CN116063921B - High-transparency polyurethane wear-resistant paint and preparation method and application thereof - Google Patents

High-transparency polyurethane wear-resistant paint and preparation method and application thereof Download PDF

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CN116063921B
CN116063921B CN202310244630.2A CN202310244630A CN116063921B CN 116063921 B CN116063921 B CN 116063921B CN 202310244630 A CN202310244630 A CN 202310244630A CN 116063921 B CN116063921 B CN 116063921B
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parts
wear
transparency
polyurethane
coating
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CN116063921A (en
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杨小牛
李金歌
李洋
胡凌峰
赵晓礼
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Changchun Institute of Applied Chemistry of CAS
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Changchun Institute of Applied Chemistry of CAS
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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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/69—Polymers of conjugated dienes
    • 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
    • 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
    • C09D7/48—Stabilisers against degradation by oxygen, light or heat
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T30/00—Transportation of goods or passengers via railways, e.g. energy recovery or reducing air resistance

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention provides a high-transparency polyurethane wear-resistant paint and a preparation method and application thereof, wherein the wear-resistant paint comprises the following raw materials in parts by mass: 60 parts of polyolefin polyol, 25-65 parts of non-aromatic isocyanate, 1-20 parts of curing agent, 0-2 parts of catalyst, 0.5-3 parts of ultraviolet absorber, 0-1 part of wetting agent, 0.1-1 part of leveling agent and 100-500 parts of solvent. According to the invention, the polyolefin polyol is adopted to ensure that unsaturated double bonds exist in polyurethane molecular chains, so that the double bonds in the molecular structure of the coating are oxidized into aldehyde groups after ozone treatment, and the formed aldehyde groups can form hydrogen bonds with carbamate groups of polyurethane, so that the wear resistance of the coating is improved; the non-aromatic isocyanate and the curing agent ensure that the polyurethane molecular chain has no benzene ring structure, so that the light transmittance of the coating in the visible light range is more than 95 percent; the weather resistance is excellent; can be used for the surfaces of train and automobile glass, aircraft windows and cabins, precise instruments, and the like, and prolongs the service life.

Description

High-transparency polyurethane wear-resistant paint and preparation method and application thereof
Technical Field
The invention belongs to the technical field of anti-erosion wear coating, and particularly relates to high-transparency polyurethane wear-resistant paint and a preparation method and application thereof.
Background
The aircraft transparent part refers to parts such as an aircraft cockpit cover, a windshield, an aircraft cabin, a porthole and the like, wherein the aircraft cockpit is a working space for a pilot to finish flight tasks such as piloting, communication, navigation and the like. In order to ensure clear and good flight view of pilots, aircraft cabins are generally made of transparent and impact-resistant high polymer materials. However, since aircraft usually perform flight tasks in various severe environments, the aircraft transparency is very susceptible to erosive wear, which seriously affects the flight view and safety of the pilot. Thus, the protective coating of the aircraft transparency is critical to the reliability and safety of the aircraft.
Since 1920, aircraft transparency has been made of flat annealed glass, curved composite glass, thermally quenched glass, organic glass or tempered glass-multilayer plastic composite materials. Plexiglass is a popular name for polymethyl methacrylate and is now widely used in civilian and military aircraft. However, the organic glass itself has poor abrasion resistance, so the abrasion resistant coating is particularly important for organic glass. Most of the existing organic glass wear-resistant coatings are polysiloxane, and the coatings are high in hardness and good in wear resistance, but the thickness of the coatings is only 3-5 microns, so that the high light transmittance performance and the erosion and wear resistance cannot be ensured.
Currently, jiang Nada discloses a quick-drying fluorine-containing modified UV-cured hyperbranched waterborne polyurethane coating (CN 115612395A), which is hydrophobic and has high glossiness, high fullness and good hardness and substrate adhesion, but the preparation method is complex and no mention of wear resistance is made. The Jiangsu iron anchor glass Co., ltd. Invented a transparent conductive rain erosion resistant coating (CN 115322666A) which has a three-layer structure, has good wear resistance and conductivity, can resist the impact of raindrops, and also has excellent weather resistance, but the preparation method is complex. The transparent durable antifouling paint (CN 113527995A) prepared by the university of Zhongshan has high adhesive force to base materials such as glass, good luster, high transparency and high wear resistance, can be used in the fields of electronic touch screens, precise instrument surfaces, fabric surfaces and the like, and has weather resistance to be evaluated. In addition, the Zhaoqing Haohun resin technology Co., ltd.utilized polyolefin polyol to prepare a one-component aqueous polyurethane coating (CN 114045098A) which has excellent abrasion resistance but low light transmittance.
