vacuum drying for 4 hours at 80 ℃ to obtain the intermediate product;
(6)N 2 under the protection, placing 224-230.5g of intermediate product, 0.16-0.20mol of triethylamine and 800mL of dichloromethane into a flask, stirring uniformly under ice bath conditions, maintaining the temperature of a reaction system at 0-5 ℃, then starting to continuously dropwise add 200mL of dichloromethane solution containing 0.16-0.20mol of acryloyl chloride into the reaction system through a constant pressure dropping funnel, monitoring the reaction system by adopting FTIR, stirring until the OH-absorption peak in the reaction system is not reduced on an infrared spectrum, stopping dropwise addition, ending the reaction, filtering the reaction system, removing filtrate, adding 600mL of saturated sodium bicarbonate aqueous solution into the obtained solid product, washing for 3 times, washing 3 times with 1000mL of deionized water, and drying to constant weight in vacuum at 50 ℃ to obtain a target product VI;
Specifically, the diisocyanate is at least one of isophorone diisocyanate or dicyclohexylmethane-4, 4' -diisocyanate.
Specifically, the silane coupling agent is at least one of KH570, KH172, KH151 or KH 590.
Specifically, the photoinitiator is at least one of photoinitiators 184, 1173, TPO-L, BP.
Specifically, the reactive diluent is at least one of ethyl acrylate, isooctyl acrylate, isobornyl acrylate, N-acryloylmorpholine, 1, 6-hexanediol diacrylate, neopentyl glycol diacrylate and trimethylolpropane triacrylate.
Specifically, a UTG coating obtained with an impact resistant self-repairing coating according to said UTG, the preparation method of which comprises the following steps:
s1: under the condition of keeping the ambient humidity less than or equal to 60 percent, uniformly mixing a leveling agent and a solvent according to the formula amount, sequentially adding polyurethane acrylic ester, a functional monomer, a reactive diluent, a silane coupling agent, a defoaming agent and a leveling agent, stirring at the rotating speed of 1000-1500r/min for 40-60min, adding a photoinitiator, continuously stirring at the rotating speed of 800-1200r/min for 10-20min, standing for 20min, filtering with filter cloth with the aperture of 1 mu m, and taking filtrate to obtain the UTG impact-resistant self-repairing paint;
S2: uniformly coating the UTG obtained in the step S1 on the surface of a smooth UTG film by using an impact-resistant self-repairing coating, heating at 60-80 ℃ for 4-5min, and then carrying out UV irradiation on the coating layer with the irradiation energy of 700-800mJ/cm 2 The irradiation time is 30-40s, and the UTG coating primary product is obtained;
s3: finally, the initial product of the UTG coating obtained in the step S2 is placed in a constant temperature chamber and kept stand for 72 hours at the temperature of 60 ℃ to obtain the UTG coating.
The invention has the following beneficial effects:
(1) The invention provides an impact-resistant self-repairing coating for UTG, wherein the main resin is polyurethane acrylic ester, and the polyurethane acrylic ester endows a UTG coating formed by curing with excellent hardness and flexibility and strong plasticity;
(2) The invention provides an impact-resistant self-repairing coating for UTG, which is prepared by adding a self-made functional monomer into a material system, wherein the functional monomer is of a microsphere structure of a hard core and a soft shell, a core layer of the functional monomer is of an inorganic silica nanoparticle, a shell layer of the functional monomer is of a polyurethane acrylate structure, a large amount of silicon elements in the core layer structure are easy to migrate and enrich to the surface of a coating in the infrared leveling process of the coating, the performance of the material is improved, and in addition, the shell layer polyurethane structure of the functional monomer does not contain benzene rings and is not easy to yellow; the shell layer of the functional monomer can play roles of an isolating layer and a compatilizer, so that the problem that nano-sized particles are easy to agglomerate and difficult to disperse is solved; the shell layer of the functional monomer is of a polyurethane acrylic ester structure, can form a homogeneous structure with the main resin, and has no influence on the transmittance of the film; the functional monomer is of a microsphere structure with a hard core and a soft shell, has excellent impact resistance and energy absorption effects, and is very beneficial to improving the impact resistance of the obtained film material;
(3) The self-made functional monomer is added into the impact-resistant self-repairing coating for UTG, and the polyurethane structure of the shell layer of the functional monomer contains a large number of disulfide bonds, so that the cured coating is endowed with excellent self-repairing property;
(4) The self-made functional monomer is added into the impact-resistant self-repairing paint for UTG, the nano structure of the functional monomer has excellent light homogenizing property, the silicon element also has anti-reflection property on a film material, and the functional monomer is microspherical, can fill holes on the UTG surface, and is beneficial to improving the interfacial adhesion between a coating and UTG sheets;
(5) The impact-resistant self-repairing paint for UTG, which is obtained by the invention, is also added with a silane coupling agent with vinyl, one end of the silane coupling agent can be bonded into a polyurethane acrylate main resin structure in a chemical bond mode, and the other end of the silane coupling agent can be subjected to grafting reaction with the surface of UTG sheets, so that the interfacial adhesion between the cured coating and UTG sheets can be further improved.
The specific embodiment is as follows:
the present invention will be described in detail with reference to examples. It is to be understood that the following examples are illustrative of embodiments of the present invention and are not intended to limit the scope of the invention.
The nano SiO employed in the following examples of the present invention 2 Is produced by Cabot corporation and has an average particle diameter of 100nm.
The solvent adopted in the following examples of the invention is a solution of isopropanol and butanone in a mass ratio of 2:1.
The defoamer used in the following examples of the present invention was BYK1719.
The leveling agent used in the following examples of the present invention was BYK3455.
UTG employed in the following examples of the present invention is sheet material available from schottky company and has a thickness of 100 μm.
Example 1
An impact-resistant self-repairing coating for UTG comprises the following raw materials in 100 weight percent:
polyurethane acrylic ester CN8009 NS 25 parts;
polyurethane acrylic ester CN965 NS 20 parts;
15 parts of functional monomer;
3 parts of trimethylolpropane triacrylate;
6 parts of 1, 6-hexanediol diacrylate;
6 parts of isooctyl acrylate;
570 parts of silane coupling agent KH;
184 parts of a photoinitiator;
0.1 part of defoaming agent;
0.6 part of leveling agent;
the balance of solvent.
