CN112608673A - SiO with core-shell structure2Preparation method of modified bio-based UV (ultraviolet) curing waterborne polyurethane coating - Google Patents
SiO with core-shell structure2Preparation method of modified bio-based UV (ultraviolet) curing waterborne polyurethane coating Download PDFInfo
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- 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
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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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
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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
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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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6662—Compounds of group C08G18/42 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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Abstract
SiO with core-shell structure2A preparation method of a modified UV-cured waterborne polyurethane coating belongs to the technical field of functional nano materials. According to the invention, the organic-inorganic core-shell structure is introduced, so that the mechanical property and the water resistance of the castor oil-based waterborne polyurethane coating can be effectively improved. By inorganic nanoThe nano particles with the core-shell structure, which are prepared by taking the rice particles as shells and the polymer as cores, have excellent dispersion stability, the organic cores and the inorganic shells are connected through hydrogen bonds and covalent bonds, and the core-shell nano silicon dioxide particles prepared by adopting the silane coupling agent are connected with double bonds, so that the stability of the nano particles can be effectively enhanced when the nano particles are applied to a photocuring material, and the nano particles have good application prospect in the field of photocuring materials.
Description
Technical Field
The invention relates to a SiO with a core-shell structure2A preparation method of a modified bio-based UV (ultraviolet) curing water-based polyurethane coating belongs to the technical field of functional nano materials.
Background
The bio-based waterborne polyurethane has the advantages of low VOC (volatile organic compound) emission, renewability, good biodegradability, biocompatibility and the like, but the introduction of castor oil influences the mechanical property and water resistance of a coating film, and the silica nanoparticles are one of the most widely researched oxide nano materials.
According to the invention, the organic-inorganic core-shell structure is introduced, so that the mechanical property and the water resistance of the castor oil-based waterborne polyurethane coating can be effectively improved. The core-shell structure nano particle with the inorganic nano particle as the shell and the polymer as the core has excellent dispersion stability, the organic core and the inorganic shell are connected through hydrogen bonds and covalent bonds, and the core-shell nano silicon dioxide particle prepared by adopting the silane coupling agent is connected with double bonds, so that the stability of the nano particle can be effectively enhanced when the core-shell nano silicon dioxide particle is applied to a photocuring material, and the core-shell structure nano particle has a good application prospect in the field of photocuring materials.
Disclosure of Invention
The invention aims to overcome the defects and provide the SiO with the core-shell structure2The preparation method of the modified bio-based UV-cured waterborne polyurethane coating comprises the step of carrying out self-assembly sol-gel by taking castor oil-based waterborne polyurethane colloidal particles with double bonds as templatesAfter the ultraviolet curing technology is used for forming the film, the core shells are connected by covalent bonds, so that the stability of the aqueous polyurethane emulsion is improved, and the mechanical property and the water resistance of the film after photocuring are improved.
The technical scheme of the invention is that the SiO has a core-shell structure2The preparation method of the modified bio-based UV curing waterborne polyurethane coating comprises the following steps:
(1) and (3) drying: dehydrating and drying a silane compound and polyester dihydric alcohol;
(2) preparing the castor oil-based waterborne polyurethane emulsion: adding a certain amount of catalyst and diisocyanate into a reaction container, and dropwise adding the dried polyester dihydric alcohol obtained in the step (1) to react to obtain a primary polymer; adding ricinoleic acid for continuous reaction, then adding an active blocking agent, a polymerization inhibitor and a solvent A for reaction, adding a neutralizing agent for shearing, finally adding deionized water, shearing and emulsifying, and decompressing and rotary-steaming to remove the solvent A to obtain the ricinoleic-based waterborne polyurethane emulsion;
(3) modification: adding the silane compound obtained by drying in the step (1), the castor oil-based waterborne polyurethane emulsion prepared in the step (2) and deionized water into a container, and reacting under slow magnetic stirring; then adding tetraethyl silicate to continue reaction to obtain SiO with a core-shell structure2Modified waterborne polyurethane coatings.
Further, the polyester diol in the step (1) is at least one of polycarbonate diol, polycaprolactone diol and adipic acid polyester diol;
the silane compound is specifically 3- (methacryloyloxy) propyltrimethoxysilane and/or 3- (methacryloyloxy) propyltriethoxysilane.
