CN110628311A - Preparation method of polyurethane-based transparent antifouling coating - Google Patents
Preparation method of polyurethane-based transparent antifouling coating Download PDFInfo
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- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/02—Esters
- C08B31/04—Esters of organic acids, e.g. alkenyl-succinated starch
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- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
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- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- 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
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
- C09D5/1675—Polyorganosiloxane-containing compositions
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Abstract
The invention discloses a preparation method of a polyurethane-based transparent antifouling coating. The method takes natural macromolecules with hydroxyl groups as raw materials, and prepares an acylated natural macromolecular compound by chemical modification; then, the residual hydroxyl of the acylation product is used as polyhydric alcohol, polyisocyanate compound is used as a cross-linking agent, a small amount of polyorganosiloxane with terminal hydroxyl is used as a functional component, and the polyurethane-based transparent antifouling coating with the light transmittance (T) of more than 95 percent and the thickness of 30-40 mu m is prepared through cross-linking reaction. The prepared coating has excellent performances of high transparency, thermal stability, corrosion resistance, degradability, high surface hardness and the like, is very easy to shrink when marking liquid pollutants such as printing ink, paint and the like, is repeatedly wiped without leaving traces, and has good antifouling performance. A lower sliding angle can be obtained for most test fluids. In addition, the functional surface can be prepared on various surfaces of wood, metal, cotton fiber and the like, and has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of preparation of antifouling surface materials, and particularly relates to a preparation method of a polyurethane-based transparent antifouling coating.
Background
"smart" surfaces, such as self-cleaning windows, oil-resistant dining tables, anti-fouling automotive windshields and rearview mirrors, graffiti barrier walls and other anti-fouling coatings, can repel water and oil-contaminated contaminants, helping to clean and beautify our world. At present, three methods can be mainly used for constructing an anti-fouling surface to endow the surface of the material with excellent amphiphobicity: 1) forming a rough surface with a micro-nano structure by various processing methods, and performing hydrophobic modification treatment on the surface; 2) constructing a porous layer and then infusing a low surface energy liquid therein to form a liquid infused porous surface; 3) and (3) carrying out graft modification on the surface by using a polymer with low surface energy to form the polymer brush. While the contact angle of water or simulated oil (hexadecane) on the surface of such a polymer brush is not high enough to fall into the ultra-hydrophobic category, the sliding angle is very low, i.e. water or oil can easily slide on the surface without leaving a clear trace, and such experiments are also commonly used to explain the anti-fouling performance of the material surface. Although the surface treatment methods can realize the anti-fouling performance of the material surface, the preparation process is relatively complicated, and most systems use fluorine-containing substances or polymers, so the cost is high; moreover, the light transmittance of the material is usually sacrificed; in addition, the durability of the anti-fouling property is poor due to the fact that the surface is easy to wear and consume, and the like, so that the daily life of people from a laboratory to the anti-fouling surface is greatly limited.
Disclosure of Invention
In order to solve the problems of pollution resistance, light transmittance and durability of surface materials, and the problems of cost, process and environment in the preparation process, the invention provides a construction method of a biodegradable polyurethane-based transparent antifouling coating with low cost and simple and convenient process. Firstly, dissolving a small amount of polyorganosiloxane with terminal hydroxyl and enough polyisocyanate compound in an organic solvent to perform a first pre-reaction, so that PDMS-OH is grafted to the polyisocyanate compound as completely as possible, and avoiding the macroscopic phase separation and optical problems of a final coating caused by free PDMS; then, natural polymers are acylated and modified to prepare an acylated natural polymer compound with a certain degree of substitution and good solubility in organic solvents such as butanone, dimethyl carbonate (DMC), N-Dimethylformamide (DMF), acetone, chloroform and the like; and then, taking the acylated product as polyol, a polyisocyanate compound as a cross-linking agent and a small amount of polyorganosiloxane with terminal hydroxyl as a functional component to prepare the polyurethane-based transparent antifouling coating with the light transmittance (T) of more than 95 percent and the thickness of 30-40 mu m.