The functional monomer is prepared by the following method:
(1) Nano SiO 2 Placing the mixture into a four-neck flask filled with 200mL of ethyl acetate, performing ultrasonic dispersion for 1h, adding a silane coupling agent KH550 and deionized water, slowly heating to 70 ℃, and heating and stirring for 10h; after the reaction is finished, cooling to room temperature, filtering, washing with 600mL of ethyl acetate, and vacuum drying at 80 ℃ to constant weight to obtain an intermediate product I;
the SiO is 2 The dosage ratio of the silane coupling agent KH550 to the deionized water is 5.00g:35.00g:3.00g;
the intermediate I infrared data are as follows:
3438cm -1 : -OH weakening; 1109cm -1 、801cm -1 : -Si-O-presence; 2928cm -1 : -C-H is present; 1560cm -1 : -N-H is present;
(2) Placing the intermediate product I and isophorone diisocyanate into 500mL of N, N-dimethylformamide, stirring at room temperature for reaction for 3 hours, removing the solvent by reduced pressure distillation after the reaction is finished, and drying in vacuum at 80 ℃ for 4 hours to obtain an intermediate product II;
the dosage ratio of the intermediate product I to isophorone diisocyanate is 33g:0.16 to 0.18mol;
the intermediate II infrared data are as follows:
3438cm -1 : -OH is present; 1109cm -1 、801cm -1 : -Si-O-presence; 2928cm -1 : -C-H is present; 1560cm -1 : -N-H is present; 1702cm -1 : -c=o present; 2270cm -1 : -NCO present;
(3)N 2 under the protection, 68g of an intermediate product II, dibutyltin dilaurate and 1000mL of N, N-dimethylformamide are placed in a flask, the temperature of a reaction system is raised to 110 ℃, then 800mL of N, N-dimethylformamide solution containing 0.16mol of polypropylene glycol 600 is dropwise added through a peristaltic pump while stirring, the progress of the reaction system is monitored by adopting FTIR, the absorption peak of NCO-in an infrared spectrum continuously dropwise added into the reaction system disappears, the dropwise addition is stopped, the reaction is ended, the solution is concentrated, 1000mL of dichloromethane is slowly added, the reaction product is filtered, the filtrate is taken, the dichloromethane is removed by reduced pressure distillation, and vacuum drying is carried out for 4 hours at 80 ℃ to obtain an intermediate product III;
The dosage of the dibutyl tin dilaurate is 0.5% of the mass of the intermediate product II;
the intermediate III infrared data are as follows:
3440cm -1 : -OH is present; 1109cm -1 、801cm -1 : -Si-O-presence; 2928cm -1 : -C-H is present; 1560cm -1 : -N-H is present; 1722cm -1 : -c=o present; 2270cm -1 : -the NCO vanishes.
(4)N 2 Under the protection, 164g of intermediate product III and 1000mL of N, N-dimethylformamide are placed in a flask, the temperature of a reaction system is raised to 80 ℃, 800mL of N, N-dimethylformamide solution containing 0.16mol of isophorone diisocyanate and 2g of dibutyltin dilaurate is added dropwise through a peristaltic pump while stirring, and the mixture is stirred at constant temperature for reaction for 10 hours to obtain a solution containing intermediate product IV;
the intermediate IV infrared data are as follows:
3438cm -1 : -OH present and reduced; 1109cm -1 、801cm -1 : -Si-O-presence; 2928cm -1 : -C-H is present; 1560cm -1 : -N-H is present; 1722cm -1 : -c=o present; 2270cm -1 : -NCO present;
(5) Raising the temperature of the solution containing the intermediate product IV obtained in the step (4) to 110 ℃, then dropwise adding 500mL of N, N-dimethylformamide solution containing 0.16mol of 2,2' -dithiodiethanol by a peristaltic pump under stirring, reacting at constant temperature until the absorption peak of NCO-in a reaction system disappears on an infrared spectrum, stopping dropwise adding, concentrating the solution after the reaction is finished, slowly adding 1000mL of dichloromethane, filtering, taking filtrate, distilling under reduced pressure to remove the dichloromethane, and vacuum drying for 4h at 80 ℃ to obtain the intermediate product V;
The intermediate product V infrared data is as follows:
3438cm -1 : -OH present and enhanced; 1109cm -1 、801cm -1 : -Si-O-presence; 2928cm -1 : -C-H is present; 1560cm -1 : -N-H is present; 1722cm -1 : -c=o present; 2270cm -1 : -NCO vanishing; 535cm -1 : -S-present.
(6)N 2 Under the protection, 224g of intermediate product V, 0.16mol of triethylamine and 800mL of dichloromethane are placed in a flask, stirred uniformly under ice bath condition, then the temperature of a reaction system is maintained at 0-5 ℃, then 200mL of dichloromethane solution containing 0.16mol of acryloyl chloride is continuously dripped into the reaction system through a constant pressure dropping funnel, the reaction system is monitored by adopting FTIR, the stirring reaction is carried out until the OH-absorption peak in the reaction system is not reduced on infrared spectrum, the dripping is stopped, the reaction is ended, then the reaction system is filtered, filtrate is removed, 600mL of saturated sodium bicarbonate aqueous solution is added into the obtained solid product for washing 3 times, 1000mL of deionized water is used for washing 3 times, and vacuum drying is carried out at 50 ℃ until the weight is constant, thus obtaining a target product VI;
the obtained infrared data of the target product VI are as follows:
3438cm -1 : -OH present and reduced; 1109cm -1 、801cm -1 : -Si-O-presence; 2928cm -1 ：-C-H is present; 1560cm -1 : -N-H is present; 1725cm -1 : -c=o present; 535cm -1 : -S-presence; 1614cm -1 、811cm -1 : -c=c-present.
The UTG coating prepared by the impact-resistant self-repairing coating by using the UTG obtained above is prepared by the following steps:
s1: under the condition of keeping the ambient humidity less than or equal to 60 percent, uniformly mixing a leveling agent and a solvent according to the formula amount, sequentially adding polyurethane acrylic ester, a functional monomer, a reactive diluent, a silane coupling agent, a defoaming agent and a leveling agent, stirring at the rotating speed of 1200r/min for 60min, adding a photoinitiator, continuously stirring at the rotating speed of 800r/min for 20min, standing for 20min, filtering with filter cloth with the aperture of 1 mu m, and taking filtrate to obtain the UTG impact-resistant self-repairing coating;
s2: uniformly coating the UTG obtained in the step S1 on the surface of a flat and clean UTG film by using an impact-resistant self-repairing coating, heating at 70 ℃ for 4.5min, and then carrying out UV irradiation on the coating layer with the irradiation energy of 700mJ/cm 2 The irradiation time is 40s, and a UTG coating primary product is obtained;
s3: finally, the initial product of the UTG coating obtained in the step S2 is placed in a constant temperature chamber and kept stand at 60 ℃ for 72 hours, so as to obtain the UTG coating with the thickness of 100 mu m.
Example 2
An impact-resistant self-repairing coating for UTG comprises the following raw materials in 100 weight percent:
polyurethane acrylic ester CN9006 NS 5 parts;
Polyurethane acrylic ester CN8009 NS 10 parts;
polyurethane acrylic ester CN965 NS 35 parts;
5 parts of neopentyl glycol diacrylate;
10 parts of isooctyl acrylate;
5 parts of N-acryloylmorpholine;
15-20 parts of a reactive diluent;
172 parts of a silane coupling agent KH;
1 part of photoinitiator BP;
184 parts of a photoinitiator;
0.2 parts of defoamer;
1.0 part of leveling agent;
the balance of solvent.
