CN111849347B - Polysiloxane and application thereof - Google Patents
Polysiloxane and application thereof Download PDFInfo
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- CN111849347B CN111849347B CN202010802276.7A CN202010802276A CN111849347B CN 111849347 B CN111849347 B CN 111849347B CN 202010802276 A CN202010802276 A CN 202010802276A CN 111849347 B CN111849347 B CN 111849347B
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
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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
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- 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
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic 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
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/794—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aromatic isocyanates or isothiocyanates
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/054—Forming anti-misting or drip-proofing coatings
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- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/10—Block or graft copolymers containing polysiloxane sequences
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
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- C08J2483/10—Block- or graft-copolymers containing polysiloxane sequences
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Abstract
The invention discloses polysiloxane and application thereof, wherein the polysiloxane is prepared by reacting semi-closed isocyanate prepolymer with organic polymer silanol. The polysiloxane has an anti-fog function, and when the polysiloxane is applied to the anti-fog coating, UV curing can be realized and the hardness of the coating can be improved.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to polysiloxane and application thereof.
Background
The high-transparency material is an indispensable material in daily life and production, but the fogging phenomenon is easy to occur in the using process, so that the light transmittance of the surface of the material is reduced, the sight is influenced, a lot of inconvenience is brought to life, and even serious harm is caused. In recent years, the anti-fog technology is gradually paid more attention, and a series of advanced technologies and relatively mature products have been formed due to the fastest development progress of the hydrophilic anti-fog coating. The hydrophilic antifogging paint is a functional material, and is a chemical product with antifogging function, which is prepared by using a high polymer material with hydrophilic groups as a main component and matching with other auxiliary agents and organic solvents in corresponding proportions, and is one of the most effective ways for antifogging at the present stage.
The transparent organosiloxane polymer is used for antifogging various transparent glass and plastic material surfaces, such as optical lenses, goggles, face masks, helmet panels, automobile parts, and the like, but it is in a form of heat curing, requires a long curing time and high energy consumption, is low in production efficiency, is not suitable for continuous industrial production, and has low hardness and poor scratch resistance. The UV (ultraviolet) light-cured antifogging coating has higher light transmittance than the heat-cured antifogging coating, can realize instant curing under ultraviolet light, and is very suitable for continuous industrial production. Therefore, it is necessary to develop a new UV-curable material with high hardness for antifogging.
Disclosure of Invention
In order to solve the technical problems mentioned in the background art, the invention aims to provide polysiloxane and application thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
in one aspect, the present invention provides a polysiloxane formed by the reaction of a semi-blocked isocyanate prepolymer with an organic polymer silanol.
Further, the molar ratio of the semi-blocked isocyanate prepolymer to the organic polymer silanol is 6:1-1: 1; preferably 4:1 to 2: 1.
Further, the polysiloxane has a functionality of 1 to 18, preferably 2 to 18, more preferably 2 to 6, more preferably 3 to 5.
Further, the semi-closed isocyanate prepolymer is formed by reacting diisocyanate with a functional monomer containing hydroxyl;
preferably, the diisocyanate comprises one or a combination of at least two of isophorone diisocyanate (IPDI), Toluene Diisocyanate (TDI), Hexamethylene Diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI), liquefied MDI;
preferably, the hydroxyl-containing functional monomer comprises one or a combination of at least two of hydroxyethyl methacrylate (HEMA), hydroxyethyl acrylate (HEA), hydroxypropyl acrylate (HPA), 4-hydroxybutyl acrylate (4HBA), pentaerythritol triacrylate (PETA);
preferably, the molar ratio of-NCO in the diisocyanate and-OH in the hydroxyl-containing functional monomer is 2 to 4: 1.
further, the organic polymer silanol is obtained by the hydrolysis reaction of an organic siloxane polymer;
the organic siloxane polymer is formed by the reaction of a surfactant and alkoxy silane functionalized by isocyanate groups; the surfactant is one or more of nonionic polyalcohol polymer with polyoxyethylene segments and cationic quaternary ammonium salt surfactant;
preferably, the molecular weight of the nonionic polyol polymer having polyoxyethylene segments is 400-50000, preferably 400-30000; more preferably, the nonionic polyol polymer having polyoxyethylene segments includes one or a combination of at least two of polyethylene glycol 400, polyethylene glycol 600, polyethylene glycol 800, polyethylene glycol 1000, polyoxyethylene-polyoxypropylene (PEO-PPO) block copolymer;
preferably, the cationic quaternary ammonium surfactant comprises two hydrophilic groups capable of reacting with isocyanate and a hydrophobic hydrocarbon chain of at least 16 carbons, preferably, the hydrophilic groups are hydroxyl groups; more preferably, the cationic quaternary ammonium salt surfactant comprises one or a combination of at least two of octadecyl dihydroxypropyl ammonium chloride (Cirrasol G-265), octadecyl methyl dihydroxyethyl ammonium bromide, hexadecyl dihydroxyethyl amine oxide;
preferably, the isocyanate-functional alkoxysilane comprises one or a combination of two of isocyanate propyl triethoxysilane, 3-isocyanate propyl trimethoxysilane; more preferably, the isocyanate-functional alkoxysilane is isocyanatopropyltriethoxysilane;
preferably, the molar ratio of-NCO in the isocyanate-functional alkoxysilane to-OH in the surfactant is 1: 1-2, more preferably 1: 1;
preferably, the method of the organosiloxane polymer hydrolysis reaction is: adding an organic siloxane polymer into a mixed solution of acid/water/ethanol for reaction, wherein the molar ratio of the organic siloxane polymer to the water to the acid to the ethanol is 1: 2-6: 0.001-0.005: 10-40 parts of; the acid is at least one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid and citric acid;
preferably, the specific method of the organosiloxane polymer hydrolysis reaction is: mixing an organic siloxane polymer, water, acid and ethanol according to a molar ratio of 1: 2-6: 0.001-0.005: 10-40, adding the mixture into a container dropwise at room temperature, after the mixture is added, heating to 30-40 ℃ for reaction for 0.5-2h, and then reacting at 60-80 ℃ for 1-3h to obtain the organic polymer silanol.
In another aspect, the present invention provides the use of a polysiloxane as described in any one of the above in an anti-fog coating.
In another aspect, the invention provides an antifogging coating, which comprises the following components: a polymer capable of being cured by UV, a non-reactive ionic surfactant, a hydrophilic functional monomer, a photoinitiator, a flatting agent and a solvent; the UV-curable polymer is a polysiloxane as described in any one of the above.