The preparation method of the polyurethane-based transparent antifouling coating comprises the following steps:
1) dissolving polyorganosiloxane with terminal hydroxyl and polyisocyanate compound in an organic solvent for carrying out a first pre-reaction;
2) carrying out acylation modification on the natural polymer with hydroxyl to obtain an acylated natural polymer;
3) and dissolving the acylated natural polymer by using an organic solvent, then adding the dissolved acylated natural polymer into a system which completes the first pre-reaction to perform a second pre-crosslinking reaction, and finally performing film coating and curing to obtain the polyurethane-based transparent antifouling coating.
The specific reaction conditions of the step 1) are as follows: taking polyorganosiloxane with terminal hydroxyl as a functional component, taking a polyisocyanate compound as a crosslinking agent, and carrying out a first pre-reaction in an organic solvent, wherein the temperature is set to be 25-80 ℃ and the reaction time is 3-72 h.
The weight average molecular weight Mw of the polyorganosiloxane with the terminal hydroxyl is 1000-10000, and the adding amount is 0.2-3.5 wt% of the total raw material amount.
The polyisocyanate compound is a compound having two or more isocyanate groups. Specifically one or more selected from isophorone diisocyanate and its trimer, hexamethylene diisocyanate and its trimer, triphenylmethane triisocyanate and biuret.
The organic solvent in the step 1) is a good solvent of polyorganosiloxane with terminal hydroxyl, specifically one or more selected from butanone, isopropanol, acetone and n-hexane, and the addition amount is 85-95 wt% of the total raw material amount.
The acylation modification method adopted in the step 2) is a solvent method, a water-coal method or a high-temperature high-pressure method; the acylation amount of the obtained acylated natural polymer is 60-90%.
The specific reaction conditions of the step 2) are as follows: activating natural polymer with hydroxyl in solvent, slowly adding acylating agent and catalyst, reacting at 60-80 deg.C for 3-36 hr, washing with deionized water, filtering, and drying to obtain acylated natural polymer.
The natural polymer with hydroxyl is a bio-based polymer with hydroxyl. Specifically selected from one or more of starch, cyclodextrin, cellulose, lignin, chitosan, chitin, and oligosaccharide.
The solvent in the step 2) is selected from one or more of glacial acetic acid, N-Dimethylformamide (DMF) and pyridine; the acylating reagent is one or more of carboxylic acid, carboxylic ester, acid anhydride, acyl chloride and ketene; the catalyst is organic acid.
The specific reaction conditions of the step 3) are as follows: dissolving the acylated natural polymer by using an organic solvent, adding the dissolved acylated natural polymer into a system which finishes the first pre-reaction, diluting the obtained mixed solution by using the solvent, then carrying out the second pre-crosslinking reaction for 3-8h at 60-80 ℃, filtering the obtained product by using a microporous filter membrane after the reaction is finished, coating the obtained product, and finally curing the obtained product at the temperature of 100 ℃ and 150 ℃ to obtain the polyurethane-based transparent antifouling coating.
The molar ratio of-OH of the acylated natural polymer to-NCO of the polyisocyanate compound in the step 3) is 1:1-1: 1.5.
The organic solvent for dissolving the acylated natural polymer in the step 3) is one or more of butanone, DMC and DMF, the solvent for diluting the mixed solution is DMC and/or DMF, and the dilution multiple is 2-5 times of volume.
The film forming method in the step 3) may be a solvent evaporation film forming method, a hot melt film forming method, or a chemical film forming method.
In order to solve the problems of dirt resistance, light transmittance and durability of the surface of a material at the same time, in the preparation process of polyurethane, the low-molecular-weight liquid polyorganosiloxane is chemically bonded to form a polymer brush, the low-surface-energy polyorganosiloxane endows the surface of the material with dirt resistance, and the use of fluorine-containing compounds is avoided; the chemically bonded liquid polymer forms nano micro-domains through microphase separation, and when the surface of the material is abraded by external force, a new polymer brush can be formed, so that the self-replenishment function is realized, the durability is improved, and meanwhile, the light transmittance of the surface material is endowed. In addition, the polyurethane-based transparent antifouling coating can be prepared by reacting the polyisocyanate with the natural high polymer material polyol which is cheap and easily available and has biodegradability, biocompatibility, nontoxicity and high reactivity, and the process is simple and convenient and has low cost.