The functional monomer is prepared by the following method:
(1) Nano SiO 2 Placing the mixture into a four-neck flask filled with 200mL of ethyl acetate, performing ultrasonic dispersion for 1h, adding a silane coupling agent KH550 and deionized water, slowly heating to 80 ℃, and heating and stirring for 6h; after the reaction is finished, cooling to room temperature, filtering, washing with 600mL of ethyl acetate, and vacuum drying at 80 ℃ to constant weight to obtain an intermediate product I;
the SiO is 2 The dosage ratio of the silane coupling agent KH550 to the deionized water is 5.00g:35.00g:3.00g;
the intermediate I infrared data are as follows:
3438cm -1 : -OH weakening; 1109cm -1 、801cm -1 : -Si-O-presence; 2928cm -1 : -C-H is present; 1560cm -1 : -N-H is present;
(2) Placing the intermediate product I and isophorone diisocyanate into 500mL of N, N-dimethylformamide, stirring at room temperature for reaction for 3 hours, removing the solvent by reduced pressure distillation after the reaction is finished, and drying in vacuum at 80 ℃ for 4 hours to obtain an intermediate product II;
the dosage ratio of the intermediate product I to isophorone diisocyanate is 33g:0.16 to 0.18mol;
the intermediate II infrared data are as follows:
3438cm -1 : -OH is present; 1109cm -1 、801cm -1 : -Si-O-presence; 2928cm -1 : -C-H is present; 1560cm -1 : -N-H is present; 1702cm -1 : -c=o present; 2270cm -1 : -NCO present;
(3)N 2 under protection, 68g of intermediate II, dibutyltin dilaurate, 1000mL of N, N-dimethylformamide are placed in a fireThe temperature of the reaction system is raised to 120 ℃ in a bottle, then 800mL of N, N-dimethylformamide solution containing 0.16mol of polypropylene glycol 600 is dropwise added by a peristaltic pump while stirring, the reaction system is monitored by FTIR, the absorption peak of NCO-in the reaction system continuously drops to disappear, the dropwise addition is stopped, the reaction is finished, the solution is concentrated, 1000mL of dichloromethane is slowly added, the reaction product is filtered, the filtrate is taken, the dichloromethane is removed by reduced pressure distillation, and the intermediate product III is obtained by vacuum drying for 4 hours at 80 ℃;
The dosage of the dibutyl tin dilaurate is 0.5% of the mass of the intermediate product II;
the intermediate III infrared data are as follows:
3440cm -1 : -OH is present; 1109cm -1 、801cm -1 : -Si-O-presence; 2928cm -1 : -C-H is present; 1560cm -1 : -N-H is present; 1722cm -1 : -c=o present; 2270cm -1 : -NCO vanishing;
(4)N 2 under the protection, 164g of intermediate product III and 1000mL of N, N-dimethylformamide are placed in a flask, the temperature of a reaction system is raised to 70 ℃, 800mL of N, N-dimethylformamide solution containing 0.16mol of dicyclohexylmethane-4, 4' -diisocyanate and 2g of dibutyltin dilaurate is dropwise added through a peristaltic pump while stirring, and the mixture is stirred at constant temperature for reaction for 12 hours to obtain a solution containing intermediate product IV;
the intermediate IV infrared data are as follows:
3438cm -1 : -OH present and reduced; 1109cm -1 、801cm -1 : -Si-O-presence; 2928cm -1 : -C-H is present; 1560cm -1 : -N-H is present; 1722cm -1 : -c=o present; 2270cm -1 : -NCO present;
(5) Raising the temperature of the solution containing the intermediate product IV obtained in the step (4) to 100 ℃, then dropwise adding 500mL of N, N-dimethylformamide solution containing 0.16mol of 2,2' -dithiodiethanol by a peristaltic pump under stirring, reacting at constant temperature until the absorption peak of NCO-in a reaction system disappears on an infrared spectrum, stopping dropwise adding, concentrating the solution after the reaction is finished, slowly adding 1000mL of dichloromethane, filtering, taking filtrate, distilling under reduced pressure to remove the dichloromethane, and vacuum drying for 4h at 80 ℃ to obtain the intermediate product V;
The intermediate product V infrared data is as follows:
3438cm -1 : -OH present and enhanced; 1109cm -1 、801cm -1 : -Si-O-presence; 2928cm -1 : -C-H is present; 1560cm -1 : -N-H is present; 1722cm -1 : -c=o present; 2270cm -1 : -NCO vanishing; 535cm -1 : -S-present.
(6)N 2 Under the protection, 230.5g of an intermediate product V, 0.16mol of triethylamine and 800mL of dichloromethane are placed in a flask, stirred uniformly under the ice bath condition, then the temperature of a reaction system is maintained at 0-5 ℃, then 200mL of dichloromethane solution containing 0.16mol of acryloyl chloride is continuously dripped into the reaction system through a constant pressure dropping funnel, the reaction system is monitored by FTIR, the stirring reaction is carried out until the OH-absorption peak in the reaction system is not reduced on the infrared spectrum, the dripping is stopped, the reaction is ended, then the reaction system is filtered, the filtrate is removed, 600mL of saturated sodium bicarbonate aqueous solution is added into the obtained solid product to wash for 3 times, 1000mL of deionized water is used to wash for 3 times, and the solid product is dried to constant weight under vacuum at 50 ℃ to obtain a target product VI;
the obtained infrared data of the target product VI are as follows: 3438cm -1 : -OH present and reduced; 1109cm -1 、801cm -1 : -Si-O-presence; 2928cm -1 : -C-H is present; 1560cm -1 : -N-H is present; 1725cm -1 : -c=o present; 535cm -1 : -S-presence; 1614cm -1 、811cm -1 : -c=c-present.
The UTG coating prepared by the impact-resistant self-repairing coating by using the UTG obtained above is prepared by the following steps:
s1: under the condition of keeping the ambient humidity less than or equal to 60 percent, uniformly mixing a leveling agent and a solvent according to the formula amount, sequentially adding polyurethane acrylic ester, a functional monomer, a reactive diluent, a silane coupling agent, a defoaming agent and a leveling agent, stirring at the rotating speed of 1500r/min for 50min, adding a photoinitiator, continuously stirring at the rotating speed of 1000r/min for 15min, standing for 20min, filtering with filter cloth with the aperture of 1 mu m, and taking filtrate to obtain the UTG impact-resistant self-repairing coating;
s2: uniformly coating the UTG obtained in the step S1 on the surface of a flat and clean UTG film by using an impact-resistant self-repairing coating, heating at 60 ℃ for 5min, and then carrying out UV irradiation on the coating layer, wherein the irradiation energy is 700mJ/cm 2 The irradiation time is 40s, and a UTG coating primary product is obtained;
s3: finally, the initial product of the UTG coating obtained in the step S2 is placed in a constant temperature chamber and kept stand at 60 ℃ for 72 hours, so as to obtain the UTG coating with the thickness of 100 mu m.
Example 3
An impact-resistant self-repairing coating for UTG comprises the following raw materials in 100 weight percent:
Polyurethane acrylic ester CN8009 NS 25 parts;
15 parts of polyurethane acrylic ester CN965 NS;
12 parts of functional monomer;
7 parts of trimethylolpropane triacrylate;
8 parts of 1, 6-hexanediol diacrylate;
0.5 part of silane coupling agent KH 151;
1 part of photo initiator TPO-L;
0.1 part of defoaming agent;
0.5 part of leveling agent;
the balance of solvent.
