CN111607320B - Waterborne polyurethane-silica sol composite antifogging agent and preparation method and application thereof - Google Patents

Waterborne polyurethane-silica sol composite antifogging agent and preparation method and application thereof Download PDF

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CN111607320B
CN111607320B CN202010505677.6A CN202010505677A CN111607320B CN 111607320 B CN111607320 B CN 111607320B CN 202010505677 A CN202010505677 A CN 202010505677A CN 111607320 B CN111607320 B CN 111607320B
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silica sol
double bonds
polyurethane
polymerization reaction
hydrophilic
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CN111607320A (en
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周峰
张丽慧
马正峰
蔡美荣
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Lanzhou Institute of Chemical Physics LICP of CAS
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Lanzhou Institute of Chemical Physics LICP of CAS
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Abstract

The invention relates to the technical field of antifogging agents, and particularly relates to a waterborne polyurethane-silica sol composite antifogging agent as well as a preparation method and application thereof. The invention provides a waterborne polyurethane-silica sol composite antifogging agent, which is prepared from hydrophilic polyurethane containing C ═ C double bonds, silica sol containing C ═ C double bonds and a solvent; the mass ratio of the hydrophilic polyurethane containing C ═ C double bonds, the silica sol containing C ═ C double bonds and the solvent is 5-15: 0.5-5: 95-80; the solid content of the silica sol containing C ═ C double bonds is 20-50%. The waterborne polyurethane-silica sol composite antifogging agent provided by the invention can form a cross-linking structure under the ultraviolet irradiation condition, so that the antifogging aging is effectively prolonged, and the formed coating has high mechanical strength and transparency and is more widely applied.

Description

Waterborne polyurethane-silica sol composite antifogging agent and preparation method and application thereof
Technical Field
The invention relates to the technical field of antifogging agents, and particularly relates to a waterborne polyurethane-silica sol composite antifogging agent as well as a preparation method and application thereof.
Background
The phenomenon of fogging of glasses, goggles, glass windows, bathroom mirrors, polymer films of greenhouses, automobile windshields and rearview mirrors is frequently encountered in daily life, great inconvenience is brought to work, life and production, and even danger is caused. When an obvious temperature difference occurs between the material and the environment, and the saturated vapor pressure of water is reduced to be lower than the partial pressure of water vapor in the air, the water vapor is condensed into water drops on the surface of the material, and the phenomenon of water mist is caused. The small droplets in the mist diffuse the light, severely affecting the light transmittance of the material.
There are generally two approaches to solving the fogging problem: the hydrophilic surface promotes the micro liquid drops to be rapidly spread into a water film, so that the light transmittance of the material is guaranteed; the hydrophobic surface encourages the surface micro droplets to fuse into large droplets and roll off quickly, thereby reducing the adverse effects of mist.
Among them, polyurethane type polymers are valued and widely studied in the field of antifogging because of the advantages of flexible molecular design, high film transmittance, high controllability of molecular structure, and the like. Researchers strive to balance the antifogging effect and the coating film mechanical property of the antifogging coating, and generally obtain a more efficient, long-acting and wear-resistant antifogging functional coating through acrylic acid modification, curing crosslinking, organic/inorganic compounding and the like. Types of acrylic modification such as: patent CN201610512064.9 synthesizes acrylic acid modified polyurethane by using acrylic acid graft modified polyester polyol, hydrophilic chain extender and diisocyanate as raw materials. Types of thermal/light curing such as: patent CN201410222093.2 discloses a method for forming a polymer antifogging coating by ultraviolet light curing with urethane acrylate oligomer as a matrix resin; in patent CN201910257347.7, an antifogging coating with excellent water resistance and high adhesion is formed by curing a soft-structure polyurethane prepolymer, a hard-structure polyurethane prepolymer and a carbon-carbon double bond-containing cross-linking agent through a photoinitiator; the patent CN201910257367.4 prepares the normal temperature curing type antifogging coating by means of the principle that aziridine groups and carboxyl groups of polyurethane prepolymers are crosslinked and cured at normal temperature. Composite material types such as: in patent CN201910257887.5, a composite polyurethane antifogging material is formed by heating and curing silica microspheres with isocyanate end-capped macromolecular chains and a polyfunctional group curing agent. The prior art emphasizes the antifogging performance and is difficult to consider the convenience in the practical application process, so that the application and popularization are limited. At present, antifogging products taking micromolecular surfactants as main components occupy most market shares due to convenient and safe use, but have the defects of insufficient effect durability, poor abrasion resistance and the like.