Disclosure of Invention
In view of the above, the invention aims to provide a high-transparency polyurethane wear-resistant paint, a preparation method and application thereof, and a coating prepared from the high-transparency polyurethane wear-resistant paint has high light transmittance in a visible light range, sand erosion and abrasion resistance, excellent weather resistance and good substrate adhesion.
The invention provides a high-transparency polyurethane wear-resistant paint which comprises the following raw materials in parts by mass:
60 parts of polyolefin polyol, 25-65 parts of non-aromatic isocyanate, 1-20 parts of curing agent, 0-2 parts of catalyst, 0.5-3 parts of ultraviolet absorber, 0-1 part of wetting agent, 0.1-1 part of leveling agent and 100-500 parts of solvent.
In the present invention, the polyolefin polyol is a hydroxyl-terminated polybutadiene and/or a hydroxyl-terminated epoxidized polybutadiene resin.
In the present invention, the polyolefin polyol has a number average molecular weight of 2000 to 5000.
In the present invention, the non-aromatic isocyanate is one or more of isophorone diisocyanate, dicyclohexylmethane diisocyanate, trimethyl-1, 6-hexamethylene diisocyanate, methylcyclohexyl diisocyanate, cyclohexanedimethylene diisocyanate, hexamethylene diisocyanate trimer, hexamethylene diisocyanate biuret, and isophorone diisocyanate trimer.
In the present invention, the curing agent is selected from one or more of 1, 2-propanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 2-pentanediol, neopentyl glycol, 2-methyl-2, 4-pentanediol, 1, 2-hexanediol, 1, 2-octanediol, and 1, 2-decanediol.
The invention provides a preparation method of the high-transparency polyurethane wear-resistant paint, which comprises the following steps:
uniformly mixing an ultraviolet absorbent, a wetting agent, a leveling agent and a solvent to obtain a functional solvent;
mixing polyolefin polyol, non-aromatic isocyanate, a curing agent and a catalyst with the functional solvent to obtain a reaction solution;
and (3) reacting the reaction liquid under a sealing condition to obtain the high-transparency polyurethane wear-resistant paint.
In the invention, the reaction temperature is 20-70 ℃ and the reaction time is 0.5-78 h under the sealed condition.
The invention provides a high-transparency polyurethane wear-resistant coating, which is prepared by coating the high-transparency polyurethane wear-resistant paint in the technical scheme and performing ozone treatment after curing.
In the invention, the curing temperature is 20-120 ℃, and the curing time is 6-48 h;
the concentration of ozone in the ozone treatment is 5-200 pphm; the ozone treatment time is 5-200 h.
The invention provides application of the high-transparency polyurethane wear-resistant coating on the surface of a protection part in the technical scheme;
the protection part comprises train glass, automobile glass, aircraft windows, aircraft cabins or precise instruments.
The invention provides a high-transparency polyurethane wear-resistant paint which comprises the following raw materials in parts by mass: 60 parts of polyolefin polyol, 25-65 parts of non-aromatic isocyanate, 1-20 parts of curing agent, 0-2 parts of catalyst, 0.5-3 parts of ultraviolet absorber, 0-1 part of wetting agent, 0.1-1 part of leveling agent and 100-500 parts of solvent. According to the invention, the polyolefin polyol is adopted to ensure that unsaturated double bonds exist in polyurethane molecular chains, so that the double bonds in the molecular structure of the coating are oxidized into aldehyde groups after ozone treatment, and the newly formed aldehyde groups can form hydrogen bonds with carbamate groups of polyurethane, so that the wear resistance of the coating is improved; the non-aromatic isocyanate and the micromolecular polyol curing agent ensure that the polyurethane molecular chain has no benzene ring structure, so that the light transmittance of the coating in the visible light range is more than 95%; the ultraviolet absorber, wetting agent and leveling agent ensure that the coating can be attached to a substrate while having excellent weatherability. The high-transparency polyurethane wear-resistant paint provided by the invention has the advantages of simple preparation method and mild conditions; the prepared coating has high transparency and sand erosion abrasion resistance, has excellent weather resistance and good substrate adhesion, can be used for train and automobile glass, aircraft windows and cabin covers, precise instrument surfaces and the like, and prolongs the service life. The experimental results show that: the haze of the coating before friction is 0.14-1.26, and the haze after friction is 0.99-2.96.