The functional monomer is prepared by the following method:
(1) Nano SiO 2 Placing the mixture into a four-neck flask filled with 200mL of ethyl acetate, performing ultrasonic dispersion for 1h, adding a silane coupling agent KH550 and deionized water, slowly heating to 60 ℃, heating and stirring for reaction for 14h, cooling to room temperature after the reaction is finished, filtering, washing with 600mL of ethyl acetate, and performing vacuum drying at 80 ℃ to constant weight to obtain an intermediate product I;
the SiO is 2 The dosage ratio of the silane coupling agent KH550 to the deionized water is 5.00g:35.00g:3.00g;
the intermediate I infrared data are as follows:
3438cm -1 : -OH weakening; 1109cm -1 、801cm -1 : -Si-O-presence; 2928cm -1 : -C-H is present; 1560cm -1 : -N-H is present.
(2) Placing the intermediate product I and isophorone diisocyanate into 500mL of N, N-dimethylformamide, stirring at room temperature for reaction for 4 hours, distilling under reduced pressure after the reaction is finished, and vacuum drying at 80 ℃ for 4 hours to obtain an intermediate product II;
the dosage ratio of the intermediate product I to isophorone diisocyanate is as follows: 33g:0.16mol;
the intermediate II infrared data are as follows:
3438cm -1 : -OH is present; 1109cm -1 、801cm -1 : -Si-O-presence; 2928cm -1 : -C-H is present; 1560cm -1 : -N-H is present; 1702cm -1 : -c=o present; 2270cm -1 : -NCO present.
(3)N 2 Under the protection, 68g of an intermediate product II, dibutyltin dilaurate and 1000mL of N, N-dimethylformamide are placed in a flask, the temperature of a reaction system is raised to 100 ℃, then 800mL of N, N-dimethylformamide solution containing 0.18mol of polypropylene glycol 600 is dropwise added through a peristaltic pump while stirring, the progress of the reaction system is monitored by adopting FTIR, the absorption peak of NCO-in an infrared spectrum continuously dropwise added into the reaction system disappears, the dropwise addition is stopped, the reaction is ended, the solution is concentrated, 1000mL of dichloromethane is slowly added, the reaction product is filtered, the filtrate is taken, the dichloromethane is removed by reduced pressure distillation, and vacuum drying is carried out for 4 hours at 80 ℃ to obtain an intermediate product III;
The dosage of the dibutyl tin dilaurate is 0.5% of the mass of the intermediate product II;
the intermediate III infrared data are as follows:
3440cm -1 : -OH is present; 1109cm -1 、801cm -1 : -Si-O-presence; 2928cm -1 : -C-H is present; 1560cm -1 : -N-H is present; 1722cm -1 : -c=o present; 2270cm -1 : -the NCO vanishes.
(4)N 2 Under the protection, 164g of intermediate product III and 1000mL of N, N-dimethylformamide are placed in a flask, the temperature of a reaction system is raised to 100 ℃, 800mL of N, N-dimethylformamide solution containing 0.16mol of isophorone diisocyanate and 2g of dibutyltin dilaurate is added dropwise through a peristaltic pump while stirring, and the mixture is stirred at constant temperature for reaction for 8 hours to obtain a solution containing intermediate product IV;
the dosage of the dibutyl tin dilaurate is 0.5% of the total mass of the intermediate product III and isophorone diisocyanate;
the intermediate IV infrared data are as follows:
3438cm -1 : -OH present and reduced; 1109cm -1 、801cm -1 : -Si-O-presence; 2928cm -1 : -C-H is present; 1560cm -1 : -N-H is present; 1722cm -1 : -c=o present; 2270cm -1 : -NCO present;
(5) Raising the temperature of the solution containing the intermediate product IV obtained in the step (4) to 120 ℃, then dropwise adding 500mL of N, N-dimethylformamide solution containing 0.16mol of 2,2' -dithiodiethanol by a peristaltic pump under stirring, reacting at constant temperature until the absorption peak of NCO-in a reaction system disappears on an infrared spectrum, stopping dropwise adding, concentrating the solution after the reaction is finished, slowly adding 1000mL of dichloromethane, filtering, taking filtrate, distilling under reduced pressure to remove the dichloromethane, and vacuum drying for 4h at 80 ℃ to obtain the intermediate product V;
Intermediate V infrared data are as follows: 3438cm -1 : -OH present and enhanced; 1109cm -1 、801cm -1 : -Si-O-presence; 2928cm -1 : -C-H is present; 1560cm -1 : -N-H is present; 1722cm -1 : -c=o present; 2270cm -1 : -NCO vanishing; 535cm -1 : -S-present.
(6)N 2 224g of intermediate V, 0.20mol of triethylamine and 800mL of methylene chloride are placed in a flask under protection and stirred under ice bath conditionUniformly stirring, maintaining the temperature of a reaction system at 0-5 ℃, then starting to continuously dropwise add 200mL of methylene dichloride solution containing 0.20mol of acryloyl chloride into the reaction system through a constant pressure dropping funnel, monitoring the reaction system by adopting FTIR, stirring and reacting until the OH-absorption peak in the reaction system is not reduced on the infrared spectrum, stopping dropwise adding, ending the reaction, filtering the reaction system, removing filtrate, adding 600mL of saturated sodium bicarbonate aqueous solution into the obtained solid product, washing 3 times with 1000mL of deionized water, and vacuum drying at 50 ℃ until the weight is constant to obtain a target product VI;
the obtained infrared data of the target product VI are as follows:
3438cm -1 : -OH present and reduced; 1109cm -1 、801cm -1 : -Si-O-presence; 2928cm -1 : -C-H is present; 1560cm -1 : -N-H is present; 1725cm -1 : -c=o present; 535cm -1 : -S-presence; 1614cm -1 、811cm -1 : -c=c-present.
UTG coating obtained with an impact-resistant self-healing coating according to said UTG, prepared by the following method:
s1: under the condition of keeping the ambient humidity less than or equal to 60 percent, uniformly mixing a leveling agent and a solvent according to the formula amount, sequentially adding polyurethane acrylic ester, a functional monomer, a reactive diluent, a silane coupling agent, a defoaming agent and a leveling agent, stirring at the rotating speed of 1000r/min for 40min, adding a photoinitiator, continuously stirring at the rotating speed of 800r/min for 20min, standing for 20min, filtering with filter cloth with the aperture of 1 mu m, and taking filtrate to obtain the UTG impact-resistant self-repairing coating;
s2: uniformly coating the UTG obtained in the step S1 on the surface of a flat and clean UTG film by using an impact-resistant self-repairing coating, heating at 80 ℃ for 4min, and then carrying out UV irradiation on the coating layer, wherein the irradiation energy is 700mJ/cm 2 The irradiation time is 40s, and a UTG coating primary product is obtained;
s3: finally, the initial product of the UTG coating obtained in the step S2 is placed in a constant temperature chamber and kept stand for 72 hours at the temperature of 60 ℃ to obtain the UTG coating.