The light transmittance (T) of the polyurethane-based transparent antifouling coating prepared by the method is more than 95%, and the thickness of the coating is 30-40 mu m. The preparation process provided by the invention is simple and convenient, the functional component PDMS introduced into the system is simple and flexible, the molecular weight and the dosage are easy to regulate and control, the raw materials are cheap and easy to obtain, and the preparation method has the advantages of biodegradability, biocompatibility, nontoxicity, high reactivity and the like. The prepared polyurethane-based transparent antifouling coating has excellent performances of high transparency, thermal stability, corrosion resistance, degradability, high surface hardness and the like, is very easy to shrink when marking liquid pollutants such as printing ink, paint and the like, is repeatedly wiped without leaving marks, and has good antifouling performance. For most test fluids, such as water, hexadecane, diiodomethane, tetrahydrofuran, ethanol, etc., lower sliding angles can be obtained. In addition, the intelligent surface can be prepared on various surfaces of wood, metal, cotton fiber and the like, and has wide application prospect.
Detailed Description
In order to make the technical solution of the present invention better understood by those skilled in the art, the following will describe in detail a method for preparing a polyurethane-based transparent antifouling coating layer provided by the present invention with reference to the following examples.
Firstly, adding amylose into a three-necked bottle, adding glacial acetic acid, stirring for 5min, adding acetic anhydride, stirring for 15min, adding a methanesulfonic acid catalyst, and reacting for 3h at 75 ℃. After the reaction is finished, the reactant is moved into a constant pressure funnel, slowly dripped into the stirred deionized water for washing, after the dripping is finished, vacuum filtration is started, the deionized water is used for leaching, and the acetic acid is washed off to be neutral. And finally drying the obtained product at 60 ℃ for 3h to obtain the acetylated starch.
The preparation method of the polyurethane-based transparent antifouling coating comprises the following steps: polydimethylsiloxane (PDMS-OH) and hexamethylene diisocyanate trimer (HDIT) are accurately weighed and placed into a 3mL transparent glass bottle, butanone is added, the mixture is shaken and dissolved, and the mixture is placed into a 75 ℃ oven for primary pre-reaction. And accurately weighing acetylated starch to be dissolved in DMF, adding the acetylated starch into a first pre-reaction system after the first pre-reaction is finished, diluting the obtained mixed solution with an organic solvent, and carrying out a second pre-crosslinking reaction for 4 hours at 75 ℃. And finally, filtering by using a 0.45-micrometer microporous filter membrane, sucking 0.4mL of filtrate by using an injector, coating a film on the treated glass slide, immediately sealing the system by using a preservative film after the film coating is finished, reserving a small hole to slowly volatilize the solvent for 60-90min, then increasing airflow for 10-15min to volatilize the residual low-boiling-point solvent, and finally placing the glass slide into a 120-DEG C oven for high-temperature curing for 15 h.
Example 1
Preparation of acetylated starch: accurately weighing 5g of amylose, adding the amylose into a three-necked bottle, adding 10.79g of glacial acetic acid, stirring for 5min, adding 9.45g of acetic anhydride, stirring for 15min, adding 0.18g of methanesulfonic acid catalyst, and reacting for 24h at 75 ℃. After the reaction is finished, the reactant is moved into a constant pressure funnel, slowly dripped into the stirred deionized water for washing, after the dripping is finished, vacuum filtration is started, the deionized water is used for leaching, and the acetic acid is washed off to be neutral. And finally drying the obtained product at 60 ℃ for 3h to obtain the product.