Drawings
FIG. 1 shows a highly transparent polyurethane abrasion-resistant coating prepared in application example 1 of the present invention.
Detailed Description
The invention provides a high-transparency polyurethane wear-resistant paint which comprises the following raw materials in parts by mass:
60 parts of polyolefin polyol, 25-65 parts of non-aromatic isocyanate, 1-20 parts of curing agent, 0-2 parts of catalyst, 0.5-3 parts of ultraviolet absorber, 0-1 part of wetting agent, 0.1-1 part of leveling agent and 100-500 parts of solvent.
The preparation raw materials of the high-transparency polyurethane wear-resistant paint provided by the invention comprise 60 parts of polyolefin polyol, and in the specific embodiment of the invention, the dosage of the polyolefin polyol is 60 parts; the polyolefin polyol is selected from hydroxyl-terminated polybutadiene and/or hydroxyl-terminated epoxidized polybutadiene resin, preferably hydroxyl-terminated polybutadiene; the polyolefin polyol has a number average molecular weight of 2000 to 5000, preferably 2000 to 3500. In specific embodiments, the polyolefin polyol is a hydroxyl-terminated polybutadiene with a number average molecular weight of 4000, a hydroxyl-terminated polybutadiene with a number average molecular weight of 2660, a hydroxyl-terminated epoxidized polybutadiene with a number average molecular weight of 4000, or a hydroxyl-terminated polybutadiene with a number average molecular weight of 3500.
The high-transparency polyurethane wear-resistant paint provided by the invention is prepared from 25-65 parts of non-aromatic isocyanate, wherein in the specific embodiment of the invention, the dosage of the non-aromatic isocyanate is 31.5 parts, 53.5 parts, 63.7 parts, 33.2 parts or 45.9 parts; the non-aromatic isocyanate is selected from one or more of isophorone diisocyanate, dicyclohexylmethane diisocyanate, trimethyl-1, 6-hexamethylene diisocyanate, methylcyclohexyl diisocyanate, cyclohexanedimethylene diisocyanate trimer, hexamethylene diisocyanate biuret and isophorone diisocyanate trimer, preferably from one or more of isophorone diisocyanate, dicyclohexylmethane diisocyanate, trimethyl-1, 6-hexamethylene diisocyanate trimer and isophorone diisocyanate trimer, more preferably from one or more of isophorone diisocyanate, trimethyl-1, 6-hexamethylene diisocyanate trimer and isophorone diisocyanate trimer.
The preparation raw materials of the high-transparency polyurethane wear-resistant paint provided by the invention comprise 1-20 parts of curing agent, preferably 5-15 parts; the curing agent is small molecular dihydric alcohol. The curing agent is preferably one or more selected from the group consisting of 1, 2-propanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 2-pentanediol, neopentyl glycol, 2-methyl-2, 4-pentanediol, 1, 2-hexanediol, 1, 2-octanediol and 1, 2-decanediol, more preferably one or more selected from the group consisting of 1, 4-butanediol, 1, 2-hexanediol, 1, 2-octanediol, 1, 2-decanediol and 1, 3-butanediol. In specific embodiments, the curing agent is 1, 4-butanediol, or a mixture of 1, 2-hexanediol, 1, 2-octanediol and 1, 2-sunflower glycol in a mass ratio of 4.8:0.5:0.9; or a mixture of 1, 3-butanediol and 1, 4-butanediol in a mass ratio of 2.1:0.9; or 1, 3-propanediol.
The preparation raw materials of the high-transparency polyurethane wear-resistant paint provided by the invention comprise 0-2 parts of catalyst, preferably 0.5-1.5 parts; the catalyst is selected from one or more of bismuth isooctanoate, potassium isooctanoate, stannous octoate, dibutyl tin dilaurate, triethylene diamine, 1, 8-diazabicyclo [5.4.0] undec-7-ene, 1, 4-dimethylpiperazine, triethylene diamine, bis (dimethylaminoethyl) ether, dimethylcyclohexylamine and pentamethyldiethylenetriamine, preferably stannous octoate and/or dibutyl tin dilaurate.
The high-transparency polyurethane wear-resistant paint provided by the invention is prepared from 0.5-3 parts of ultraviolet absorbent. In particular embodiments, the ultraviolet light absorber is selected from one or more of UV1CAS57834-33-0, UV-326, UV-9, and UV-921.
The high-transparency polyurethane wear-resistant paint provided by the invention comprises 0-1 part of wetting agent. In particular embodiments, the wetting agent is selected from one or more of GS-2565, BYK306, WSS-760 and WSS-4000.