Example 4
An impact-resistant self-repairing coating for UTG comprises the following raw materials in 100 weight percent:
10 parts of polyurethane acrylic ester CN9006 NS;
Polyurethane acrylic ester CN965 NS 35 parts;
16 parts of functional monomer;
8 parts of 1, 6-hexanediol diacrylate;
2 parts of neopentyl glycol diacrylate;
5 parts of ethyl acrylate;
3 parts of isobornyl acrylate;
1.5 parts of silane coupling agent KH 590;
1173 parts of photoinitiator;
0.15 parts of defoamer;
0.8 part of leveling agent;
the balance of solvent.
The functional monomer is prepared by the following method:
(1) Nano SiO 2 Placing the mixture into a four-neck flask filled with 200mL of ethyl acetate, performing ultrasonic dispersion for 1h, adding a silane coupling agent KH550 and deionized water, slowly heating to 70 ℃, heating and stirring for reaction for 6h, cooling to room temperature after the reaction is finished, filtering, washing with 600mL of ethyl acetate, and performing vacuum drying at 80 ℃ to constant weight to obtain an intermediate product I;
the SiO is 2 The dosage ratio of the silane coupling agent KH550 to the deionized water is as follows: 5.00g:35.00g:3.00g;
the intermediate I infrared data are as follows:
3438cm -1 : -OH weakening; 1109cm -1 、801cm -1 : -Si-O-presence; 2928cm -1 : -C-H is present; 1560cm -1 : -N-H is present.
(2) Placing the intermediate product I and isophorone diisocyanate into 500mL of N, N-dimethylformamide, stirring at room temperature for reaction for 3 hours, distilling under reduced pressure after the reaction is finished, and vacuum drying at 80 ℃ for 4 hours to obtain an intermediate product II;
the dosage ratio of the intermediate product I to isophorone diisocyanate is 33g:0.16 to 0.18mol;
the intermediate II infrared data are as follows:
3438cm -1 : -OH is present; 1109cm -1 、801cm -1 : -Si-O-presence; 2928cm -1 : -C-H is present; 1560cm -1 : -N-H is present; 1702cm -1 : -c=o present; 2270cm -1 : -NCO present.
(3)N 2 Under the protection, 68g of an intermediate product II, dibutyltin dilaurate and 1000mL of N, N-dimethylformamide are placed in a flask, the temperature of a reaction system is raised to 115 ℃, then 800mL of N, N-dimethylformamide solution containing 0.16mol of polypropylene glycol 600 is dropwise added through a peristaltic pump while stirring, the progress of the reaction system is monitored by adopting FTIR, the absorption peak of NCO-in an infrared spectrum continuously dropwise added into the reaction system disappears, the dropwise addition is stopped, the reaction is ended, the solution is concentrated, 1000mL of dichloromethane is slowly added, the reaction product is filtered, the filtrate is taken, the dichloromethane is removed by reduced pressure distillation, and vacuum drying is carried out for 4 hours at 80 ℃ to obtain an intermediate product III;
The dosage of the dibutyl tin dilaurate is 0.5% of the mass of the intermediate product II;
the intermediate III infrared data are as follows:
3440cm -1 : -OH is present; 1109cm -1 、801cm -1 : -Si-O-presence; 2928cm -1 : -C-H is present; 1560cm -1 : -N-H is present; 1722cm -1 : -c=o present; 2270cm -1 : -the NCO vanishes.
(4)N 2 Under protection, 164g of intermediate III, 1000mL of N, N-dimethylformamide were placed in a flask, and the temperature of the reaction system was raised to 90℃and 800mL of an N, N-dimethylformamide solution containing 0.16mol of dicyclohexylmethane-4, 4' -diisocyanate, 2g of dibutyltin dilaurate was added dropwise by peristaltic pump while stirringStirring at constant temperature for reaction for 10h to obtain a solution containing an intermediate product IV;
the intermediate IV infrared data are as follows:
3438cm -1 : -OH present and reduced; 1109cm -1 、801cm -1 : -Si-O-presence; 2928cm -1 : -C-H is present; 1560cm -1 : -N-H is present; 1722cm -1 : -c=o present; 2270cm -1 : -NCO present;
(5) Raising the temperature of the solution containing the intermediate product IV obtained in the step (4) to 105 ℃, then dropwise adding 500mL of N, N-dimethylformamide solution containing 0.16mol of 2,2' -dithiodiethanol by a peristaltic pump under stirring, reacting at constant temperature until the absorption peak of NCO-in a reaction system disappears on an infrared spectrum, stopping dropwise adding, concentrating the solution after the reaction is finished, slowly adding 1000mL of dichloromethane, filtering, taking filtrate, distilling under reduced pressure to remove the dichloromethane, and vacuum drying for 4h at 80 ℃ to obtain the intermediate product V;
The intermediate product V infrared data is as follows:
3438cm -1 : -OH present and enhanced; 1109cm -1 、801cm -1 : -Si-O-presence; 2928cm -1 : -C-H is present; 1560cm -1 : -N-H is present; 1722cm -1 : -c=o present; 2270cm -1 : -NCO vanishing; 535cm -1 : -S-present.
(6)N 2 Under the protection, 230.5g of an intermediate product V, 0.20mol of triethylamine and 800mL of dichloromethane are placed in a flask, stirred uniformly under the ice bath condition, then the temperature of a reaction system is maintained at 0-5 ℃, then 200mL of dichloromethane solution containing 0.20mol of acryloyl chloride is continuously dripped into the reaction system through a constant pressure dropping funnel, the reaction system is monitored by adopting FTIR, the stirring reaction is carried out until the OH-absorption peak in the reaction system is not reduced on an infrared spectrum, the dripping is stopped, the reaction is ended, then the reaction system is filtered, filtrate is removed, 600mL of saturated sodium bicarbonate aqueous solution is added into the obtained solid product for washing 3 times, 1000mL of deionized water is used for washing 3 times, and vacuum drying is carried out at 50 ℃ until the weight is constant, thus obtaining a target product VI;
the obtained infrared data of the target product VI are as follows:
3438cm -1 : -OH present and reduced; 1109cm -1 、801cm -1 : -Si-O-presence; 2928cm -1 : -C-H is present; 1560cm -1 : -N-H is present; 1725cm -1 : -c=o present; 535cm -1 : -S-presence; 1614cm -1 、811cm -1 : -c=c-present.
UTG coating obtained with an impact-resistant self-healing coating according to said UTG, prepared by the following method:
s1: under the condition of keeping the ambient humidity less than or equal to 60 percent, uniformly mixing a leveling agent and a solvent according to the formula amount, sequentially adding polyurethane acrylic ester, a functional monomer, a reactive diluent, a silane coupling agent, a defoaming agent and a leveling agent, stirring at the rotating speed of 1400r/min for 40min, adding a photoinitiator, continuously stirring at the rotating speed of 1000r/min for 10min, standing for 20min, filtering with filter cloth with the aperture of 1 mu m, and taking filtrate to obtain the UTG impact-resistant self-repairing coating;
s2: uniformly coating the UTG obtained in the step S1 on the surface of a flat and clean UTG film by using an impact-resistant self-repairing coating, heating at 70 ℃ for 4min, and then carrying out UV irradiation on the coating layer with the irradiation energy of 700mJ/cm 2 The irradiation time is 40s, and a UTG coating primary product is obtained;
s3: finally, the initial product of the UTG coating obtained in the step S2 is placed in a constant temperature chamber and kept stand for 72 hours at the temperature of 60 ℃ to obtain the UTG coating.