Further, the coating is prepared from the following components in parts by mass: 40-80 parts of UV-curable polymer, 5-10 parts of non-reactive ionic surfactant, 5-20 parts of hydrophilic functional monomer, 3-5 parts of photoinitiator, 0.5-1.0 part of flatting agent and 50-150 parts of solvent; the UV-curable polymer is a polysiloxane as described in any one of the above;
preferably, the non-reactive ionic surfactant is an anionic surfactant comprising at least one hydrophilic group and one hydrophobic hydrocarbon chain containing 6-12 carbons, wherein the hydrophilic group is one or a combination of two of carboxylate and sulfonate; more preferably, the non-reactive ionic surfactant comprises one or a combination of at least two of dioctyl sodium sulfosuccinate, disodium lauryl sulfosuccinate, sodium di-n-decyl sulfosuccinate, and sodium dihexyl sulfosuccinate;
preferably, the hydrophilic functional monomer comprises one or a combination of at least two of beta-acryloxypropionic acid (beta-CEA), hydroxyethyl acrylate (HEA), hydroxyethyl methacrylate (HEMA), hydroxypropyl acrylate (HPA), 4-hydroxybutyl acrylate (4HBA), methacrylic acid (MAA), Acrylic Acid (AA), N-vinyl pyrrolidone (NVP), polyethylene glycol 400 diacrylate (PEG400DA), polyethylene glycol 600 diacrylate (PEG600DA), polyethylene glycol 1000 diacrylate (PEG1000 DA);
preferably, the photoinitiator is a hydrogen abstraction type aqueous photoinitiator; more preferably, the photoinitiator comprises one or a combination of two of photoinitiator 500 and photoinitiator 2959;
preferably, the leveling agent comprises one or a combination of two of a fluorine wetting leveling agent FSWET1010 and a fluorine-containing leveling agent FS 3100;
preferably, the solvent comprises one or a combination of at least two of deionized water, ethanol, isopropanol.
The invention further provides a preparation method of the antifogging coating, which comprises the following steps: mixing the UV-curable polymer, a non-reactive ionic surfactant, a hydrophilic functional monomer, a photoinitiator, a leveling agent and a solvent to obtain the antifogging coating;
preferably, the method specifically comprises the following steps: adding the UV-curable polymer into a container, sequentially adding a solvent and stirring under a stirring state, adding a non-reactive ionic surfactant and stirring, adding a hydrophilic functional monomer and stirring, adding a photoinitiator and stirring, and adding a leveling agent and stirring to obtain the antifogging coating.
The invention further provides an application of the antifogging coating in preparing an antifogging coating.
The invention further provides an antifogging coating, which is prepared by the following method: coating any one of the antifogging coatings on a substrate, and curing to form the antifogging coating;
preferably, the substrate comprises glass, plastic, metal; more preferably, in practical applications, the glass includes automotive glass (such as front and rear windshields and rearview mirrors), building glass (such as inner sides of doors and windows), advertising boards, bathroom mirrors and public transportation glass (such as trains, airplanes, buses, coach front and rear windshields and rearview mirrors); the metal comprises an iron plate, a copper plate and an aluminum alloy plate;
preferably, the coating method comprises blade coating, wiping, spin coating and spray coating;
preferably, the curing method is pre-drying at 50-80 ℃ for 1-5min, and then curing by 250-2000mJ ultraviolet light.
The invention has the beneficial effects that: the invention designs high-hardness UV-curable polysiloxane with an antifogging function, and the polysiloxane is applied to an antifogging coating formula to obtain the antifogging coating protected by the application.
Detailed Description
In order to better understand the content of the invention, the invention is further described in detail by the following specific embodiments, it should be understood that the following embodiments are only illustrative of the invention, not limiting the content of the invention, and any technical solution that does not substantially change the content of the invention still falls into the protection scope of the invention.
The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
EXAMPLE 1 preparation of antifog coating
(a) Preparation of semi-blocked isocyanate prepolymer: in a 500mL three-necked flask, 133.38g (0.6mol) of isophorone diisocyanate IPDI and 0.2g (0.1 wt%) of dibutyltin dilaurate DBTDL were placed and stirred; 0.5394g (0.262 wt%) of p-hydroxyanisole MEHQ, 1.0788g (0.525 wt%) of 2, 6-di-tert-butyl-4-methylphenol BHT and 70.05g (0.602mol) of hydroxyethyl acrylate HEA are weighed in sequence, fully mixed until completely dissolved, transferred to a constant pressure dropping funnel, slowly dropped into the three-neck flask at room temperature (the reaction is violent in heat release, the dropping speed is controlled to avoid local overheating), after dropping, the temperature is raised to 70 ℃ for reaction until the content of isocyanate group (-NCO) of the mixture reaches a theoretical value (determined by a n-butylamine hydrochloride method), cooled to obtain a semi-closed isocyanate prepolymer which is marked as IPDI-HEA, dried, sealed and stored;
(b) preparation of the organic Polymer silanol: in a 250mL three-necked flask, 104G of Isocyanatopropyltriethoxysilane (IPTS) and 80G of polyethylene glycol 400 were stirred and mixed uniformly, 0.01G of dibutyltin dilaurate DBTDL was added, reaction was carried out at 70 ℃ for 4 hours until the end point (the-NCO content measured by the dibutylamine hydrochloride method was 0), and in addition, 104G of isocyanatopropyltriethoxysilane IPTS and 206G of octadecyl dihydroxypropyl ammonium chloride G-265 were stirred and mixed (ethyl acetate as a solvent) in a 500mL three-necked flask, 0.02G of dibutyltin dilaurate DBTDL was added, and reaction was carried out at 70 ℃ for 4 hours until the end point to form functional organosiloxane polymers, respectively, according to the following reaction formulae:
transferring the two reaction products into a new three-mouth bottle, uniformly mixing, preparing a mixed solution by weighing 60.48g of water, 0.602g of 37% concentrated hydrochloric acid and 115.92g of ethanol, uniformly stirring, measuring the pH to be 2-3, dripping into the three-mouth bottle at room temperature, slightly reducing the temperature after dripping, heating to 40 ℃ for reaction for 1h, then reacting at 60 ℃ for 3h to obtain organic polymer silanol, and removing alcohol and water by reduced pressure distillation for later use;
(c) preparation of UV-curable polysiloxanes: stirring and mixing the organic polymer silanol prepared in the step (b) with IPDI-HEA, and reacting at 80 ℃ until-NCO completely disappears to obtain UV-curable polysiloxane with the functionality of 2.3;
(d) preparing the UV-curable antifogging coating: adding 70g of the UV-curable polysiloxane into a material cylinder of a dispersion machine, sequentially adding 150g of water at 1000rpm, stirring for 30min, 6.0g of dioctyl sodium sulfosuccinate, stirring for 20min, 9.0g of polyethylene glycol 600 diacrylate PEG600DA, 9.0g of hydroxypropyl acrylate HPA, stirring for 10min, 5.0g of photoinitiator 500Irgacure500, stirring for 5min, and stirring for 5min by 1.0g of fluorine wetting leveling agent FSWET1010 to obtain the UV-curable antifogging paint;
(e) preparing a UV antifogging coating: uniformly coating the antifogging coating prepared in the step (d) on a clean PET film by using a wire rod, pre-drying for 3min in an oven at 80 ℃, then placing on a conveyor belt type UV curing machine, and curing by using 1000mJ ultraviolet light to obtain the antifogging coating.