The preparation raw materials of the high-transparency polyurethane wear-resistant paint provided by the invention comprise 0.1-1 part of flatting agent. In a specific embodiment, the leveling agent is selected from one or more of ZY-1603, GS-1165, KLE-500, RESIFLOW L-65F-50 and KLE-4365.
The high-transparency polyurethane wear-resistant paint provided by the invention is prepared from 100-500 parts of solvent, wherein the solvent is preferably one or more of toluene, 1, 4-dioxane, cyclohexanone, tetrahydrofuran, butyl acetate and xylene. In a specific embodiment, the solvent is a mixture of toluene, 1, 4-dioxane and cyclohexanone in a mass ratio of 30:25:45; or a mixture of toluene and tetrahydrofuran in a mass ratio of 60:40; or butyl acetate, xylene and cyclohexanone in a mass ratio of 15:40:45; or a mixture of dimethylformamide and toluene in a mass ratio of 75:25; or propylene glycol methyl ether acetate.
The invention provides a preparation method of the high-transparency polyurethane wear-resistant paint, which comprises the following steps:
uniformly mixing an ultraviolet absorbent, a wetting agent, a leveling agent and a solvent to obtain a functional solvent;
mixing polyolefin polyol, non-aromatic isocyanate, a curing agent and a catalyst with the functional solvent to obtain a reaction solution;
and (3) reacting the reaction liquid under a sealing condition to obtain the high-transparency polyurethane wear-resistant paint.
In the preparation process of the reaction liquid, the polyolefin polyol, the non-aromatic isocyanate and the curing agent are preferably added into the functional solvent respectively, and the catalyst is added after the mixture is stirred uniformly.
In the invention, the reaction temperature of the reaction liquid under the sealing condition is 20-70 ℃ and the reaction time is 0.5-78 h. The reaction is preferably carried out under stirring. And after the reaction is finished, standing at room temperature for defoaming, and filtering to obtain the high-transparency polyurethane wear-resistant paint.
The invention provides a high-transparency polyurethane wear-resistant coating, which is prepared by coating the high-transparency polyurethane wear-resistant paint in the technical scheme and performing ozone treatment after curing.
In the invention, the coating prepared by the high-transparency polyurethane wear-resistant paint needs ozone treatment, so that unsaturated olefin groups derived from polyalcohol in a polyurethane molecular structure can be oxidized into aldehyde groups, the newly formed aldehyde groups can form hydrogen bonds with carbamate groups, the mechanical property of the material is improved, and the sand erosion and wear resistance of the coating is further improved.
In the present invention, the curing temperature is 20 to 120 ℃, preferably 70 to 100 ℃; the curing time is 6 to 48 hours, preferably 24 to 36 hours; the spatial cleanliness of the curing is higher than the level of hundred thousand, preferably higher than the level of hundred thousand. The high cleanliness is maintained during curing, and the coating can be prevented from falling into dust when being coated on a substrate material, so that the light transmittance is affected.
The ozone concentration of the ozone treatment is 5 to 200pphm, preferably 20 to 100pphm; the ozone treatment time is 5 to 200 hours, preferably 40 to 100 hours.
The invention provides application of the high-transparency polyurethane wear-resistant coating on the surface of a protection part in the technical scheme;
the protection part comprises train glass, automobile glass, aircraft windows, aircraft cabins or precise instruments.
In order to further illustrate the present invention, the following examples are provided to describe in detail a highly transparent polyurethane abrasion resistant paint, a method for preparing the same and its use, but they should not be construed as limiting the scope of the present invention.
Example 1
Toluene, 1, 4-dioxane and cyclohexanone are prepared into a solvent according to the mass ratio of 30:25:45, and then 0.8g of ultraviolet absorber (UV 1CAS57834-33-0, qingda Daida chemical engineering limited public), 0.8g of wetting agent (GS-2565, GS chemical) and 0.8g of flatting agent (KLE-4365 flatting agent, guangzhou, europe chemical new material Co., ltd.) are added into 250g of solvent, and the mixture is stirred uniformly to prepare the functional solvent. To 250g of the above functional solvent were added 60g of hydroxyl-terminated polybutadiene (number average molecular weight: 4000), 31.5g of isophorone diisocyanate and 10.6g of 1, 4-butanediol, and 0.5g of stannous octoate was added to prepare a reaction solution. And (3) sealing and stirring the reaction liquid at 30 ℃ for reaction for 8 hours, standing at room temperature for defoaming, and filtering to obtain the high-transparency polyurethane wear-resistant paint.