Example 5
An impact-resistant self-repairing coating for UTG comprises the following raw materials in 100 weight percent:
polyurethane acrylic ester CN9006 NS 8 parts;
Polyurethane acrylic ester CN8009 NS 10 parts;
polyurethane acrylic CN965 NS 32 parts;
20 parts of functional monomer;
10 parts of neopentyl glycol diacrylate;
6 parts of isooctyl acrylate;
4 parts of isobornyl acrylate;
570 parts of silane coupling agent KH;
1 part of photoinitiator BP;
1173 parts of photoinitiator;
0.2 parts of defoamer;
1.0 part of leveling agent;
the balance of solvent.
The functional monomer is prepared by the following method:
(1) Nano SiO 2 Placing the mixture into a four-neck flask filled with 200mL of ethyl acetate, performing ultrasonic dispersion for 1h, adding a silane coupling agent KH550 and deionized water, slowly heating to 70 ℃, heating and stirring for reaction for 14h, cooling to room temperature after the reaction is finished, filtering, washing with 600mL of ethyl acetate, and performing vacuum drying at 80 ℃ to constant weight to obtain an intermediate product I;
the SiO is 2 The dosage ratio of the silane coupling agent KH550 to the deionized water is 5.00g:35.00g:3.00g;
The intermediate I infrared data are as follows:
3438cm -1 : -OH weakening; 1109cm -1 、801cm -1 : -Si-O-presence; 2928cm -1 : -C-H is present; 1560cm -1 : -N-H is present.
(2) Placing the intermediate product I and isophorone diisocyanate into 500mL of N, N-dimethylformamide, stirring at room temperature for reaction for 4 hours, distilling under reduced pressure after the reaction is finished, and vacuum drying at 80 ℃ for 4 hours to obtain an intermediate product II;
the dosage ratio of the intermediate product I to isophorone diisocyanate is as follows: 33g:0.16 to 0.18mol;
the intermediate II infrared data are as follows: 3438cm -1 : -OH is present; 1109cm -1 、801cm -1 : -Si-O-presence; 2928cm -1 : -C-H is present; 1560cm -1 : -N-H is present; 1702cm -1 : -c=o present; 2270cm -1 : -NCO present.
(3)N 2 Under the protection, 68g of an intermediate product II, dibutyltin dilaurate and 1000mL of N, N-dimethylformamide are placed in a flask, the temperature of a reaction system is raised to 105 ℃, then 800mL of N, N-dimethylformamide solution containing 0.17mol of polypropylene glycol 600 is dropwise added through a peristaltic pump while stirring, the progress of the reaction system is monitored by adopting FTIR, the absorption peak of NCO-in an infrared spectrum continuously dropwise added into the reaction system disappears, the dropwise addition is stopped, the reaction is ended, the solution is concentrated, 1000mL of dichloromethane is slowly added, the reaction product is filtered, the filtrate is taken, the dichloromethane is removed by reduced pressure distillation, and vacuum drying is carried out for 4 hours at 80 ℃ to obtain an intermediate product III;
The dosage of the dibutyl tin dilaurate is 0.5% of the mass of the intermediate product II;
the intermediate III infrared data are as follows:
3440cm -1 : -OH is present; 1109cm -1 、801cm -1 : -Si-O-presence; 2928cm -1 : -C-H is present; 1560cm -1 : -N-H is present; 1722cm -1 : -c=o present; 2270cm -1 : -the NCO vanishes.
(4)N 2 Under the protection, 164g of intermediate product III and 1000mL of N, N-dimethylformamide are placed in a flask, the temperature of a reaction system is raised to 80 ℃, 800mL of N, N-dimethylformamide solution containing 0.16mol of isophorone diisocyanate and 2g of dibutyltin dilaurate is added dropwise through a peristaltic pump while stirring, and the mixture is stirred at constant temperature for reaction for 12 hours to obtain a solution containing intermediate product IV;
the intermediate IV infrared data are as follows:
3438cm -1 : -OH present and reduced; 1109cm -1 、801cm -1 : -Si-O-presence; 2928cm -1 : -C-H is present; 1560cm -1 : -N-H is present; 1722cm -1 : -c=o present; 2270cm -1 : -NCO present;
(5) Raising the temperature of the solution containing the intermediate product IV obtained in the step (4) to 115 ℃, then dropwise adding 500mL of N, N-dimethylformamide solution containing 0.16mol of 2,2' -dithiodiethanol by a peristaltic pump under stirring, reacting at constant temperature until the absorption peak of NCO-in a reaction system disappears on an infrared spectrum, stopping dropwise adding, concentrating the solution after the reaction is finished, slowly adding 1000mL of dichloromethane, filtering, taking filtrate, distilling under reduced pressure to remove the dichloromethane, and vacuum drying for 4h at 80 ℃ to obtain the intermediate product V;
The intermediate product V infrared data is as follows:
3438cm -1 : -OH present and enhanced; 1109cm -1 、801cm -1 : -Si-O-presence; 2928cm -1 : -C-H is present; 1560cm -1 : -N-H is present; 1722cm -1 : -c=o present; 2270cm -1 : -NCO vanishing; 535cm -1 : -S-present.
(6)N 2 Under the protection, 224g of intermediate product V, 0.18mol of triethylamine and 800mL of dichloromethane are placed in a flask, stirred uniformly under ice bath condition, then the temperature of a reaction system is maintained at 0-5 ℃, then 200mL of dichloromethane solution containing 0.18mol of acryloyl chloride is continuously dripped into the reaction system through a constant pressure dropping funnel, the reaction system is monitored by adopting FTIR, the stirring reaction is carried out until the OH-absorption peak in the reaction system is not reduced on infrared spectrum, the dripping is stopped, the reaction is ended, then the reaction system is filtered, filtrate is removed, 600mL of saturated sodium bicarbonate aqueous solution is added into the obtained solid product for washing 3 times, 1000mL of deionized water is used for washing 3 times, and vacuum drying is carried out at 50 ℃ until the weight is constant, thus obtaining a target product VI;
the obtained infrared data of the target product VI are as follows:
3438cm -1 : -OH present and reduced; 1109cm -1 、801cm -1 : -Si-O-presence; 2928cm -1 : -C-H is present; 1560cm -1 : -N-H is present; 1725cm -1 : -c=o present; 535cm -1 : -S-presence; 1614cm -1 、811cm -1 : -c=c-present.
A UTG coating obtained with an impact resistant self-healing coating according to UTG, prepared as follows:
s1: under the condition of keeping the ambient humidity less than or equal to 60 percent, uniformly mixing a leveling agent and a solvent according to the formula amount, sequentially adding polyurethane acrylic ester, a functional monomer, a reactive diluent, a silane coupling agent, a defoaming agent and a leveling agent, stirring at the rotating speed of 1500r/min for 60min, adding a photoinitiator, continuously stirring at the rotating speed of 1200r/min for 15min, standing for 20min, filtering with filter cloth with the aperture of 1 mu m, and taking filtrate to obtain the UTG impact-resistant self-repairing coating;
s2: uniformly coating the UTG obtained in the step S1 on the surface of a flat and clean UTG film by using an impact-resistant self-repairing coating, heating at 70 ℃ for 5min, and then carrying out UV irradiation on the coating layer with the irradiation energy of 800mJ/cm 2 The irradiation time is 30s, and a UTG coating primary product is obtained;
s3: finally, the initial product of the UTG coating obtained in the step S2 is placed in a constant temperature chamber and kept stand for 72 hours at the temperature of 60 ℃ to obtain the UTG coating.