EXAMPLE 2 preparation of antifog coating
(a) Preparation of semi-blocked isocyanate prepolymer: in a 500mL three-necked flask, 266.76g (1.2mol) of isophorone diisocyanate IPDI and 0.4g (0.1 wt%) of dibutyltin dilaurate DBTDL were placed and stirred; 1.0788g (0.262 wt%) of p-hydroxyanisole MEHQ, 2.1576g (0.525 wt%) of 2, 6-di-tert-butyl-4-methylphenol BHT and 140.1g (1.204mol) of hydroxyethyl acrylate HEA are weighed in sequence, fully mixed until the mixture is completely dissolved, transferred to a constant pressure dropping funnel, slowly dripped into the three-neck flask at room temperature (the reaction is violent in heat release, the dripping speed is controlled to avoid local overheating), after the dripping is finished and the reaction is continued at room temperature for 30min, the temperature is raised to 70 ℃ for reaction until the content of isocyanate group (-NCO) of the mixture reaches a theoretical value (determined by a n-butylamine hydrochloride method), the temperature is lowered to obtain a semi-closed isocyanate prepolymer which is marked as IPDI-HEA, and the semi-closed isocyanate prepolymer is dried, sealed and stored;
(b) preparation of the organic Polymer silanol: in a 500mL three-necked flask, 35G of Isocyanatopropyltriethoxysilane (IPTS) and 330G of polyoxyethylene-polyoxypropylene block copolymer PEO/PPO (molecular weight 5000) were mixed by stirring, 0.02G of dibutyltin dilaurate DBTDL was added, reaction was carried out at 70 ℃ for 4 hours until the end point (the NCO content was 0 as determined by the di-n-butylamine hydrochloride method), 104G of isocyanatopropyltriethoxysilane IPTS and 206G of octadecyl dihydroxypropyl ammonium chloride G-265 were mixed by stirring (ethyl acetate as a solvent) in a 500mL three-necked flask, 0.02G of dibutyltin dilaurate DBTDL was added, reaction was carried out at 70 ℃ for 4 hours until the end point, and functional organosiloxane polymers were formed, respectively, according to the following reaction formulas:
transferring the two reaction products into a new three-mouth bottle, uniformly mixing, weighing 40.32g of water, 0.402g of 37% concentrated hydrochloric acid and 77.28g of ethanol to prepare a mixed solution, uniformly stirring, measuring the pH value to be 2-3, dripping the mixed solution into the three-mouth bottle at room temperature, slightly reducing the temperature after dripping, heating to 40 ℃, reacting for 1h, then reacting for 3h at 60 ℃ to obtain organic polymer silanol, and removing the alcohol and the water by reduced pressure distillation for later use;
(c) preparation of UV-curable polysiloxanes: stirring and mixing the organic polymer silanol prepared in the step (b) with IPDI-HEA, and reacting at 80 ℃ until-NCO completely disappears to obtain UV-curable polysiloxane with functionality of 4;
(d) preparing the UV-curable antifogging coating: adding 70g of the UV-curable polysiloxane into a material cylinder of a dispersion machine, sequentially adding 150g of water at 1000rpm, stirring for 30min, stirring for 20min by 8.0g of dioctyl sodium sulfosuccinate, stirring for 10min by 6.0g of polyethylene glycol 600 diacrylate PEG600DA, stirring for 10.0g of 4-hydroxybutylacrylate 4HBA, stirring for 5min by 5.0g of photoinitiator 500Irgacure500, and stirring for 5min by 1.0g of fluorine-containing leveling agent FS3100 to obtain the UV-curable antifogging paint;
(e) preparing a UV antifogging coating: uniformly coating the antifogging coating prepared in the step (d) on a clean PET film by using a wire rod, pre-drying for 3min in an oven at 80 ℃, then placing on a conveyor belt type UV curing machine, and curing by using 800mJ ultraviolet light to obtain the antifogging coating.