Example 2
Toluene and tetrahydrofuran were prepared into a solvent at a mass ratio of 60:40, and then 0.5g of an ultraviolet absorber (UV 1CAS57834-33-0, tsingtao Dedazhi chemical Co., ltd.), 0.3g of a wetting agent (BYK 306, pick Germany) and 0.4g of a leveling agent (RESIFLOW L-65F-50, estren) were added to 200g of the solvent, followed by stirring to prepare a functional solvent. To 200g of the above functional solvent were added 60g of hydroxyl-terminated polybutadiene (number average molecular weight: 4000), 53.5g of isophorone diisocyanate trimer and 2.7g of 1, 3-propanediol, and 0.3g of dibutyltin dilaurate was added to prepare a reaction solution. And (3) sealing and stirring the reaction liquid at 50 ℃ for reaction for 1h, standing at room temperature for defoaming and filtering to obtain the high-transparency polyurethane wear-resistant paint.
Example 3
Butyl acetate, dimethylbenzene and cyclohexanone are prepared into a solvent according to a mass ratio of 15:40:45, 1g of ultraviolet absorber (UV-326, nanjing Milan chemical industry Co., ltd.) and 1.5g of flatting agent (KLE-500 flatting agent, guangzhou Europe Chen Qi chemical new material Co., ltd.) are added into 400g of solvent, and the mixture is stirred uniformly to prepare the functional solvent. 60g of hydroxyl-terminated polybutadiene (number average molecular weight: 2660), 55.2g of isophorone diisocyanate trimer and 8.5g of hexamethylene diisocyanate trimer, 2.1g of 1, 3-butanediol and 0.9g of 1, 4-butanediol were added to 400g of the above-mentioned functional solvent, and 1.5g of triethylene diamine was added to prepare a reaction solution. And (3) sealing and stirring the reaction liquid at 20 ℃ for reaction for 16 hours, standing at room temperature for defoaming, and filtering to obtain the high-transparency polyurethane wear-resistant paint.
Example 4
Preparing solvent from dimethylformamide and toluene at a mass ratio of 75:25, adding 0.5g of ultraviolet absorber (UV-9, nanjing Milan chemical Co., ltd.), 1.0g of wetting agent (WSS-760, new Penta Material (Hangzhou Co., ltd.), and 0.2g of leveling agent (GS-1165, GS chemical) into 300g of solvent, and stirring to obtain functional solvent. To 300g of the above functional solvent were added 60g of hydroxyl-terminated epoxidized polybutadiene (number average molecular weight: 4000), 33.2g of trimethyl-1, 6-hexamethylene diisocyanate, 4.8g of 1, 2-hexanediol, 0.5g of 1, 2-octanediol and 0.9g of 1, 2-sunflower glycol, and 0.3g of dibutyltin dilaurate and 0.3g of stannous octoate were added to prepare a reaction solution. And (3) sealing and stirring the reaction liquid at 20 ℃ for reaction for 8 hours, standing at room temperature for defoaming, and filtering to obtain the high-transparency polyurethane wear-resistant paint.
Example 5
2g of an ultraviolet absorber (UV-921, guangzhou God New Material technology Co., ltd.), 0.6g of a wetting agent (WSS-4000, WU.S. Chemicals Co., ltd.) and 0.4g of a leveling agent (ZY-1603, shanghai catalpa chemical Co., ltd.) were added to 100g of propylene glycol methyl ether acetate solvent, and stirred uniformly to prepare a functional solvent. To 100g of the above functional solvent were added 60g of hydroxyl-terminated polybutadiene (number average molecular weight: 3500), 45.9g of isophorone diisocyanate trimer, and 11.9g of 1, 4-butanediol, and 0.2g of bismuth isooctanoate was added to prepare a reaction solution. And (3) sealing and stirring the reaction liquid at 40 ℃ for reaction for 24 hours, standing at room temperature for defoaming, and filtering to obtain the high-transparency polyurethane wear-resistant paint.
The above examples are formulated as highly transparent polyurethane abrasion resistant paints and the preferred highly transparent polyurethane abrasion resistant coating embodiments of the present invention are described below in connection with the application examples, but it should be understood that these descriptions are merely to further illustrate the features and advantages of the present invention and are not limiting on the claims of the present invention.