Comparative example 1 the same as example 1 was carried out, except that comparative example 1 replaced the functional monomer of example 1 with an equivalent weight percent of trimethylolpropane triacrylate.
Comparative example 2 the same as example 1 was carried out, except that the intermediate product V obtained in example 1 was used as a functional monomer in comparative example 2.
Comparative example 3 the same as example 1 was different in that the UTG impact-resistant self-repairing paint obtained in comparative example 3 was composed of, in 100% by weight, the following raw materials:
polyurethane acrylic ester CN8009 NS 25 parts;
polyurethane acrylic ester CN965 NS 20 parts;
15 parts of a functional monomer (same as in example 1);
3 parts of trimethylolpropane triacrylate;
6 parts of 1, 6-hexanediol diacrylate;
6 parts of isooctyl acrylate;
184 parts of a photoinitiator;
0.1 part of defoaming agent;
0.6 part of leveling agent;
the balance of solvent.
Comparative example 4 the same as example 1 was different in that the UTG impact-resistant self-repairing paint obtained in comparative example 4 was composed of, in 100% by weight, the following raw materials:
polyurethane acrylic ester CN8009 NS 25 parts;
polyurethane acrylic ester CN965 NS 20 parts;
15 parts of a functional monomer (same as in example 1);
3 parts of trimethylolpropane triacrylate;
6 parts of 1, 6-hexanediol diacrylate;
6 parts of isooctyl acrylate;
1 part of silane coupling agent KH 560;
184 parts of a photoinitiator;
0.1 part of defoaming agent;
0.6 part of leveling agent;
the balance of solvent.
Comparative example 5 the same as example 1 was different in that the solvent in comparative example 5 was butanone.
Comparative example 6 the same as example 1, except that the UTG impact-resistant self-repairing paint obtained in comparative example 6 was composed of, in 100% by weight, the following raw materials:
polyurethane acrylic ester CN8009 NS 25 parts;
polyurethane acrylic ester CN965 NS 20 parts;
10 parts of functional monomer (same as in example 1);
3 parts of trimethylolpropane triacrylate;
6 parts of 1, 6-hexanediol diacrylate;
6 parts of isooctyl acrylate;
570 parts of silane coupling agent KH;
184 parts of a photoinitiator;
0.1 part of defoaming agent;
0.6 part of leveling agent;
the balance of solvent.
Comparative example 7 the same as example 1 was different in that the UTG impact-resistant self-repairing paint obtained in comparative example 7 was composed of, in 100% by weight, the following raw materials:
polyurethane acrylic ester CN8009 NS 25 parts;
polyurethane acrylic ester CN965 NS 20 parts;
20 parts of a functional monomer (same as in example 1);
3 parts of trimethylolpropane triacrylate;
6 parts of 1, 6-hexanediol diacrylate;
6 parts of isooctyl acrylate;
570 parts of silane coupling agent KH;
184 parts of a photoinitiator;
0.1 part of defoaming agent;
0.6 part of leveling agent;
the balance of solvent.
Performance testing
The coatings UTG obtained in inventive examples 1-5 and comparative examples 1-7 were subjected to the relevant performance tests, the test results being shown in Table 1.
The test method comprises the following steps:
(1) Thickness: the test was conducted according to the method described in JIS-K7105.
(2) Transmittance, haze: the test was conducted according to the method described in JIS-K7361.
(3) Ball falling impact: the UTG coating is horizontally placed on a plane at 23.5 ℃, a steel ball (diameter phi 20 mm) of 32g freely falls from a position of 60cm, and the coating is placed under a microscope to observe the appearance of the film surface, and no obvious mark is marked as '4'; slight dents, noted "3"; has obvious dent, which is marked as '2'; obvious marks such as cracks, stress whitening or breakage are marked as '1'.
(4) Self-repairing efficiency: the copper brush is used for carrying out back and forth operation on the coating at the temperature of 23.5 ℃ under the force of 1kg, the film surface repair condition is observed after 10 back and forth, and the film surface repair condition is repaired in seconds or self-repaired within 10 seconds and is marked as '5'; self-repair within 60s, noted "4"; self-repairing within 120s, which is marked as '3'; self-repairing within 10min, and marking as '2'; over 10min or scratch, recorded as "1".
(5) Adhesion force: adhesion testing was performed as described in ASTM D3359-17.
(6) Bending resistance: the UTG coating was cut into rectangular samples of 10mm×120mm, the short sides of the samples were fixed with an adhesive tape, the samples were mounted on a tensionless U-fold tester (apparatus name DLDMLH-FS, manufactured by yuasa system corporation), the outer diameter Φ of the bent portion of the tester was set to 4mm, the radius R was set to 2mm, the samples were folded in half, and a dynamic bending test of 180 ° was performed 20 ten thousand times to examine whether or not a crack or a crack was generated in the bent portion, and if no crack or a crack was generated in the bent portion, the test was evaluated as (j), and if a crack or a crack was generated in the bent portion, the test was evaluated as (x).
TABLE 1
First, as can be seen from a comparison of examples 1 to 5 and comparative examples 1 to 7 in Table 1, the UTG coating obtained in the present invention has excellent optical properties;
second, comparing examples 1-5 with comparative examples 1-7, it is clear that the UTG coating obtained by the invention has excellent buffering and energy absorption properties and self-repairing properties due to the unique structure of the functional microspheres;
thirdly, comparing examples 1-5 with comparative examples 1-5, the functional microspheres in the UTG coating obtained by the invention can fill UTG surface holes, have excellent anchoring effect and have excellent adhesion with UTG; from the comparison of the values of examples 1-5 and comparative examples 3-5, the silane coupling agent plays an important role between UTG and the coating under the condition of alcoholysis; comparing examples 1-5 with comparative examples 6-7, it is seen that optimizing the formulation ratio maximizes the coating performance.
With the above-described preferred embodiments according to the present invention as an illustration, the above-described descriptions can be used by persons skilled in the relevant art to make various changes and modifications without departing from the scope of the technical idea of the present invention. The technical scope of the present invention is not limited to the description, but must be determined according to the scope of claims.