Preparation of a polyurethane-based transparent antifouling coating of 0.5% by weight PDMS-OH: 1.05mg of polydimethylsiloxane (PDMS-OH) and 50mg of hexamethylene diisocyanate trimer (HDIT) were weighed out accuratelyPutting into a 3mL transparent glass bottle, adding 0.5mL butanone, shaking, dissolving, and placing into a 75 ℃ oven for carrying out primary pre-reaction for 72 h. Then 160mg of acetylated starch was accurately weighed and dissolved in a small amount of DMF, and after the first preliminary reaction was completed, it was added to the first preliminary reaction system, and the resulting mixed solution was treated with an organic solvent (V)DMC:DMF1:2) and then a second pre-crosslinking reaction was carried out at 75 ℃ for 4 h. Filtering the pre-reaction solution by using a 0.45-micron microporous filter membrane, sucking 0.4mL of filtrate by using an injector to coat a film on the treated glass slide, immediately closing the system by using a preservative film after the film coating is finished, leaving a small hole to allow the solvent to slowly volatilize for 60min, increasing airflow for 15min to volatilize the residual low-boiling-point solvent, and finally placing the glass slide into a 120-DEG C oven for high-temperature curing for 15 h.
Example 2
Preparation of acetylated starch: accurately weighing 5g of amylose, adding the amylose into a three-necked bottle, adding 10.79g of glacial acetic acid, stirring for 5min, adding 9.45g of acetic anhydride, stirring for 15min, adding 0.18g of methanesulfonic acid catalyst, and reacting for 24h at 75 ℃. After the reaction is finished, the reactant is moved into a constant pressure funnel, slowly dripped into the stirred deionized water for washing, after the dripping is finished, vacuum filtration is started, the deionized water is used for leaching, and the acetic acid is washed off to be neutral. And finally drying the obtained product at 60 ℃ for 3h to obtain the product.
Preparation of a 1 wt% PDMS-OH polyurethane-based transparent antifouling coating: 2.10mg of polydimethylsiloxane (PDMS-OH) and 50mg of hexamethylene diisocyanate trimer (HDIT) were accurately weighed out and put in a 3mL transparent glass bottle, 0.5mL of butanone was added thereto, shaken and dissolved, and put in a 75 ℃ oven to carry out a first pre-reaction for 72 hours. Then, 160mg of acetylated starch was accurately weighed and dissolved in DMF, and after the first preliminary reaction was completed, it was added to the first preliminary reaction system, and the resulting mixed solution was treated with an organic solvent (V)DMC:DMF1:2) and then a second pre-crosslinking reaction was carried out at 75 ℃ for 4 h. Filtering the pre-reaction solution with 0.45 μm microporous membrane, sucking 0.4mL filtrate with injector, coating on the treated glass slide, immediately sealing the system with preservative film after coating, leaving a small hole for slowly volatilizing solvent for 90min, and increasing airflow for 10min to make residual solventThe remained low boiling point solvent is volatilized, and finally the mixture is put into a 120 ℃ oven for high-temperature curing for 15 hours.
Example 3
Preparation of acetylated starch: accurately weighing 5g of amylose, adding the amylose into a three-necked bottle, adding 10.79g of glacial acetic acid, stirring for 5min, adding 9.45g of acetic anhydride, stirring for 15min, adding 0.18g of methanesulfonic acid catalyst, and reacting for 24h at 75 ℃. After the reaction is finished, the reactant is moved into a constant pressure funnel, slowly dripped into the stirred deionized water for washing, after the dripping is finished, vacuum filtration is started, the deionized water is used for leaching, and the acetic acid is washed off to be neutral. And finally drying the obtained product at 60 ℃ for 3h to obtain the product.
Preparation of a polyurethane-based transparent antifouling coating of 2.5% by weight PDMS-OH: 5.25mg of polydimethylsiloxane (PDMS-OH) and 50mg of hexamethylene diisocyanate trimer (HDIT) were accurately weighed out and put in a 3mL transparent glass bottle, 0.5mL of butanone was added thereto, shaken and dissolved, and put in a 75 ℃ oven to carry out a first pre-reaction for 72 hours. Then, 160mg of acetylated starch was accurately weighed and dissolved in DMF, and after the first preliminary reaction was completed, it was added to the first preliminary reaction system, and the resulting mixed solution was treated with an organic solvent (V)DMC:DMF1:2) and then a second pre-crosslinking reaction was carried out at 75 ℃ for 4 h. Filtering the pre-reaction solution by using a 0.45-micron microporous filter membrane, sucking 0.4mL of filtrate by using an injector to coat a film on the treated glass slide, immediately closing the system by using a preservative film after the film coating is finished, leaving a small hole to allow the solvent to slowly volatilize for 80min, increasing airflow for 10min to volatilize the residual low-boiling-point solvent, and finally placing the glass slide into a 120-DEG C oven for high-temperature curing for 15 h.