Further, in the step (2), the catalyst is dibutyltin dilaurate and/or stannous octoate;
the diisocyanate is at least one of toluene diisocyanate TDI, 4' -diphenylmethane diisocyanate MDI and isophorone diisocyanate IPDI;
the active end-capping reagent is at least one of hydroxyethyl acrylate HEA, hydroxyethyl methacrylate HEMA, hydroxypropyl acrylate HPA, hydroxypropyl methacrylate HPMA and pentaerythritol triacrylate PETA;
the polymerization inhibitor is hydroquinone and/or p-methoxyphenol;
the neutralizing agent is triethylamine;
the solvent A is acetone.
Further, the step (1) is specifically as follows: and (3) placing the silane compound and the polyester dihydric alcohol in a vacuum drying oven, and carrying out vacuum dehydration treatment for 30min at the temperature of 80-100 ℃ to obtain the dried silane compound and polyester dihydric alcohol raw materials.
Further, the step (2) is specifically as follows:
a. adding 0.03-0.04g of catalyst and 4.45-4.46g of diisocyanate into a three-neck flask, raising the temperature to 50-55 ℃, dropwise adding 8-8.1g of dried polyester dihydric alcohol obtained in the step (1), reacting for 2-3h, and finishing when NCO reaches a theoretical value to obtain a protomer;
b. controlling the temperature of the initial polymer at 60-65 ℃, adding 1.47-1.48g of ricinoleic acid, and reacting for 2-3h until the NCO reaches a theoretical value;
c. controlling the temperature at 60-65 ℃, adding 1.52-1.53g of active blocking agent, 0.04-0.05g of polymerization inhibitor and 8-10mL of solvent A, and reacting for 2.5-3 h;
d. cooling the reaction temperature to room temperature, adding 0.55-0.6g of neutralizing agent, shearing at a high speed of 800r/min for 30min at 600-.
Further, the step (3) is specifically: weighing 0.69-0.70g of silane compound obtained by drying in the step (1), 29-30g of castor oil-based waterborne polyurethane emulsion prepared in the step (2) and 13.5-13.6g of deionized water, adding the mixture into a conical flask, controlling the temperature to be 55-60 ℃, reacting for 1-1.5h under slow magnetic stirring, adding 0.69-0.70g of tetraethyl silicate TEOS, and reacting for 3-3.5h to obtain SiO with a core-shell structure2Modified waterborne polyurethane coatings.
SiO with core-shell structure2Application of modified UV-cured waterborne polyurethane coating and preparation method thereofThe coating film was formed as a coating material.
Further, the steps are as follows: taking SiO with core-shell structure2Adding a photoinitiator into the modified waterborne polyurethane coating, uniformly mixing, pouring the emulsion into a polytetrafluoroethylene groove, standing at room temperature, baking, and performing ultraviolet curing to obtain a coating film.
Further, the photoinitiator is specifically 1173 photoinitiator.
Further, the method comprises the following specific steps: taking 5-5.1g of SiO with a core-shell structure2Adding 0.23-0.25g of photoinitiator into the modified waterborne polyurethane coating, uniformly stirring the modified waterborne polyurethane coating in a dark room temperature, pouring the emulsion into a polytetrafluoroethylene groove, standing for 1d at the room temperature, baking for 2-3h in a baking oven at 60 ℃, and then putting the baking oven into an ultraviolet curing machine for curing for 40-50s to obtain the coating.
The invention has the beneficial effects that: according to the invention, the coating with the castor oil-based waterborne polyurethane core and the nano-silica particle shell is prepared through the reaction, the water resistance and the mechanical property of the coating are improved to a certain extent, and the coating can be widely applied to surfaces of vehicle windows, doors and windows and the like with water resistance and weather resistance requirements.
Drawings
FIG. 1 is a schematic view showing the water contact angle of sample 1 of application example 1.
Fig. 2 is a schematic view of water contact angle of sample 2 of application example 1.