Therefore, the method has the advantages of easy realization, wider application, more convenient use and longer antifogging durability in the preparation, production and application processes.
Disclosure of Invention
The invention aims to provide the waterborne polyurethane-silica sol composite antifogging agent, and the preparation method and the application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a waterborne polyurethane-silica sol composite antifogging agent, which is prepared from hydrophilic polyurethane containing C ═ C double bonds, silica sol containing C ═ C double bonds, an ultraviolet initiator and a solvent; the mass ratio of the hydrophilic polyurethane containing C ═ C double bonds, the silica sol containing C ═ C double bonds and the solvent is 5-15: 0.5-5: 80-95; the solid content of the silica sol containing C ═ C double bonds is 20-50%.
Preferably, the mass of the ultraviolet initiator accounts for 1-1.5% of the total mass of the waterborne polyurethane-silica sol composite antifogging agent.
Preferably, the preparation method of the hydrophilic polyurethane containing C ═ C double bonds comprises the following steps:
mixing polyethylene glycol, diisocyanate and a first hydrophilic chain extender in an organic solvent, and carrying out a first polymerization reaction under the action of a catalyst to obtain a-NCO-group-terminated polyurethane prepolymer;
mixing the-NCO-group-terminated polyurethane prepolymer, an acrylate monomer containing C-C double bonds and a polymerization inhibitor, and carrying out a second polymerization reaction to obtain hydrophilic polyurethane containing C-C double bonds;
mixing polyethylene glycol and diisocyanate in an organic solvent, and carrying out a third polymerization reaction under the action of a catalyst to obtain a-NCO-group-terminated polyurethane prepolymer;
mixing the-NCO-group-terminated polyurethane prepolymer, an acrylate monomer containing C-C double bonds and a polymerization inhibitor, and carrying out a fourth polymerization reaction to obtain polyurethane containing C-C double bonds;
and mixing the polyurethane containing the C-C double bond with a second hydrophilic chain extender, and carrying out chain extension reaction to obtain the hydrophilic polyurethane containing the C-C double bond.
Preferably, the polyethylene glycol is one or more of PEG-300, PEG-400, PEG-800, PEG-1000, PEG-2000 and PEG-4000;
the diisocyanate is one or more of isophorone diisocyanate, 1, 6-hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane-4, 4' -diisocyanate and 4, 4-dicyclohexylmethane diisocyanate;
the first hydrophilic chain extender is one or more of dimethylolpropionic acid, dimethylolbutyric acid and 1, 2-dihydroxy-3-sodium propane sulfonate;
the second hydrophilic chain extender is 2- [ (2-aminoethyl) amino ] ethanesulfonic acid sodium salt;
the organic solvent is acetone, ethyl acetate or N, N-dimethylformamide;
the catalyst is dibutyltin dilaurate, stannous octoate, 1, 4-dimethyl piperazine or an organic bismuth catalyst;
the acrylic ester monomer containing C ═ C double bonds is one or more of hydroxyethyl methacrylate, hydroxyethyl acrylate and hydroxypropyl acrylate;
the polymerization inhibitor is hydroquinone or p-benzoquinone.
Preferably, the temperature of the first polymerization reaction and the temperature of the third polymerization reaction are 75-100 ℃ independently, and the time of the first polymerization reaction and the time of the third polymerization reaction are 3-6 h independently;
the temperature of the second polymerization reaction and the temperature of the fourth polymerization reaction are 75-100 ℃ independently, and the time of the second polymerization reaction and the time of the fourth polymerization reaction are 2-5 h independently;
the temperature of the chain extension reaction is 30-45 ℃; the time of the chain extension reaction is 0.5-1.5 h.