Claims (7)

1. An impact-resistant self-repairing coating for UTG is characterized by comprising the following raw materials in parts by weight:
2. an impact self-repairing paint for UTG according to claim 1, wherein the preparation method of the functional monomer comprises the following steps:
(1) Nano SiO 2 Placing the mixture into a four-neck flask filled with 200mL of ethyl acetate, performing ultrasonic dispersion for 1h, adding a silane coupling agent KH550 and deionized water, slowly heating to 60-80 ℃, heating and stirring for reaction for 6-14h, cooling to room temperature after the reaction is finished, filtering, washing with 600mL of ethyl acetate, and performing vacuum drying at 80 ℃ to constant weight to obtain an intermediate product I;
the SiO is 2 The dosage ratio of the silane coupling agent KH550 to the deionized water is 5.00g:35.00g:3.00g;
(2) Placing the intermediate product I and isophorone diisocyanate into 500mL of N, N-dimethylformamide, stirring at room temperature for reaction for 2-4h, removing the solvent by reduced pressure distillation after the reaction is finished, and drying at 80 ℃ in vacuum for 4h to obtain an intermediate product II;
the dosage ratio of the intermediate product I to isophorone diisocyanate is 33g:0.16 to 0.18mol;
(3)N 2 under the protection, placing an intermediate product II, dibutyltin dilaurate and 1000mL of N, N-dimethylformamide into a flask, heating the reaction system to 100-120 ℃, then dropwise adding 800mL of N, N-dimethylformamide solution containing 0.16-0.18mol of polypropylene glycol 600 by a peristaltic pump while stirring, monitoring the progress of the reaction system by adopting FTIR, continuously dropwise adding NCO-in the reaction system until the absorption peak on an infrared spectrum disappears, stopping dropwise adding, ending the reaction, concentrating the solution, slowly adding 1000mL of dichloromethane, filtering the reaction product, taking filtrate, distilling under reduced pressure to remove the dichloromethane, and vacuum drying for 4 hours at 80 ℃ to obtain an intermediate product III;
The dosage ratio of the intermediate product II to the polypropylene glycol 600 is as follows: 68g:0.16 to 0.18mol;
the dosage of the dibutyl tin dilaurate is 0.5% of the mass of the intermediate product II;
(4)N 2 under the protection, 164g of intermediate product III and 1000mL of N, N-dimethylformamide are placed in a flask, the temperature of a reaction system is raised to 70-100 ℃, 800mL of N, N-dimethylformamide solution containing 0.16mol of diisocyanate and 2g of dibutyltin dilaurate is dropwise added through a peristaltic pump while stirring, and the mixture is stirred at constant temperature for reaction for 8-12 hours to obtain a solution containing an intermediate product IV;
(5) Raising the temperature of the solution containing the intermediate product IV to 100-120 ℃, then dropwise adding 500mL of N, N-dimethylformamide solution containing 0.16mol of 2,2' -dithiodiethanol by a peristaltic pump under stirring, reacting at constant temperature until the absorption peak of NCO-in a reaction system disappears on an infrared spectrum, stopping dropwise adding, concentrating the solution after the reaction is finished, slowly adding 1000mL of dichloromethane, filtering, taking filtrate, distilling under reduced pressure to remove the dichloromethane, and drying in vacuum for 4 hours at 80 ℃ to obtain the intermediate product;
(6)N 2 under the protection, 224-230.5g of intermediate product, 0.16-0.20mol of triethylamine and 800mL of dichloromethane are placed in a flask, stirred uniformly under ice bath condition, then the temperature of a reaction system is maintained at 0-5 ℃, then 200mL of dichloromethane solution containing 0.16-0.20mol of acryloyl chloride is continuously dripped into the reaction system through a constant pressure dropping funnel, the reaction system is monitored by FTIR, the stirring reaction is carried out until the OH-absorption peak in the reaction system is not reduced on the infrared spectrum, the dripping is stopped, the reaction is finished, then the reaction system is filtered, the filtrate is removed, 600mL of saturated sodium bicarbonate aqueous solution is added into the obtained solid product to wash for 3 times, 1000mL of deionized water is used for washing 3 times, and the solid product is dried to constant weight under vacuum at 50 ℃ to obtain the target product VI.
3. An impact self-healing paint for UTG according to claim 3, wherein: the diisocyanate is at least one of isophorone diisocyanate or dicyclohexylmethane-4, 4' -diisocyanate.
4. An impact resistant self-healing coating for UTG as defined in claim 1, wherein: the silane coupling agent is at least one of KH570, KH172, KH151 or KH 590.
5. An impact resistant self-healing coating for UTG as defined in claim 1, wherein: the photoinitiator is at least one of photoinitiators 184, 1173 and TPO-L, BP.
6. An impact resistant self-healing coating for UTG as defined in claim 1, wherein: the reactive diluent is at least one of ethyl acrylate, isooctyl acrylate, isobornyl acrylate, N-acryloylmorpholine, 1, 6-hexanediol diacrylate, neopentyl glycol diacrylate and trimethylolpropane triacrylate.
7. A coating of UTG as set forth in any one of claims 1 to 6 obtained UTG with an impact resistant self-healing coating, characterized in that: the preparation method comprises the following steps:
s1: under the condition of keeping the ambient humidity less than or equal to 60 percent, uniformly mixing a leveling agent and a solvent according to the formula amount, sequentially adding polyurethane acrylic ester, a functional monomer, a reactive diluent, a silane coupling agent, a defoaming agent and a leveling agent, stirring at the rotating speed of 1000-1500r/min for 40-60min, adding a photoinitiator, continuously stirring at the rotating speed of 800-1200r/min for 10-20min, standing for 20min, filtering with filter cloth with the aperture of 1 mu m, and taking filtrate to obtain the UTG impact-resistant self-repairing paint;
S2: uniformly coating the UTG obtained in the step S1 on the surface of a smooth UTG film by using an impact-resistant self-repairing coating, heating at 60-80 ℃ for 4-5min, and then carrying out UV irradiation on the coating layer with the irradiation energy of 700-800mJ/cm 2 The irradiation time is 30-40s, and the UTG coating primary product is obtained;
s3: and then placing the UTG coating primary product obtained in the step S2 in a constant temperature chamber, and standing at 60 ℃ for 72h to obtain the UTG coating.
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Publication number Priority date Publication date Assignee Title
CN109233423A (en) * 2018-09-26 2019-01-18 广州市嵩达新材料科技有限公司 A kind of modified Nano particle and preparation method thereof and super-hydrophobic selfreparing photocureable coating prepared therefrom
JP2020164677A (en) * 2019-03-29 2020-10-08 Jnc株式会社 Photopolymerizable coating composition and article obtained using the same
CN111793409A (en) * 2020-07-28 2020-10-20 上海蓝宝涂料有限公司 Vacuum electroplating UV (ultraviolet) photocuring base coat and preparation method thereof
CN116355384A (en) * 2023-04-17 2023-06-30 苏州易昇光学材料股份有限公司 Buffering and energy-absorbing GPU film

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109233423A (en) * 2018-09-26 2019-01-18 广州市嵩达新材料科技有限公司 A kind of modified Nano particle and preparation method thereof and super-hydrophobic selfreparing photocureable coating prepared therefrom
JP2020164677A (en) * 2019-03-29 2020-10-08 Jnc株式会社 Photopolymerizable coating composition and article obtained using the same
CN111793409A (en) * 2020-07-28 2020-10-20 上海蓝宝涂料有限公司 Vacuum electroplating UV (ultraviolet) photocuring base coat and preparation method thereof
CN116355384A (en) * 2023-04-17 2023-06-30 苏州易昇光学材料股份有限公司 Buffering and energy-absorbing GPU film

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