Detailed Description
Experimental example 1
(1) And (3) drying: placing 3- (methacryloyloxy) propyl trimethoxy silane and polycarbonate diol in a vacuum drying oven, and performing vacuum dehydration treatment at 80-100 ℃ for 30min to obtain a dried raw material;
(2) preparing the castor oil-based waterborne polyurethane emulsion: adding 0.04g of dibutyltin dilaurate and 4.45g of isophorone diisocyanate (IPDI) into a 250mL three-neck flask, heating to 50-55 ℃, dropwise adding 8g of polycarbonate diol, reacting for 2-3h, and finishing when NCO reaches a theoretical value to obtain a protomer; controlling the temperature of the initial polymer at 60-65 ℃, adding 1.48g of ricinoleic acid for reaction for 2-3h, controlling the temperature at 60-65 ℃ after NCO reaches a theoretical value, adding 1.525g of PETA, 0.04g of p-methoxyphenol and 10mL of acetone for reaction for 2.5-3 h; cooling the reaction temperature to room temperature, adding 0.575g of TEA, shearing at 700r/min for 30min, adding 30g of deionized water, shearing at 1000r/min for 30min, and removing acetone at 0.07MPa and 55 ℃ to obtain the castor oil-based waterborne polyurethane emulsion for later use;
(3) modification: weighing 0.7g of 3- (methacryloyloxy) propyltrimethoxysilane, 30g of the castor oil-based waterborne polyurethane emulsion prepared in the step (2) and 13.6g of deionized water, adding the mixture into a 100mL conical flask, controlling the temperature to be 55-60 ℃, reacting for 1-1.5h under slow magnetic stirring, adding 0.7g of tetraethyl silicate (TEOS) and reacting for 3-3.5h to obtain the SiO with the core-shell structure2Modified waterborne polyurethane coatings.
Application examples
5g of SiO having a core-shell structure, prepared in example 1, were weighed2Adding 0.25g of 1173 photoinitiator into the modified waterborne polyurethane coating, uniformly stirring the modified waterborne polyurethane coating in a dark room temperature, pouring the emulsion into a polytetrafluoroethylene groove, standing for 1d at the room temperature, baking for 2-3h in a 60 ℃ baking oven, and then putting the baking oven into an ultraviolet curing machine for curing for 40-50s to obtain a finished coating.
5g of SiO having a core-shell structure, prepared in example 1, were weighed2Adding 0.25g of 1173 photoinitiator into the modified waterborne polyurethane coating, uniformly stirring the modified waterborne polyurethane coating in the dark at room temperature, uniformly coating the emulsion on a transparent glass slide, standing the transparent glass slide for 1d at room temperature, baking the transparent glass slide in an oven at 60 ℃ for 2-3h, and then putting the transparent glass slide into an ultraviolet curing machine for curing for 40-50s to obtain a finished coating. It was then used for water contact angle, adhesion and pencil hardness tests.
Cutting a part of a coating film obtained after photocuring in a polytetrafluoroethylene groove, weighing the cut coating film as m1, soaking the cut coating film in deionized water for one day, taking the coating film out, slightly wiping the surface of the coating film with absorbent paper to remove excessive water, weighing the coating film as m2, and calculating according to a formula: water absorption = (m 2-m 1)/m 1 × 100% water absorption. The results are shown in Table 1.
Preparation of sample strips: the finished coating film obtained in the polytetrafluoroethylene tank was cut into a dumbbell shape according to the mold, and used for the test of tensile strength and elongation at break. Finally, sample 2 was obtained. The basic properties are shown in table 2, and the water contact angle is shown in fig. 2.
Comparative examples
The common silicon modified UV-cured waterborne polyurethane coating is used as a contrast, and the synthesis method comprises the following steps: the waterborne polyurethane synthesized by replacing polyester dihydric alcohol with hydroxyl-terminated polyether modified silicone oil (PDMS) in a certain proportion (5-10%). After the coating material was obtained, UV curing was performed under the same conditions as in the application examples to obtain a coating film.
Preparation of sample strips: the finished coating film obtained in the polytetrafluoroethylene tank was cut into a dumbbell shape according to the mold, and used for the test of tensile strength and elongation at break. Finally, sample 1 was obtained.
Weighing the coating film obtained after photocuring, marking as m1, soaking in deionized water for one day, taking out, lightly wiping the surface of the coating film by using absorbent paper to remove excessive water, weighing, marking as m2, and calculating according to a formula: water absorption = (m 2-m 1)/m 1 × 100% water absorption. The results are shown in Table 1.
TABLE 1 Water absorption of sample 1 and sample 2
As is clear from table 1, the water absorption of sample 1 was 8.85%, and the water absorption of sample 2 was 6.96%. This is because the coating film containing silica has a denser crosslinked network structure due to the increased crosslinking density and the protective effect of the silica shell, and water is difficult to permeate into the coating film.
The basic properties of the coating film are shown in Table 2, and the water contact angle is shown in FIG. 1.
Fig. 1 is a water contact angle of sample 1, fig. 2 is a water contact angle of sample 2, the water contact angle of sample 1 is 88 °, and the water contact angle of sample 2 is 99 °. As can be seen from the figure, the water contact angle of sample 2 prepared in the example of the present invention is much larger than that of sample 1, indicating that sample 2 has good hydrophobicity.