EXAMPLE 3 preparation of antifogging coating
(a) Preparation of semi-blocked isocyanate prepolymer: in a 500mL three-necked flask, 266.76g (1.2mol) of isophorone diisocyanate IPDI and 0.4g (0.1 wt%) of dibutyltin dilaurate DBTDL were placed and stirred; 1.0788g (0.262 wt%) of p-hydroxyanisole MEHQ, 2.1576g (0.525 wt%) of 2, 6-di-tert-butyl-4-methylphenol BHT and 140.1g (1.204mol) of hydroxyethyl acrylate HEA are weighed in sequence, fully mixed until the mixture is completely dissolved, transferred to a constant pressure dropping funnel, slowly dripped into the three-neck flask at room temperature (the reaction is violent in heat release, the dripping speed is controlled to avoid local overheating), after the dripping is finished and the reaction is continued at room temperature for 30min, the temperature is raised to 70 ℃ for reaction until the content of isocyanate group (-NCO) of the mixture reaches a theoretical value (determined by a n-butylamine hydrochloride method), the temperature is lowered to obtain a semi-closed isocyanate prepolymer which is marked as IPDI-HEA, and the semi-closed isocyanate prepolymer is dried, sealed and stored;
(b) preparation of the organic Polymer silanol: in a 500mL three-necked flask, 35G of Isocyanatopropyltriethoxysilane (IPTS) and 330G of polyoxyethylene-polyoxypropylene block copolymer PEO/PPO (molecular weight 5000) were mixed by stirring, 0.02G of dibutyltin dilaurate DBTDL was added, reaction was carried out at 70 ℃ for 4 hours until the end point (the NCO content was 0 as determined by the di-n-butylamine hydrochloride method), 104G of isocyanatopropyltriethoxysilane IPTS and 206G of octadecyl dihydroxypropyl ammonium chloride G-265 were mixed by stirring (ethyl acetate as a solvent) in a 500mL three-necked flask, 0.02G of dibutyltin dilaurate DBTDL was added, reaction was carried out at 70 ℃ for 4 hours until the end point, and functional organosiloxane polymers were formed, respectively, according to the following reaction formulas:
transferring the two reaction products into a new three-mouth bottle, uniformly mixing, weighing 40.32g of water, 0.402g of 37% concentrated hydrochloric acid and 77.28g of ethanol to prepare a mixed solution, uniformly stirring, measuring the pH value to be 2-3, dripping the mixed solution into the three-mouth bottle at room temperature, slightly reducing the temperature after dripping, heating to 40 ℃, reacting for 1h, then reacting for 3h at 60 ℃ to obtain organic polymer silanol, and removing the alcohol and the water by reduced pressure distillation for later use;
(c) preparation of UV-curable polysiloxanes: stirring and mixing the organic polymer silanol prepared in the step (b) with IPDI-HEA, and reacting at 80 ℃ until-NCO completely disappears to obtain UV-curable polysiloxane with functionality of 6;
(d) preparing the UV-curable antifogging coating: adding 70g of the UV-curable polysiloxane into a material cylinder of a dispersion machine, sequentially adding 150g of water at 1000rpm, stirring for 30min, 4.0g of dioctyl sodium sulfosuccinate, stirring for 20min, 12.0g of polyethylene glycol 400 diacrylate PEG400DA, 8.0g of hydroxyethyl acrylate HEA, stirring for 10min, 5.0g of photoinitiator 2959Irgacure2959, stirring for 5min, and stirring for 5min by 1.0g of a fluorine wetting leveling agent FSWET1010 to obtain the UV-curable antifogging paint.
(e) Preparing a UV antifogging coating: uniformly coating the antifogging coating prepared in the step (d) on a clean PET film by using a wire rod, pre-drying for 3min in an oven at 80 ℃, then placing on a conveyor belt type UV curing machine, and curing by using 800mJ ultraviolet light to obtain the antifogging coating.
EXAMPLE 4 preparation of antifogging coating
(a) Preparation of semi-blocked isocyanate prepolymer: a1000 mL three-necked flask was charged with 333.45g (1.5mol) of isophorone diisocyanate IPDI and 0.5g (0.1 wt%) of dibutyltin dilaurate DBTDL and stirring was started; 1.3485g (0.262 wt%) of p-hydroxyanisole MEHQ, 2.697g (0.525 wt%) of 2, 6-di-tert-butyl-4-methylphenol BHT and 174.64g (1.504mol) of hydroxyethyl acrylate HEA are weighed in sequence, fully mixed until completely dissolved, transferred to a constant pressure dropping funnel, slowly dropped into the three-neck flask at room temperature (the reaction is violent in heat release, the dropping speed is controlled to avoid local overheating), after dropping, the temperature is raised to 70 ℃ for reaction until the content of isocyanate group (-NCO) of the mixture reaches a theoretical value (determined by a n-butylamine hydrochloride method), cooled to obtain a semi-closed isocyanate prepolymer which is marked as IPDI-HEA, dried, sealed and stored;
(b) preparation of the organic Polymer silanol: in a 250mL three-necked flask, 104G of Isocyanatopropyltriethoxysilane (IPTS) and 80G of polyethylene glycol 400 were stirred and mixed uniformly, 0.01G of dibutyltin dilaurate DBTDL was added, reaction was carried out at 70 ℃ for 4 hours until the end point (the-NCO content measured by the dibutylamine hydrochloride method was 0), and in a 500mL three-necked flask, 104G of isocyanatopropyltriethoxysilane IPTS and 206G of octadecyl dihydroxypropyl ammonium chloride G-265 were stirred and mixed (ethyl acetate as a solvent), 0.02G of DBTDL was added, and reaction was carried out at 70 ℃ for 4 hours until the end point, to form functional organosiloxane polymers, respectively, according to the following reaction formulae:
transferring the two reaction products into a new three-mouth bottle, uniformly mixing, preparing a mixed solution by weighing 60.48g of water, 0.602g of 37% concentrated hydrochloric acid and 115.92g of ethanol, uniformly stirring, measuring the pH to be 2-3, dripping into the three-mouth bottle at room temperature, slightly reducing the temperature after dripping, heating to 40 ℃ for reaction for 1h, then reacting at 60 ℃ for 3h to obtain organic polymer silanol, and removing alcohol and water by reduced pressure distillation for later use;
(c) preparation of UV-curable polysiloxanes: stirring and mixing the organic polymer silanol prepared in the step (b) with IPDI-HEA, and reacting at 80 ℃ until-NCO completely disappears to obtain UV-curable polysiloxane with functionality of 5;
(d) preparing the UV-curable antifogging coating: adding 65g of the UV-curable polysiloxane into a material cylinder of a dispersion machine, sequentially adding 150g of water at 1000rpm, stirring for 30min, 9.0g of dioctyl sodium sulfosuccinate, stirring for 20min, 13.0g of polyethylene glycol 800 diacrylate PEG800DA, 7.0g of beta-CEA, stirring for 10min, 5.0g of photoinitiator 500Irgacure500, stirring for 5min, and stirring for 5min by 1.0g of fluorine wetting leveling agent FSWET1010 to obtain the UV-curable antifogging coating;
(e) preparing a UV antifogging coating: uniformly coating the antifogging coating prepared in the step (d) on a clean PET film by using a wire rod, pre-drying for 3min in an oven at 80 ℃, then placing on a conveyor belt type UV curing machine, and curing by using 800mJ ultraviolet light to obtain the antifogging coating.