Preferably, the method for preparing the silica sol containing C ═ C double bonds comprises the following steps:
dissolving a silane coupling agent containing C ═ C double bonds and tetraethoxysilane in an aqueous solvent, adjusting the pH value to 3-4, and carrying out hydrolysis reaction to obtain silica sol containing C ═ C double bonds.
The invention provides a preparation method of the waterborne polyurethane-silica sol composite antifogging agent, which comprises the following steps:
mixing hydrophilic polyurethane containing C ═ C double bonds with a solvent to obtain a polymer dispersion;
and mixing the polymer dispersion, silica sol containing C-C double bonds and an ultraviolet initiator to obtain the waterborne polyurethane-silica sol composite antifogging agent.
The invention also provides an application of the waterborne polyurethane-silica sol composite antifogging agent prepared by the technical scheme or the waterborne polyurethane-silica sol composite antifogging agent prepared by the preparation method of the technical scheme in antifogging products.
Preferably, the application comprises the steps of: and coating the waterborne polyurethane-silica sol composite antifogging agent on the surface of a substrate to be treated, and naturally airing to form a coating.
Preferably, after the natural drying, the method further comprises the step of carrying out ultraviolet irradiation on the obtained film layer to obtain the coating film.
The invention provides a waterborne polyurethane-silica sol composite antifogging agent, which is prepared from hydrophilic polyurethane containing C ═ C double bonds, silica sol containing C ═ C double bonds, an ultraviolet initiator and a solvent; the mass ratio of the hydrophilic polyurethane containing C ═ C double bonds, the silica sol containing C ═ C double bonds and the solvent is 8-10: 2-5: 90-92; the solid content of the silica sol containing C ═ C double bonds is 20-50%. In the invention, the hydrophilic polyurethane containing C ═ C double bonds has free radical polymerization reaction activity, the C ═ C double bonds contained in the molecules can be crosslinked to form a net structure under the ultraviolet irradiation condition, hydrophilic molecules are not easy to run off along with water drops, and the service life is longer; under the condition of ultraviolet irradiation, the silica sol containing C ═ C double bonds forms a cross-linked structure between silica sols, so that the coating film has high mechanical strength and transparency. The invention controls the mass ratio of the hydrophilic polyurethane containing C-C double bonds to the silica sol containing C-C double bonds in the range, is favorable for ensuring the stability of the antifogging coating and obtains good antifogging effect.
The invention also provides a preparation method of the waterborne polyurethane-silica sol composite antifogging agent, and the preparation method provided by the invention is simple, convenient and easy to operate and is suitable for industrial production.
Drawings
FIG. 1 is a schematic diagram of the film forming and anti-fogging mechanism of the waterborne polyurethane-silica sol composite anti-fogging agent provided by the invention;
FIG. 2 shows the results of the transparency and the cotton gauze wiping resistance of the coating film formed by the composite antifogging agent prepared in example 1 of the present invention;
FIG. 3 shows the antifogging property test results of the waterborne polyurethane-silica sol composite antifogging agent prepared in example 2 of the present invention on a non-UV-cured sample and a UV-cured sample;
fig. 4 is a diagram showing the antifogging performance effect of the waterborne polyurethane-silica sol composite antifogging agent prepared in example 2 of the present invention on glass and glasses.
Detailed Description
The invention provides a waterborne polyurethane-silica sol composite antifogging agent, which is prepared from hydrophilic polyurethane containing C ═ C double bonds, silica sol containing C ═ C double bonds, an ultraviolet initiator and a solvent; the mass ratio of the hydrophilic polyurethane containing C ═ C double bonds, the silica sol containing C ═ C double bonds and the solvent is 5-15: 0.5-5: 80-95; the solid content of the silica sol containing C ═ C double bonds is 20-50%.