TABLE 2 basic Properties of coating films of sample 1 and sample 2
As can be seen from table 2, the adhesion of sample 1 and sample 2 prepared according to the present invention is not greatly different, but the pencil hardness of sample 2 is improved to a certain extent, which is increased from 1H to 3H, and the tensile strength of sample 2 is greatly increased compared to sample 1, and the elongation at break is also increased to a certain extent.
Claims (10)
1. SiO with core-shell structure2The preparation method of the modified bio-based UV curing waterborne polyurethane coating is characterized by comprising the following steps:
(1) and (3) drying: dehydrating and drying a silane compound and polyester dihydric alcohol;
(2) preparing the castor oil-based waterborne polyurethane emulsion: adding a certain amount of catalyst and diisocyanate into a reaction container, and dropwise adding the dried polyester dihydric alcohol obtained in the step (1) to react to obtain a primary polymer; adding ricinoleic acid for continuous reaction, then adding an active blocking agent, a polymerization inhibitor and a solvent A for reaction, adding a neutralizing agent for shearing, finally adding deionized water, shearing and emulsifying, and decompressing and rotary-steaming to remove the solvent A to obtain the ricinoleic-based waterborne polyurethane emulsion;
(3) modification: adding the silane compound obtained by drying in the step (1), the castor oil-based waterborne polyurethane emulsion prepared in the step (2) and deionized water into a container, and reacting under slow magnetic stirring; then adding tetraethyl silicate to continue reaction to obtain SiO with a core-shell structure2Modified waterborne polyurethane coatings.
2. SiO having a core-shell structure according to claim 12The preparation method of the modified bio-based UV curing waterborne polyurethane coating is characterized by comprising the following steps: the polyester dihydric alcohol in the step (1) is at least one of polycarbonate dihydric alcohol, polycaprolactone dihydric alcohol and adipic acid polyester dihydric alcohol;
the silane compound is specifically 3- (methacryloyloxy) propyltrimethoxysilane and/or 3- (methacryloyloxy) propyltriethoxysilane.
3. SiO having a core-shell structure according to claim 12The preparation method of the modified bio-based UV curing waterborne polyurethane coating is characterized by comprising the following steps: in the step (2), the catalyst is dibutyltin dilaurate and/or stannous octoate;
the diisocyanate is at least one of toluene diisocyanate TDI, 4' -diphenylmethane diisocyanate MDI and isophorone diisocyanate IPDI;
the active end-capping reagent is at least one of hydroxyethyl acrylate HEA, hydroxyethyl methacrylate HEMA, hydroxypropyl acrylate HPA, hydroxypropyl methacrylate HPMA and pentaerythritol triacrylate PETA;
the polymerization inhibitor is hydroquinone and/or p-methoxyphenol;
the neutralizing agent is triethylamine;
the solvent A is acetone.
4. SiO having a core-shell structure according to claim 12The preparation method of the modified bio-based UV-curable waterborne polyurethane coating is characterized in that the step (1) is specifically as follows: and (3) placing the silane compound and the polyester dihydric alcohol in a vacuum drying oven, and carrying out vacuum dehydration treatment for 30min at the temperature of 80-100 ℃ to obtain the dried silane compound and polyester dihydric alcohol raw materials.
5. SiO having a core-shell structure according to claim 12The preparation method of the modified bio-based UV-curable waterborne polyurethane coating is characterized in that the step (2) is specifically as follows:
a. adding 0.03-0.04g of catalyst and 4.45-4.46g of diisocyanate into a three-neck flask, raising the temperature to 50-55 ℃, dropwise adding 8-8.1g of dried polyester dihydric alcohol obtained in the step (1), reacting for 2-3h, and finishing when NCO reaches a theoretical value to obtain a protomer;
b. controlling the temperature of the initial polymer at 60-65 ℃, adding 1.47-1.48g of ricinoleic acid, and reacting for 2-3h until the NCO reaches a theoretical value;
c. controlling the temperature at 60-65 ℃, adding 1.52-1.53g of active blocking agent, 0.04-0.05g of polymerization inhibitor and 8-10mL of solvent A, and reacting for 2.5-3 h;
d. cooling the reaction temperature to room temperature, adding 0.55-0.6g of neutralizing agent, shearing at a high speed of 800r/min for 30min at 600-.