EXAMPLE 5 preparation of antifogging coating
(a) Preparation of semi-blocked isocyanate prepolymer: a1000 mL three-necked flask was charged with 261.25g (1.5mol) of toluene diisocyanate and 0.5g (0.1 wt%) of dibutyltin dilaurate, and stirring was started; 1.3485g (0.262 wt%) of p-hydroxyanisole, 2.697g (0.525 wt%) of 2, 6-di-tert-butyl-4-methylphenol and 195.2g (1.504mol) of hydroxypropyl acrylate are weighed in sequence, fully mixed until completely dissolved, transferred to a constant pressure dropping funnel, slowly dripped into the three-neck flask at room temperature (the reaction is violent in heat release, the dripping speed is controlled to avoid local overheating), and after dripping is finished, the room temperature reaction is continued for 30min, the temperature is increased to 70 ℃ for reaction until the content of isocyanate group (-NCO) of the mixture reaches a theoretical value (determined by a di-n-butylamine hydrochloride method), and the temperature is reduced to obtain a semi-closed isocyanate prepolymer which is marked as TDI-HPA, dried, sealed and stored;
(b) preparation of the organic Polymer silanol: in a 250mL three-necked flask, 104g of isocyanatopropyltriethoxysilane was uniformly mixed with 66.5g of polyethylene glycol 400 and 66g of a polyoxyethylene-polyoxypropylene block copolymer (molecular weight: 10000) with stirring, 0.01g of dibutyltin dilaurate was added, and after reaction at 70 ℃ for 4 hours to the end (NCO content measured by the di-n-butylamine hydrochloride method: 0), 104g of isocyanatopropyltriethoxysilane was mixed with 68.6g of octadecyl dihydroxypropyl ammonium chloride and 104.2g of octadecyl methyl dihydroxyethyl ammonium bromide with stirring (ethyl acetate as a solvent) in a 500mL three-necked flask, 0.02g of dibutyltin dilaurate was added, and after reaction at 70 ℃ for 4 hours to the end, a functional organosiloxane polymer was formed, respectively;
transferring the two reaction products into a new three-mouth bottle, uniformly mixing, preparing a mixed solution by weighing 60.48g of water, 0.602g of 37% concentrated hydrochloric acid and 115.92g of ethanol, uniformly stirring, measuring the pH to be 2-3, dripping into the three-mouth bottle at room temperature, slightly reducing the temperature after dripping, heating to 40 ℃ for reaction for 1h, then reacting at 60 ℃ for 3h to obtain organic polymer silanol, and removing alcohol and water by reduced pressure distillation for later use;
(c) preparation of UV-curable polysiloxanes: stirring and mixing the organic polymer silanol prepared in the step (b) with TDI-HPA, and reacting at 80 ℃ until-NCO completely disappears to obtain UV-curable polysiloxane with functionality of 5;
(d) preparing the UV-curable antifogging coating: adding 65g of the UV-curable polysiloxane into a material cylinder of a dispersion machine, sequentially adding 150g of water at 1000rpm, stirring for 30min, 9.0g of dioctyl sodium sulfosuccinate, stirring for 20min, 7.0g of disodium lauryl sulfosuccinate, 6.0g of polyethylene glycol 1000 diacrylate, 7.0g of 7.0g N-vinyl pyrrolidone, stirring for 10min, 5.0g of Irgacure photoinitiator 500, stirring for 5min, and stirring for 5min by 1.0g of FSWET1010 (fluorine wetting leveling agent) to obtain the UV-curable antifogging coating;
(e) preparing a UV antifogging coating: uniformly coating the antifogging coating prepared in the step (d) on a clean PET film by using a wire rod, pre-drying for 2min in an oven at 80 ℃, then placing on a conveyor belt type UV curing machine, and curing by using 800mJ ultraviolet light to obtain the antifogging coating.
EXAMPLE 6 preparation of antifogging coating
(a) Preparation of semi-blocked isocyanate prepolymer: a1000 mL three-necked flask was charged with 261.25g (1.5mol) of toluene diisocyanate and 0.5g (0.1 wt%) of dibutyltin dilaurate, and stirring was started; 1.3485g (0.262 wt%) of p-hydroxyanisole, 2.697g (0.525 wt%) of 2, 6-di-tert-butyl-4-methylphenol and 447.6g (1.502mol) of pentaerythritol triacrylate are sequentially weighed, fully mixed until completely dissolved, transferred to a constant-pressure dropping funnel, slowly dripped into the three-neck flask at room temperature (the reaction is violent in heat release, the dripping speed is controlled to avoid local overheating), and after dripping is finished, the room temperature reaction is continued for 30min, heated to 70 ℃ for reaction until the content of isocyanate group (-NCO) of the mixture reaches a theoretical value (determined by a di-n-butylamine hydrochloride method), cooled to obtain a semi-closed isocyanate prepolymer which is marked as TDI-HPA, dried, sealed and stored;
(b) preparation of the organic Polymer silanol: 2.75g of isocyanatopropyltriethoxysilane and 264g of a polyoxyethylene-polyoxypropylene block copolymer (molecular weight 50000) are mixed uniformly by stirring in a 500mL three-necked flask, 0.01g of dibutyltin dilaurate is added, the mixture is reacted at 70 ℃ for 4 hours until the end point (the NCO content measured by the di-n-butylamine hydrochloride method is 0), 59g of isocyanatopropyltriethoxysilane, 38.9g of octadecyl dihydroxypropyl ammonium chloride and 59.1g of octadecyl methyldihydroxyethyl ammonium bromide are mixed by stirring (ethyl acetate as a solvent) in a 500mL three-necked flask, 0.012g of dibutyltin dilaurate is added, and the mixture is reacted at 70 ℃ for 4 hours until the end point to respectively form a functional organosiloxane polymer;
transferring the two reaction products into a new three-mouth bottle, uniformly mixing, preparing a mixed solution by weighing 60.48g of water, 0.602g of 37% concentrated hydrochloric acid and 115.92g of ethanol, uniformly stirring, measuring the pH to be 2-3, dripping into the three-mouth bottle at room temperature, slightly reducing the temperature after dripping, heating to 40 ℃ for reaction for 1h, then reacting at 60 ℃ for 3h to obtain organic polymer silanol, and removing alcohol and water by reduced pressure distillation for later use;
(c) preparation of UV-curable polysiloxanes: stirring and mixing the organic polymer silanol prepared in the step (b) with TDI-HPA, and reacting at 80 ℃ until-NCO completely disappears to obtain UV-curable polysiloxane with functionality of 18;
(d) preparing the UV-curable antifogging coating: adding 65g of the UV-curable polysiloxane into a cylinder of a dispersion machine, sequentially adding 150g of water at 1000rpm, stirring for 30min, 6.0g of dioctyl sodium sulfosuccinate, stirring for 20min, 10.0g of disodium lauryl sulfosuccinate, 13.0g of 13.0g N-vinyl pyrrolidone, stirring for 10min, 5.0g of Irgacure photoinitiator 500, stirring for 5min, and stirring for 5min by 1.0g of a fluorine wetting leveling agent FSWET1010 to obtain the UV-curable antifogging paint;
(e) preparing a UV antifogging coating: uniformly coating the antifogging coating prepared in the step (d) on a clean PET film by using a wire rod, pre-drying for 2min in an oven at 80 ℃, then placing on a conveyor belt type UV curing machine, and curing by using 800mJ ultraviolet light to obtain the antifogging coating.