The preparation raw material of the waterborne polyurethane-silica sol composite antifogging agent provided by the invention comprises hydrophilic polyurethane containing C ═ C double bonds. In the present invention, the method for producing the hydrophilic polyurethane containing a C ═ C double bond preferably includes the first method or the second method:
mixing polyethylene glycol, diisocyanate and a first hydrophilic chain extender in an organic solvent, and carrying out a first polymerization reaction under the action of a catalyst to obtain a-NCO-group-terminated polyurethane prepolymer;
mixing the-NCO-group-terminated polyurethane prepolymer, an acrylate monomer containing C-C double bonds and a polymerization inhibitor, and carrying out a second polymerization reaction to obtain hydrophilic polyurethane containing C-C double bonds;
mixing polyethylene glycol and diisocyanate in an organic solvent, and carrying out a third polymerization reaction under the action of a catalyst to obtain a-NCO-group-terminated polyurethane prepolymer;
mixing the-NCO-group-terminated polyurethane prepolymer, an acrylate monomer containing C-C double bonds and a polymerization inhibitor, and carrying out a fourth polymerization reaction to obtain polyurethane containing C-C double bonds;
and mixing the polyurethane containing the C-C double bond with a second hydrophilic chain extender, and carrying out chain extension reaction to obtain the hydrophilic polyurethane containing the C-C double bond.
In the first method, preferably, polyethylene glycol, diisocyanate and a first hydrophilic chain extender are mixed in an organic solvent, and a first polymerization reaction is carried out under the action of a catalyst to obtain a-NCO-group-terminated polyurethane prepolymer. In the invention, the polyethylene glycol is preferably one or more of PEG-300, PEG-400, PEG-800, PEG-1000, PEG-2000 and PEG-4000, and when the polyethylene glycol comprises a plurality of polyethylene glycols, the invention has no special requirement on the proportion of each polyethylene glycol, and the proportion can be any. In the invention, the diisocyanate is preferably one or more of isophorone diisocyanate, 1, 6-hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane-4, 4' -diisocyanate and 4, 4-dicyclohexylmethane diisocyanate, and when the diisocyanate comprises a plurality of diisocyanates, the proportion of each diisocyanate in the invention has no special requirement, and any proportion can be adopted. In the invention, the first type of hydrophilic chain extender is preferably one or more of dimethylolpropionic acid, dimethylolbutyric acid and 1, 2-dihydroxy-3-sodium propane sulfonate, and when the first type of hydrophilic chain extender is 1, 2-dihydroxy-3-sodium propane sulfonate and dimethylolbutyric acid, the molar ratio of the 1, 2-dihydroxy-3-sodium propane sulfonate to the dimethylolbutyric acid is preferably 1: 1. In the present invention, the organic solvent is preferably acetone, ethyl acetate or N, N-dimethylformamide; the catalyst is preferably dibutyltin dilaurate, stannous octoate, 1, 4-dimethylpiperazine or an organic bismuth catalyst, and the organic bismuth catalyst is particularly preferably BCAT-E20 CX.
In the invention, the molar ratio of the polyethylene glycol, the diisocyanate and the first hydrophilic chain extender is preferably 1-5: 1-8: 0.1 to 3.0, more preferably 2 to 3:1 to 6:0.1 to 2.0; the dosage of the organic solvent is preferably 50-150% of the total mass of the polyethylene glycol, the diisocyanate and the first hydrophilic chain extender, and more preferably 80-100%; the dosage of the catalyst is preferably 0.3-1.0% of the total mass of the polyethylene glycol, the diisocyanate and the first hydrophilic chain extender, and more preferably 0.5-0.8%.
In the invention, the temperature of the first polymerization reaction is preferably 75-100 ℃, and more preferably 80-85 ℃; the time of the first polymerization reaction is preferably 3 to 6 hours, and more preferably 3 to 5 hours.