Application example 1
In a hundred thousand-level clean space, a clean organic glass plate is erected at 30 degrees, and the high-transparency polyurethane wear-resistant paint prepared in the example 1 is coated from left to right from the upper end. The coated substrate was placed in an oven at 70 ℃ for 24 hours and then treated with ozone at a concentration of 50pphm for 50 hours. The coating was tested for light transmittance, abrasion resistance, weatherability and substrate adhesion and the results are shown in table 1.
Application example 2
In a hundred thousand-level clean space, a clean glass plate is erected at 30 degrees, and the high-transparency polyurethane wear-resistant paint prepared in example 1 is coated from left to right from the upper end. The coated substrate was placed in an oven at 70 ℃ for 24 hours and then treated with ozone at a concentration of 50pphm for 50 hours. The coating was tested for light transmittance, abrasion resistance, weatherability and substrate adhesion and the results are shown in table 1.
Application example 3
In a hundred thousand-level clean space, a clean organic glass plate is erected at 30 degrees, and the high-transparency polyurethane wear-resistant paint prepared in the example 1 is coated from left to right from the upper end. The coated substrate was placed in an oven at 70 ℃ for 24 hours and then treated with ozone at a concentration of 25pphm for 80 hours. The coating was tested for light transmittance, abrasion resistance, weatherability and substrate adhesion and the results are shown in table 1.
Application example 4
In a hundred thousand-level clean space, a clean glass plate is placed on a spin coater, a sufficient amount of the high-transparency polyurethane wear-resistant paint prepared in the example 2 is added in the middle, and spin coating is carried out at 300 rpm/20 s. The coated substrate was placed in an 80 ℃ oven for 18 hours and then treated with ozone at a concentration of 40pphm for 60 hours. The coating was tested for light transmittance, abrasion resistance, weatherability and substrate adhesion and the results are shown in table 1.
Application example 5
In a hundred thousand-level clean space, a clean glass plate is vertically clamped and immersed in the high-transparency polyurethane wear-resistant paint prepared in example 3. The coated substrate was placed in an oven at 50 ℃ for 40 hours and then treated with ozone at a concentration of 30pphm for 110 hours. The coating was tested for light transmittance, abrasion resistance, weatherability and substrate adhesion and the results are shown in table 1.
Application example 6
The high-transparency polyurethane abrasion-resistant paint prepared in example 4 was applied to a vertically erected clean glass panel in a hundred thousand grade clean space using a spray coater. The coated substrate was placed in an oven at 70 ℃ for 24 hours and then treated with ozone at a concentration of 70pphm for 30 hours. The coating was tested for light transmittance, abrasion resistance, weatherability and substrate adhesion and the results are shown in table 1.
Application example 7
In a hundred thousand-level clean space, clean glass plates are erected at 30 degrees, and the high-transparency polyurethane wear-resistant paint prepared in example 5 is coated from left to right from the upper end. The coated substrate was placed in an oven at 70 ℃ for 24 hours and then treated with ozone at a concentration of 10pphm for 200 hours. The coating was tested for light transmittance, abrasion resistance, weatherability and substrate adhesion and the results are shown in table 1.
The key steps of the preparation of the high-transparency polyurethane wear-resistant paint and the coating thereof are hydroxyl-terminated polybutadiene polyol serving as a raw material of the wear-resistant paint and the preparation of the coating, namely ozone treatment, wherein unsaturated double bonds (provided by the hydroxyl-terminated polybutadiene polyol) in a polyurethane molecular chain are oxidized into aldehyde groups by ozone, and the newly formed aldehyde groups can form hydrogen bonds with carbamate groups, so that the wear resistance of the coating is improved. To illustrate that hydroxyl-terminated polybutadiene polyol and ozone treatment are critical to the preparation of the highly transparent polyurethane abrasion resistant paint and its coating according to the present invention, a comparison is provided.
Comparative example 1
Toluene, 1, 4-dioxane and cyclohexanone are prepared into a solvent according to the mass ratio of 30:25:45, 0.8g of wetting agent (GS-2565, GS chemical) and 0.8g of flatting agent (KLE-4365 flatting agent, guangzhou, europe and Chemie new material Co., ltd.) are added into 250g of the solvent, and the mixture is stirred uniformly to prepare a functional solvent. 60g of polytetrahydrofuran diol (number average molecular weight: 3000), 31.8g of isophorone diisocyanate and 10.0g of 1, 4-butanediol were added to 250g of the above functional solvent, and 0.5g of stannous octoate was added to prepare a reaction solution. And (3) sealing and stirring the reaction liquid at 30 ℃ for reaction for 5 hours, standing at room temperature for defoaming, and filtering to obtain the high-transparency polyurethane wear-resistant paint.