EXAMPLE 7 preparation of antifogging coating
(a) Preparation of semi-blocked isocyanate prepolymer: a1000 mL three-necked flask was charged with 470.25g (2.7mol) of toluene diisocyanate and 0.9g (0.1 wt%) of dibutyltin dilaurate, and stirring was started; 2.4273g (0.262 wt%) of p-hydroxyanisole, 4.8546g (0.525 wt%) of 2, 6-di-tert-butyl-4-methylphenol and 351.4g (2.7mol) of hydroxypropyl acrylate are weighed in sequence, fully mixed until completely dissolved, transferred to a constant pressure dropping funnel, slowly dripped into the three-neck flask at room temperature (the reaction is violent in heat release, the dripping speed is controlled to avoid local overheating), and after dripping is finished, the room temperature reaction is continued for 30min, heated to 70 ℃ for reaction until the content of isocyanate group (-NCO) of the mixture reaches a theoretical value (determined by a di-n-butylamine hydrochloride method), cooled to obtain a semi-closed isocyanate prepolymer which is marked as TDI-HPA, dried, sealed and stored;
(b) preparation of the organic Polymer silanol: 2.75g of isocyanate propyltriethoxysilane and 264g of a polyoxyethylene-polyoxypropylene block copolymer (molecular weight 50000) are stirred and mixed uniformly in a 500mL three-necked flask, 0.01g of dibutyltin dilaurate is added, the mixture is reacted at 70 ℃ for 4 hours until the end point (the NCO content is 0 as determined by the di-n-butylamine hydrochloride method), 104g of isocyanate propyltriethoxysilane, 68.6g of octadecyl dihydroxypropyl ammonium chloride and 104.2g of octadecyl methyldihydroxyethyl ammonium bromide are stirred and mixed (ethyl acetate is used as a solvent) in a 500mL three-necked flask, 0.02g of dibutyltin dilaurate is added, and the mixture is reacted at 70 ℃ for 4 hours until the end point to respectively form a functional organosiloxane polymer;
transferring the two reaction products into a new three-mouth bottle, uniformly mixing, preparing a mixed solution by weighing 60.48g of water, 0.602g of 37% concentrated hydrochloric acid and 115.92g of ethanol, uniformly stirring, measuring the pH to be 2-3, dripping into the three-mouth bottle at room temperature, slightly reducing the temperature after dripping, heating to 40 ℃ for reaction for 1h, then reacting at 60 ℃ for 3h to obtain organic polymer silanol, and removing alcohol and water by reduced pressure distillation for later use;
(c) preparation of UV-curable polysiloxanes: stirring and mixing the organic polymer silanol prepared in the step (b) with TDI-HPA, and reacting at 80 ℃ until-NCO completely disappears to obtain UV-curable polysiloxane with the functionality of 9;
(d) preparing the UV-curable antifogging coating: adding 65g of the UV-curable polysiloxane into a cylinder of a dispersion machine, sequentially adding 150g of water at 1000rpm, stirring for 30min, 6.0g of dioctyl sodium sulfosuccinate, stirring for 20min, 10.0g of disodium lauryl sulfosuccinate, 13.0g of 13.0g N-vinyl pyrrolidone, stirring for 10min, 5.0g of Irgacure photoinitiator 500, stirring for 5min, and stirring for 5min by 1.0g of a fluorine wetting leveling agent FSWET1010 to obtain the UV-curable antifogging paint;
(e) preparing a UV antifogging coating: uniformly coating the antifogging coating prepared in the step (d) on a clean PET film by using a wire rod, pre-drying for 2min in an oven at 80 ℃, then placing on a conveyor belt type UV curing machine, and curing by using 800mJ ultraviolet light to obtain the antifogging coating.
EXAMPLE 8 preparation of antifogging coating
(a) Preparation of semi-blocked isocyanate prepolymer: in a 1000mL three-necked flask, 600.18g (2.7mol) of isophorone diisocyanate and 0.9g (0.1 wt%) of dibutyltin dilaurate were added and stirring was started; 3.2265g (0.262 wt%) of p-hydroxyanisole, 6.4710g (0.525 wt%) of 2, 6-di-tert-butyl-4-methylphenol, 261.2g (2.25mol) of hydroxyethyl acrylate and 134.1g (0.45mol) of pentaerythritol triacrylate are weighed in sequence, fully mixed until completely dissolved, transferred to a constant-pressure dropping funnel, slowly dropped into the three-neck flask at room temperature (the reaction is violent in heat release, the dropping speed is controlled to avoid local overheating), after dropping, the reaction is continued at room temperature for 30min, the temperature is raised to 70 ℃ for reaction until the content of isocyanate group (-NCO) of the mixture reaches a theoretical value (determined by a di-n-butylamine hydrochloride method), the temperature is lowered to obtain a semi-closed isocyanate prepolymer which is marked as TDI-HPA, and the mixture is dried, sealed and stored;
(b) preparation of the organic Polymer silanol: 2.75g of isocyanate propyltriethoxysilane and 264g of a polyoxyethylene-polyoxypropylene block copolymer (molecular weight 50000) are stirred and mixed uniformly in a 500mL three-necked flask, 0.01g of dibutyltin dilaurate is added, the mixture is reacted at 70 ℃ for 4 hours until the end point (the NCO content is 0 as determined by the di-n-butylamine hydrochloride method), 104g of isocyanate propyltriethoxysilane, 68.6g of octadecyl dihydroxypropyl ammonium chloride and 104.2g of octadecyl methyldihydroxyethyl ammonium bromide are stirred and mixed (ethyl acetate is used as a solvent) in a 500mL three-necked flask, 0.02g of dibutyltin dilaurate is added, and the mixture is reacted at 70 ℃ for 4 hours until the end point to respectively form a functional organosiloxane polymer;
transferring the two reaction products into a new three-mouth bottle, uniformly mixing, preparing a mixed solution by weighing 60.48g of water, 0.602g of 37% concentrated hydrochloric acid and 115.92g of ethanol, uniformly stirring, measuring the pH to be 2-3, dripping into the three-mouth bottle at room temperature, slightly reducing the temperature after dripping, heating to 40 ℃ for reaction for 1h, then reacting at 60 ℃ for 3h to obtain organic polymer silanol, and removing alcohol and water by reduced pressure distillation for later use;
(c) preparation of UV-curable polysiloxanes: stirring and mixing the organic polymer silanol prepared in the step (b) with TDI-HPA, and reacting at 80 ℃ until-NCO completely disappears to obtain UV-curable polysiloxane with the functionality of 12;
(d) preparing the UV-curable antifogging coating: adding 65g of the UV-curable polysiloxane into a cylinder of a dispersion machine, sequentially adding 150g of water at 1000rpm, stirring for 30min, 6.0g of dioctyl sodium sulfosuccinate, stirring for 20min, 10.0g of disodium lauryl sulfosuccinate, 13.0g of 13.0g N-vinyl pyrrolidone, stirring for 10min, 5.0g of Irgacure photoinitiator 500, stirring for 5min, and stirring for 5min by 1.0g of a fluorine wetting leveling agent FSWET1010 to obtain the UV-curable antifogging paint;
(e) preparing a UV antifogging coating: uniformly coating the antifogging coating prepared in the step (d) on a clean PET film by using a wire rod, pre-drying for 2min in an oven at 80 ℃, then placing on a conveyor belt type UV curing machine, and curing by using 800mJ ultraviolet light to obtain the antifogging coating.