After obtaining the-NCO group-terminated polyurethane prepolymer, the present invention preferably mixes the-NCO group-terminated polyurethane prepolymer with an acrylate monomer containing a C ═ C double bond and a polymerization inhibitor, and performs a second polymerization reaction to obtain a hydrophilic polyurethane containing a C ═ C double bond.
In the invention, the acrylic ester monomer containing the C ═ C double bond is preferably one or more of hydroxyethyl methacrylate, hydroxyethyl acrylate and hydroxypropyl acrylate, and when the acrylic ester monomer containing the C ═ C double bond comprises a plurality of monomers, the proportion of each acrylic ester monomer containing the C ═ C double bond is not particularly required, and any proportion can be adopted. In the present invention, the polymerization inhibitor is preferably hydroquinone or p-benzoquinone.
In the invention, the molar ratio of the acrylate monomer containing a C ═ C double bond to the polyethylene glycol is preferably 1 to 8: 0.1 to 3.0, more preferably 1 to 5: 0.2 to 2.0. In the present invention, the amount of the polymerization inhibitor is preferably 0.1 to 1.0% by mass, more preferably 0.3 to 0.7% by mass, based on the mass of the acrylic monomer having a C ═ C double bond.
In the invention, the temperature of the second polymerization reaction is preferably 75-100 ℃, and more preferably 85-90 ℃; the time of the second polymerization reaction is preferably 2-5 hours, and more preferably 3-4 hours.
In the present invention, after the second polymerization reaction, the resulting system is preferably dried to obtain a hydrophilic polyurethane containing a C ═ C double bond. In the invention, the drying temperature is preferably 50-60 ℃, and the drying time is preferably 18-24 h.
In the second method, the invention preferably mixes polyethylene glycol and diisocyanate in an organic solvent, and carries out a third polymerization reaction under the action of a catalyst to obtain the-NCO-group-terminated polyurethane prepolymer. In the present invention, the components of the polyethylene glycol, the diisocyanate, the organic solvent and the catalyst are the same as those in the first method, and are not described herein again. In the invention, the molar ratio of the polyethylene glycol to the diisocyanate is preferably 1-5: 1-8, more preferably 2-3: 1-6; the dosage of the organic solvent is preferably 50-150% of the total mass of the polyethylene glycol and the diisocyanate, and more preferably 80-100%; the dosage of the catalyst is preferably 0.3-1.0% of the total mass of the polyethylene glycol and the diisocyanate, and more preferably 0.5-0.8%. In the invention, the temperature of the third polymerization reaction is preferably 75-100 ℃, and more preferably 80-85 ℃; the time of the third polymerization reaction is preferably 3-6 h, and more preferably 3-5 h.
After obtaining the-NCO group-terminated polyurethane prepolymer, the present invention preferably mixes the-NCO group-terminated polyurethane prepolymer with an acrylate monomer having a C ═ C double bond and a polymerization inhibitor, and performs a fourth polymerization reaction to obtain a polyurethane having a C ═ C double bond. In the present invention, the components and the amounts of the acrylic monomer containing C ═ C double bond and the polymerization inhibitor are the same as those in the above method one, and are not described herein again.
In the invention, the temperature of the fourth polymerization reaction is preferably 75-100 ℃, and more preferably 85-90 ℃; the time of the fourth polymerization reaction is preferably 2 to 5 hours, and more preferably 3 to 4 hours.
After the polyurethane containing C ═ C double bonds is obtained, in the present invention, the polyurethane containing C ═ C double bonds and the second type of hydrophilic chain extender are preferably mixed and subjected to a chain extension reaction to obtain a hydrophilic polyurethane containing C ═ C double bonds. In the present invention, the second type of hydrophilic chain extender is preferably 2- [ (2-aminoethyl) amino ] ethanesulfonic acid sodium salt; the amount of the second hydrophilic chain extender added is preferably 1 to 8% by mass of the solid content in the polyurethane containing a C ═ C double bond, and more preferably 3 to 5%. In the present invention, the method for mixing the polyurethane containing a C ═ C double bond and the second type of hydrophilic chain extender preferably includes: and dropwise adding the second hydrophilic chain extender into the polyurethane containing the C ═ C double bonds. In the invention, the dripping speed is preferably 0.5-10 mL/min, and more preferably 1-7 mL/min.