Comparative example 1 was used
In a hundred thousand-level clean space, a clean organic glass plate is erected at 30 degrees, and the high-transparency polyurethane wear-resistant paint prepared in the example 1 is coated from left to right from the upper end. The coated substrate was placed in an oven at 70 ℃ for 24 hours of curing without any treatment with ozone. The coating was tested for light transmittance, abrasion resistance, weatherability and substrate adhesion and the results are shown in table 2.
Comparative example 2 was used
In a hundred thousand-level clean space, a clean organic glass plate is erected at 30 degrees, and the high-transparency polyurethane wear-resistant paint prepared in comparative example 1 is coated from left to right from the upper end. The coated substrate was placed in an oven at 70 ℃ for 24 hours and then treated with ozone at a concentration of 50pphm for 50 hours. The coating was tested for light transmittance, abrasion resistance, weatherability and substrate adhesion and the results are shown in table 2.
The coatings prepared in application examples 1 to 7 and comparative examples 1 to 2 were tested for light transmittance, abrasion resistance, weather resistance and adhesion to a substrate. Light transmittance test: and testing the light transmittance in the wavelength range of 400-800 nm by adopting an ultraviolet-visible-near infrared spectrophotometer. Abrasion resistance test: the test is carried out by adopting a Taber vibration abrasion instrument, specifically, 900g of standard sand with the particle size of 3mm is placed into the abrasion instrument, and a single sample is subjected to a reciprocating test for 100 cycles by 16 cm. Meanwhile, the haze of the coating before and after the abrasion resistance test is tested by using an ultraviolet-visible-near infrared spectrophotometer. The change value of the haze before and after the abrasion resistance test is used for representing the abrasion resistance of the coating, and the smaller the change value of the haze is, the more abrasion resistance of the coating is indicated. Weather resistance test: reference is made to the high temperature test, low temperature test, damp heat test and mold test in the GJB150 standard. The coating is subjected to wear resistance test after high temperature test, low temperature test and wet heat test, and the haze of the coating after the wear resistance test is recorded. Meanwhile, a haze change value (haze value change=haze after high temperature/low temperature/wet heat test—haze after friction) was calculated, and the smaller the haze change value, the better the weather resistance of the coating was demonstrated. The mold test adopts strain group 2 in the standard, and the evaluation of the results adopts appearance influence evaluation, and the lower the grade is, the better the weather resistance of the coating is. Substrate adhesion test: the method is carried out by referring to the standard of ASTM D3359, specifically, a hundred sheets are cut on the surface of a coating by using a hundred sheet scraper with the lattice spacing of 1mm multiplied by 1mm, then a 3M600 test adhesive tape is used for adhering the coating with the hundred sheets cut, and finally the adhesive tape is torn and the peeling degree of the cut of the hundred sheets of the coating is observed.
TABLE 1 comparison of the Properties of the coatings of application examples 1 to 7
Table 2 comparison of the properties of the coatings of application example 1 and application comparative examples 1 to 2
Application example 1 Comparative example 1 was used Comparative example 2 was used
Transmittance of light,% 99.3～97.9 99.7～96.2 99.1～96.9
Haze before rubbing 0.38 0.69 0.81
Haze after rubbing 1.54 32.40 25.83
Haze change value after rubbing 1.16 31.71 25.02
Haze after high temperature test 3.21 78.81 46.87
Haze change value after high temperature test 1.67 46.41 21.04
Haze after low temperature test 2.08 62.29 43.58
Haze change value after low temperature test 0.54 29.89 17.75
Haze after damp heat test 3.63 90.00 57.47
Haze change value after damp heat test 2.09 57.60 31.64
Appearance influence rating of mold test 1 3 1
Adhesion to substrate 5B 5B 4B
The results show that the coatings prepared in application examples 1-7 all have extremely high light transmittance, excellent wear resistance and weather resistance, and good adhesion to the substrate. When the coating of application example 1 was not subjected to ozone treatment (i.e., application comparative example 1), although the light transmittance and substrate adhesion were not substantially changed, abrasion resistance was significantly reduced, and particularly abrasion resistance was significantly reduced after the weathering test, indicating that ozone treatment was critical for the preparation of hydroxyl-terminated polybutadiene-polyurethane abrasion resistant coatings. When the coating of application example 1 was not prepared using the abrasion resistant paint of example 1 (i.e., using comparative example 2), the abrasion resistance and weather resistance of the coating remained unsatisfactory even though the coating was subjected to ozone treatment, indicating that another key factor in ozone treatment of the coating was hydroxyl-terminated polybutadiene in the polyurethane abrasion resistant paint.