Example 4
Preparation of acetylated starch: accurately weighing 5g of amylose, adding the amylose into a three-necked bottle, adding 10.79g of glacial acetic acid, stirring for 5min, adding 9.45g of acetic anhydride, stirring for 15min, adding 0.18g of methanesulfonic acid catalyst, and reacting for 24h at 75 ℃. After the reaction is finished, the reactant is moved into a constant pressure funnel, slowly dripped into the stirred deionized water for washing, after the dripping is finished, vacuum filtration is started, the deionized water is used for leaching, and the acetic acid is washed off to be neutral. And finally drying the obtained product at 60 ℃ for 3h to obtain the product.
Preparation of a polyurethane-based transparent antifouling coating of 5% by weight PDMS-OH: 10.50mg of polydimethylsiloxane (PDMS-OH) and 50mg of hexamethylene diisocyanate trimer (HDIT) were accurately weighed out and put in a 3mL transparent glass bottle, 0.5mL of butanone was added thereto, shaken and dissolved, and put in a 75 ℃ oven to carry out a first pre-reaction for 72 hours. Then, 160mg of acetylated starch was accurately weighed and dissolved in DMF, and after the first preliminary reaction was completed, it was added to the first preliminary reaction system, and the resulting mixed solution was treated with an organic solvent (V)DMC:DMF1:2) and then a second pre-crosslinking reaction was carried out at 75 ℃ for 4 h. Filtering the pre-reaction solution by using a 0.45-micron microporous filter membrane, sucking 0.4mL of filtrate by using an injector to coat a film on the treated glass slide, immediately closing the system by using a preservative film after the film coating is finished, leaving a small hole to allow the solvent to slowly volatilize for 70min, increasing airflow for 15min to volatilize the residual low-boiling-point solvent, and finally placing the glass slide into a 120-DEG C oven for high-temperature curing for 15 h.
The present invention is described in detail with reference to the embodiments, but the present invention is not limited to the above embodiments, and any improvements and modifications made to the present invention are within the scope of the claims of the present invention.
Claims (10)
1. A preparation method of a polyurethane-based transparent antifouling coating is characterized by comprising the following steps:
1) dissolving polyorganosiloxane with terminal hydroxyl and polyisocyanate compound in an organic solvent for carrying out a first pre-reaction;
2) carrying out acylation modification on the natural polymer with hydroxyl to obtain an acylated natural polymer;
3) and dissolving the acylated natural polymer by using an organic solvent, then adding the dissolved acylated natural polymer into a system which completes the first pre-reaction to perform a second pre-crosslinking reaction, and finally performing film coating and curing to obtain the polyurethane-based transparent antifouling coating.
2. The method for preparing a polyurethane-based transparent antifouling coating according to claim 1, wherein the specific reaction conditions of step 1) are: taking polyorganosiloxane with terminal hydroxyl as a functional component, taking a polyisocyanate compound as a crosslinking agent, and carrying out a first pre-reaction in an organic solvent, wherein the temperature is set to be 25-80 ℃ and the reaction time is 3-72 h.
3. The method for preparing a polyurethane-based transparent antifouling coating according to claim 2, wherein the weight average molecular weight Mw of the hydroxyl-terminated polyorganosiloxane is 1000-10000, and the amount added is 0.2-3.5 wt% of the total raw material amount; the polyisocyanate compound is a compound with more than two isocyanate groups; the organic solvent in the step 1) is one or more selected from butanone, isopropanol, acetone and n-hexane, and the addition amount is 85-95 wt% of the total raw material amount.
4. The method for preparing a polyurethane-based transparent antifouling coating according to claim 1, wherein the method of acylation modification used in the step 2) is a solvent method, a water-coal method or a high-temperature high-pressure method; the acylation amount of the obtained acylated natural polymer is 60-90%.