Example 9 Performance testing
The performance testing items and methods for the antifog coatings produced in examples 1-8 are shown in the following table:
the results of the performance tests on the antifog coatings prepared in examples 1-8 are shown in the following table:
as can be seen from the table above, the antifogging coatings prepared in examples 1-8 have good hydrophilic antifogging property, high hardness and lasting antifogging property.
In summary, the invention creatively reacts the organic polymer silanol with the semi-closed isocyanate prepolymer to generate polysiloxane (F represents functionality, 18-F is 18 functionalities) with the maximum of 18-F, the hardness of the coating film is greatly improved, and the non-reactive ionic surfactant, the hydrophilic functional monomer, the photoinitiator, the flatting agent and the solvent are added to form the antifogging coating through photocuring reaction and instantaneous drying. Because the ionic surfactant is adopted, the initial antifogging property is effectively improved; by utilizing the interaction of anions and cations, the anion groups in the non-reactive ionic surfactant are tightly adsorbed on the surface of the coating by the cation groups in the organic siloxane polymer, so that the anions and the cations cannot be soaked away by water, the lasting anti-fog effect can be realized, the contact angle is reduced, and the anti-fog capability is enhanced; meanwhile, the coating has a framework structure of organic silicon and does not contain nano particles, so that the hardness and chemical resistance of the pencil are improved; the hydrophilic monomer has the function of adjusting the density of the functional groups, so that the coating is uniform and has good wear resistance. The coating prepared by the antifogging coating has excellent antifogging property, antifogging durability, water resistance, good transparency and surface hardness.
The above description is only a specific embodiment of the present invention, and not all embodiments, and any equivalent modifications of the technical solutions of the present invention, which are made by those skilled in the art through reading the present specification, are covered by the claims of the present invention.
Claims (39)
1. Polysiloxane, which is characterized in that the polysiloxane is prepared by reacting semi-closed isocyanate prepolymer with organic polymer silanol;
the organic polymer silanol is obtained by the hydrolysis reaction of an organic siloxane polymer;
the organic siloxane polymer is formed by the reaction of a surfactant and alkoxy silane functionalized by isocyanate groups; the surfactant is a combination of a nonionic polyol polymer having polyoxyethylene segments, a cationic quaternary ammonium surfactant;
the cationic quaternary ammonium surfactant comprises two hydrophilic groups capable of reacting with isocyanate and a hydrophobic hydrocarbon chain with at least 16 carbons.
2. Polysiloxane according to claim 1, characterized in that the molar ratio of the semi-blocked isocyanate prepolymer to the silicone polyol is from 6:1 to 1: 1.
3. The polysiloxane of claim 2, wherein the polysiloxane has a functionality of 1 to 18.
4. Polysiloxane according to claim 3, characterized in that the polysiloxane has a functionality of 2 to 18.
5. Polysiloxane according to claim 4, characterized in that the polysiloxane has a functionality of 2 to 6.
6. Polysiloxane according to claim 5, characterized in that the polysiloxane has a functionality of 3 to 6.
7. Polysiloxane according to claim 6, characterized in that the polysiloxane has a functionality of 3 to 5.
8. Polysiloxane according to claim 1, characterized in that the semi-blocked isocyanate prepolymer is obtained by reacting a diisocyanate with a functional monomer containing hydroxyl groups.
9. The polysiloxane of claim 8, wherein the diisocyanate comprises one or a combination of at least two of isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, and liquefied MDI.
10. The polysiloxane of claim 8, wherein the hydroxyl-containing functional monomer comprises one or a combination of at least two of hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, 4-hydroxybutyl acrylate, pentaerythritol triacrylate.
11. Polysiloxane according to claim 8, characterized in that the molar ratio of-NCO in the diisocyanate and-OH in the hydroxyl-containing functional monomer is 2-4: 1.
12. polysiloxane according to claim 1, characterized in that the molecular weight of the nonionic polyol polymer with polyoxyethylene segments is 400-50000.
13. Polysiloxane according to claim 12, characterized in that the molecular weight of the nonionic polyol polymer with polyoxyethylene segments is 400-30000.
14. The polysiloxane of claim 12, wherein the nonionic polyol polymer having polyoxyethylene segments comprises one or a combination of at least two of polyethylene glycol 400, polyethylene glycol 600, polyethylene glycol 800, polyethylene glycol 1000, polyoxyethylene-polyoxypropylene block copolymer.
15. Polysiloxane according to claim 1, characterized in that the hydrophilic groups are hydroxyl groups.
16. The polysiloxane of claim 1, wherein the cationic quaternary ammonium surfactant comprises one or a combination of at least two of octadecyl dihydroxypropyl ammonium chloride, octadecyl methyldiethanol ammonium bromide.
17. The polysiloxane of claim 1, wherein the isocyanate-functional alkoxysilane comprises one or a combination of two of isocyanatopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane.