As can be seen from the above examples, the invention provides a high-transparency polyurethane wear-resistant paint, which comprises the following raw materials in parts by mass: 60 parts of polyolefin polyol, 25-65 parts of non-aromatic isocyanate, 1-20 parts of curing agent, 0-2 parts of catalyst, 0.5-3 parts of ultraviolet absorber, 0-1 part of wetting agent, 0.1-1 part of leveling agent and 100-500 parts of solvent. According to the invention, the polyolefin polyol is adopted to ensure that unsaturated double bonds exist in polyurethane molecular chains, so that the double bonds in the molecular structure of the coating are oxidized into aldehyde groups after ozone treatment, and the newly formed aldehyde groups can form hydrogen bonds with carbamate groups of polyurethane, so that the wear resistance of the coating is improved; the non-aromatic isocyanate and the micromolecular polyol curing agent ensure that the polyurethane molecular chain has no benzene ring structure, so that the light transmittance of the coating in the visible light range is more than 95%; the ultraviolet absorber, wetting agent and leveling agent ensure that the coating can be attached to a substrate while having excellent weatherability. The high-transparency polyurethane wear-resistant paint provided by the invention has the advantages of simple preparation method and mild conditions; the prepared coating has high transparency and sand erosion abrasion resistance, has excellent weather resistance and good substrate adhesion, can be used for train and automobile glass, aircraft windows and cabin covers, precise instrument surfaces and the like, and prolongs the service life.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (8)

1. The high-transparency polyurethane wear-resistant coating is prepared by coating high-transparency polyurethane wear-resistant paint and performing ozone treatment after curing;
the high-transparency polyurethane wear-resistant paint comprises the following raw materials in parts by mass:
60 parts of polyolefin polyol, 25-65 parts of non-aromatic isocyanate, 1-20 parts of curing agent, 0-2 parts of catalyst, 0.5-3 parts of ultraviolet absorber, 0-1 part of wetting agent, 0.1-1 part of leveling agent and 100-500 parts of solvent;
the polyolefin polyol is hydroxyl-terminated polybutadiene and/or hydroxyl-terminated epoxidized polybutadiene resin.
2. The high transparent polyurethane wear resistant coating according to claim 1, wherein the polyolefin polyol has a number average molecular weight of 2000 to 5000.
3. The highly transparent polyurethane abrasion resistant coating according to claim 1, wherein said non-aromatic isocyanate is one or more of isophorone diisocyanate, dicyclohexylmethane diisocyanate, trimethyl-1, 6-hexamethylene diisocyanate, methylcyclohexyl diisocyanate, cyclohexanedimethylene diisocyanate, hexamethylene diisocyanate trimer, hexamethylene diisocyanate biuret and isophorone diisocyanate trimer.
4. The high transparent polyurethane wear resistant coating according to claim 1, wherein the curing agent is selected from one or more of 1, 2-propanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 2-pentanediol, neopentyl glycol, 2-methyl-2, 4-pentanediol, 1, 2-hexanediol, 1, 2-octanediol, and 1, 2-decanediol.
5. The high-transparency polyurethane wear-resistant coating according to claim 1, wherein the preparation method of the high-transparency polyurethane wear-resistant paint comprises the following steps:
uniformly mixing an ultraviolet absorbent, a wetting agent, a leveling agent and a solvent to obtain a functional solvent;
mixing polyolefin polyol, non-aromatic isocyanate, a curing agent and a catalyst with the functional solvent to obtain a reaction solution;
and (3) reacting the reaction liquid under a sealing condition to obtain the high-transparency polyurethane wear-resistant paint.
6. The high-transparency wear-resistant polyurethane coating according to claim 5, wherein the reaction temperature is 20-70 ℃ and the reaction time is 0.5-78 h under the sealing condition.
7. The high-transparency polyurethane wear-resistant coating according to claim 1, wherein the curing temperature is 20-120 ℃ and the curing time is 6-48 h;
the concentration of ozone in the ozone treatment is 5-200 pphm; the ozone treatment time is 5-200 hours.
8. Use of the highly transparent polyurethane abrasion resistant coating of claim 1 on a surface of a protective area;
the protection part comprises train glass, automobile glass, aircraft windows, aircraft cabins or precise instruments.
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