5. The method for preparing a polyurethane-based transparent antifouling coating according to claim 1, wherein the specific reaction conditions of step 2) are: activating natural polymer with hydroxyl in solvent, slowly adding acylating agent and catalyst, reacting at 60-80 deg.C for 3-36 hr, washing with deionized water, filtering, and drying to obtain acylated natural polymer.
6. The method for preparing a polyurethane-based transparent antifouling coating according to claim 5, wherein the natural polymer with hydroxyl groups is selected from one or more of starch, cyclodextrin, cellulose, lignin, chitosan, chitin and oligosaccharide.
7. The method for preparing a polyurethane-based transparent antifouling coating according to claim 5, wherein the solvent in step 2) is one or more selected from glacial acetic acid, N-dimethylformamide and pyridine; the acylating reagent is one or more of carboxylic acid, carboxylic ester, acid anhydride, acyl chloride and ketene; the catalyst is organic acid.
8. The method for preparing a polyurethane-based transparent antifouling coating according to claim 1, wherein the specific reaction conditions of step 3) are: dissolving the acylated natural polymer by using an organic solvent, adding the dissolved acylated natural polymer into a system which finishes the first pre-reaction, diluting the obtained mixed solution by using the solvent, then carrying out the second pre-crosslinking reaction for 3-8h at 60-80 ℃, filtering the obtained product by using a microporous filter membrane after the reaction is finished, coating the obtained product, and finally curing the obtained product at the temperature of 100 ℃ and 150 ℃ to obtain the polyurethane-based transparent antifouling coating.
9. The method for preparing a polyurethane-based transparent antifouling coating according to claim 8, wherein the molar ratio of-OH of the acylated natural macromolecule to-NCO of the polyisocyanate compound in the step 3) is 1:1 to 1: 1.5; the organic solvent for dissolving the acylated natural polymer is one or more of butanone, DMC and DMF, the solvent for diluting the mixed solution is DMC and/or DMF, and the dilution multiple is 2-5 times of volume.
10. The method for preparing a polyurethane-based transparent antifouling coating according to claim 8, wherein the film forming method in step 3) is replaced with a solvent evaporation film forming method, a hot melt film forming method, or a chemical film forming method.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110922562A (en) * | 2019-11-13 | 2020-03-27 | 东莞市雄林新材料科技股份有限公司 | High-light-transmittance TPU (thermoplastic polyurethane) film and preparation method thereof |
| CN113604142A (en) * | 2021-07-22 | 2021-11-05 | 吉林大学 | Dynamic oleophobic siloxane polyurethane coating and preparation method thereof |
| CN114479628A (en) * | 2021-12-24 | 2022-05-13 | 佛山市南海起弘新材料科技有限公司 | Polyurethane coating for shoes and preparation method of coating thereof |
| CN115124920A (en) * | 2022-08-05 | 2022-09-30 | 之江实验室 | Transparent self-repairing anti-contamination polyurethane coating and preparation method thereof |
| CN115558410A (en) * | 2022-11-01 | 2023-01-03 | 江南大学 | Method for preparing polyurethane environment-friendly antifouling coating |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110922562A (en) * | 2019-11-13 | 2020-03-27 | 东莞市雄林新材料科技股份有限公司 | High-light-transmittance TPU (thermoplastic polyurethane) film and preparation method thereof |
| CN113604142A (en) * | 2021-07-22 | 2021-11-05 | 吉林大学 | Dynamic oleophobic siloxane polyurethane coating and preparation method thereof |
| CN114479628A (en) * | 2021-12-24 | 2022-05-13 | 佛山市南海起弘新材料科技有限公司 | Polyurethane coating for shoes and preparation method of coating thereof |
| CN115124920A (en) * | 2022-08-05 | 2022-09-30 | 之江实验室 | Transparent self-repairing anti-contamination polyurethane coating and preparation method thereof |
| CN115558410A (en) * | 2022-11-01 | 2023-01-03 | 江南大学 | Method for preparing polyurethane environment-friendly antifouling coating |
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