18. The polysiloxane of claim 17, wherein the isocyanato-functionalized alkoxysilane is isocyanatopropyltriethoxysilane.
19. Polysiloxane according to claim 1, characterized in that the molar ratio of-NCO in the isocyanato-functionalized alkoxysilane and-OH in the surfactant is 1: 1-2.
20. The polysiloxane of claim 19, wherein the molar ratio of-NCO in the isocyanate-functional alkoxysilane to-OH in the surfactant is 1: 1.
21. the polysiloxane of claim 1, wherein the organosiloxane polymer is hydrolyzed by a process comprising: adding an organic siloxane polymer into a mixed solution of acid/water/ethanol for reaction, wherein the molar ratio of the organic siloxane polymer to the water to the acid to the ethanol is 1: 2-6: 0.001-0.005: 10-40 parts of; the acid is at least one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid and citric acid.
22. The polysiloxane of claim 21, wherein the organosiloxane polymer is hydrolyzed by a specific method comprising: mixing an organic siloxane polymer, water, acid and ethanol according to a molar ratio of 1: 2-6: 0.001-0.005: 10-40, adding the mixture into a container dropwise at room temperature, after the mixture is added, heating to 30-40 ℃ for reaction for 0.5-2h, and then reacting at 60-80 ℃ for 1-3h to obtain the organic polymer silanol.
23. Use of a polysiloxane according to any one of claims 1 to 22 in an antifog coating.
24. An antifogging coating is characterized by comprising the following components: a polymer capable of being cured by UV, a non-reactive ionic surfactant, a hydrophilic functional monomer, a photoinitiator, a flatting agent and a solvent; the UV-curable polymer is a polysiloxane according to any one of claims 1 to 22.
25. The anti-fog coating of claim 24, which is prepared from the following components in parts by mass: 40-80 parts of UV-curable polymer, 5-10 parts of non-reactive ionic surfactant, 5-20 parts of hydrophilic functional monomer, 3-5 parts of photoinitiator, 0.5-1.0 part of flatting agent and 50-150 parts of solvent; the UV-curable polymer is a polysiloxane according to any one of claims 1 to 22.
26. The anti-fog coating of claim 24 wherein the non-reactive ionic surfactant is an anionic surfactant comprising at least one hydrophilic group and one hydrophobic hydrocarbon chain containing 6-12 carbons, the hydrophilic group being one or a combination of carboxylate and sulfonate.
27. The anti-fog coating of claim 26 wherein the non-reactive ionic surfactant comprises one or a combination of at least two of dioctyl sodium sulfosuccinate, disodium lauryl sulfosuccinate, sodium di-n-decyl sulfosuccinate, dihexyl sulfosuccinate.
28. The anti-fog coating of claim 24 wherein the hydrophilic functional monomer comprises one or a combination of at least two of β -acryloxypropionic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, 4-hydroxybutyl acrylate, methacrylic acid, acrylic acid, N-vinyl pyrrolidone, polyethylene glycol 400 diacrylate, polyethylene glycol 600 diacrylate, polyethylene glycol 1000 diacrylate.
29. The anti-fog coating of claim 24 wherein the photoinitiator is a hydrogen abstraction-type aqueous photoinitiator.
30. The anti-fog coating of claim 29 wherein the photoinitiator comprises one or a combination of two of photoinitiator 500 and photoinitiator 2959.
31. The anti-fog coating of claim 24 wherein the leveling agent comprises one or a combination of two of a fluorine wetting leveling agent FSWET1010, a fluorine containing leveling agent FS 3100.
32. The anti-fog coating of claim 24 wherein the solvent comprises one or a combination of at least two of deionized water, ethanol, isopropanol.
33. The method of preparing an anti-fog coating of any of claims 24-32, comprising the steps of: and mixing the UV-curable polymer, the non-reactive ionic surfactant, the hydrophilic functional monomer, the photoinitiator, the leveling agent and the solvent to obtain the antifogging coating.
34. The preparation method of the antifogging coating of claim 33, specifically comprising the steps of: adding the UV-curable polymer into a container, sequentially adding a solvent and stirring under a stirring state, adding a non-reactive ionic surfactant and stirring, adding a hydrophilic functional monomer and stirring, adding a photoinitiator and stirring, and adding a leveling agent and stirring to obtain the antifogging coating.
35. Use of the anti-fog coating of any one of claims 24-32 in the preparation of an anti-fog coating.
36. An antifogging coating, characterized by, by preparing as follows: the anti-fog coating of any one of claims 24-32 is applied to a substrate and cured to form the anti-fog coating.
37. The anti-fog coating of claim 36 wherein the substrate comprises glass, plastic, metal.
38. The anti-fog coating of claim 36 wherein the coating method comprises knife coating, wiping, spin coating, spray coating.
39. The anti-fog coating as claimed in claim 36, wherein the curing method comprises pre-drying at 50-80 ℃ for 1-5min, and then curing by ultraviolet light of 250-2000 mJ.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005066285A2 (en) * | 2004-01-07 | 2005-07-21 | Clariant International Ltd | Hydrophilic coating based on polysilazane |
| CN102911582A (en) * | 2012-10-30 | 2013-02-06 | 中国海洋石油总公司 | Ultraviolet light cured antifogging coating |
| CN103025519A (en) * | 2010-08-18 | 2013-04-03 | Sdc科技有限公司 | Anti-fog organosiloxane coating compositions and coatings |
| CN103073700A (en) * | 2012-04-24 | 2013-05-01 | 南昌航空大学 | Preparation method for ultraviolet curing transparent wear-resistant resin |
| CN106675129A (en) * | 2016-12-09 | 2017-05-17 | 东来涂料技术（上海）有限公司 | High-hardness antifogging UV (ultraviolet) automobile varnish and preparation method thereof |
-
2020
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005066285A2 (en) * | 2004-01-07 | 2005-07-21 | Clariant International Ltd | Hydrophilic coating based on polysilazane |
| CN103025519A (en) * | 2010-08-18 | 2013-04-03 | Sdc科技有限公司 | Anti-fog organosiloxane coating compositions and coatings |
| CN103073700A (en) * | 2012-04-24 | 2013-05-01 | 南昌航空大学 | Preparation method for ultraviolet curing transparent wear-resistant resin |
| CN102911582A (en) * | 2012-10-30 | 2013-02-06 | 中国海洋石油总公司 | Ultraviolet light cured antifogging coating |
| CN106675129A (en) * | 2016-12-09 | 2017-05-17 | 东来涂料技术（上海）有限公司 | High-hardness antifogging UV (ultraviolet) automobile varnish and preparation method thereof |
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