6. SiO having a core-shell structure according to claim 12The preparation method of the modified bio-based UV-curable waterborne polyurethane coating is characterized in that the step (3) is specifically as follows: weighing 0.69-0.70g of silane compound obtained by drying in the step (1), 29-30g of castor oil-based waterborne polyurethane emulsion prepared in the step (2) and 13.5-13.6g of deionized water, adding the mixture into a conical flask, controlling the temperature to be 55-60 ℃, reacting for 1-1.5h under slow magnetic stirring, adding 0.69-0.70g of tetraethyl silicate TEOS, and reacting for 3-3.5h to obtain SiO with a core-shell structure2Modified castor oil-based waterborne polyurethane coatings.
7. SiO having a core-shell structure as claimed in claim 12The application of the modified bio-based UV curing water-based polyurethane coating is characterized in that: the resultant coating was used as a coating material to form a coating film.
8. SiO having a core-shell structure according to claim 72The application of the modified bio-based UV curing waterborne polyurethane coating is characterized by comprising the following steps: taking SiO with core-shell structure2Adding a photoinitiator into the modified waterborne polyurethane coating, uniformly mixing, pouring the emulsion into a polytetrafluoroethylene groove, standing at room temperature, baking, and performing ultraviolet curing to obtain a coating film.
9. SiO having a core-shell structure according to claim 82The application of the modified bio-based UV curing water-based polyurethane coating is characterized in that: the photoinitiator is 1173 lightAnd (3) an initiator.
10. SiO having a core-shell structure according to claim 82The application of the modified bio-based UV curing waterborne polyurethane coating is characterized by comprising the following specific steps: taking 5-5.1g of SiO with a core-shell structure2Adding 0.23-0.25g of photoinitiator into the modified waterborne polyurethane coating, uniformly stirring the modified waterborne polyurethane coating in a dark room temperature, pouring the emulsion into a polytetrafluoroethylene groove, standing for 1d at the room temperature, baking for 2-3h in a baking oven at 60 ℃, and then putting the baking oven into an ultraviolet curing machine for curing for 40-50s to obtain the coating.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107082868A (en) * | 2017-04-26 | 2017-08-22 | 运研材料科技（上海）有限公司 | A kind of nuclear shell structure nano hybrid particle, its preparation method and its anti-reflective coating compositions |
| CN109666105A (en) * | 2018-12-14 | 2019-04-23 | 江南大学 | A kind of preparation method of the high insulating moulding coating of UV curable aqueous polyurethane |
| CN109942781A (en) * | 2019-04-01 | 2019-06-28 | 东北林业大学 | A kind of UV solidification castor oil-base aqueous polyurethane dispersion and the preparation method and application thereof |
| CN110615885A (en) * | 2019-10-17 | 2019-12-27 | 广东工业大学 | Ultraviolet-curable waterborne polyurethane emulsion and preparation method and application thereof |
| CN110862409A (en) * | 2019-12-04 | 2020-03-06 | 江南大学 | Method for preparing silane compound containing dihydric alcohol structure and modified waterborne polyurethane thereof |
| CN111849333A (en) * | 2020-07-30 | 2020-10-30 | 江南大学 | SiO (silicon dioxide)2Preparation method of hydrophilic modified UV (ultraviolet) curing waterborne polyurethane antifogging coating |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107082868A (en) * | 2017-04-26 | 2017-08-22 | 运研材料科技（上海）有限公司 | A kind of nuclear shell structure nano hybrid particle, its preparation method and its anti-reflective coating compositions |
| CN109666105A (en) * | 2018-12-14 | 2019-04-23 | 江南大学 | A kind of preparation method of the high insulating moulding coating of UV curable aqueous polyurethane |
| CN109942781A (en) * | 2019-04-01 | 2019-06-28 | 东北林业大学 | A kind of UV solidification castor oil-base aqueous polyurethane dispersion and the preparation method and application thereof |
| CN110615885A (en) * | 2019-10-17 | 2019-12-27 | 广东工业大学 | Ultraviolet-curable waterborne polyurethane emulsion and preparation method and application thereof |
| CN110862409A (en) * | 2019-12-04 | 2020-03-06 | 江南大学 | Method for preparing silane compound containing dihydric alcohol structure and modified waterborne polyurethane thereof |
| CN111849333A (en) * | 2020-07-30 | 2020-10-30 | 江南大学 | SiO (silicon dioxide)2Preparation method of hydrophilic modified UV (ultraviolet) curing waterborne polyurethane antifogging coating |
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