In the invention, the temperature of the chain extension reaction is preferably 30-45 ℃, and more preferably 40 ℃; the time of the chain extension reaction is preferably 0.5-1.5 h, and more preferably 1 h. The invention introduces hydrophilic groups into waterborne polyurethane molecules through chain extension reaction.
In the present invention, after the chain extension reaction, the resulting system is preferably dried to obtain a hydrophilic polyurethane containing a C ═ C double bond. In the invention, the drying temperature is preferably 50-60 ℃, and the drying time is preferably 18-24 h.
The preparation raw material of the waterborne polyurethane-silica sol composite antifogging agent provided by the invention comprises silica sol containing C ═ C double bonds. In the invention, the solid content of the silica sol containing C ═ C double bonds is 20-50%, preferably 25-40%; the particle diameter of the particles in the silica sol containing C ═ C double bonds is preferably 15 to 100nm, and more preferably 30 to 80 nm. In the present invention, the method for preparing the silica sol containing C ═ C double bonds preferably comprises the steps of: dissolving a silane coupling agent containing C ═ C double bonds and tetraethoxysilane in an aqueous solvent, adjusting the pH value to 3-4, and carrying out hydrolysis reaction to obtain silica sol containing C ═ C double bonds.
In the invention, the silane coupling agent containing the C ═ C double bond is preferably one or more of KH-570, A-174, Z-603 and KBM-503, and when the silane coupling agent containing the C ═ C double bond comprises a plurality of silane coupling agents, the proportion of each silane coupling agent is not particularly required, and any proportion can be adopted. In the present invention, the mass ratio of the C ═ C double bond-containing silane coupling agent to tetraethoxysilane is preferably 1:0.1 to 1, and more preferably 1: 0.5.
In the present invention, the aqueous solvent is preferably a mixture of water and ethanol, a mixture of water and acetone, or a mixture of water, ethanol and acetone. In the present invention, when the aqueous solvent is a mixture of water and ethanol, the mass ratio of water to ethanol is preferably 1: 1-100; when the aqueous solvent is a mixture of water and acetone, the mass ratio of water to acetone is preferably 1: 1-100; when the aqueous solvent is a mixture of water, ethanol and acetone, the mass ratio of water, ethanol and acetone is preferably 1: 1-100: 1 to 50.
In the invention, the reagent used for adjusting the pH value to 3-4 is preferably hydrochloric acid, and the invention has no special requirement on the concentration of the hydrochloric acid and can adopt the concentration of the hydrochloric acid commonly used by the technicians in the field. According to the invention, the hydrolysis of siloxane can be promoted by adjusting the pH value of the system to 3-4.
In the invention, the temperature of the hydrolysis reaction is preferably room temperature, and the time of the hydrolysis reaction is preferably 0.5-3 h. In the hydrolysis reaction process, siloxane is hydrolyzed to release hydroxyl.
In the invention, after the hydrolysis reaction, the obtained system is preferably heated to 40-60 ℃ and kept for 5-8 h to obtain the silica sol containing C ═ C double bonds. In the heat preservation process, silicon hydroxyl is condensed to form nano silica sol.
The preparation raw materials of the composite antifogging agent provided by the invention comprise a solvent. In the invention, the solvent is preferably one or more of ethanol, water and acetone, and when the solvent is a mixture of ethanol, water and acetone, the mass ratio of ethanol to water to acetone is preferably 0.1-1: 0.05-1: 0 to 0.5. The invention utilizes a solvent to fully disperse the hydrophilic polyurethane containing C ═ C double bonds, so as to obtain the polymer dispersion.
In the invention, the mass ratio of the hydrophilic polyurethane containing C ═ C double bonds, the silica sol containing C ═ C double bonds and the solvent is 5-15: 0.5-5: 80-95, preferably 8-10: 2-5: 90-92.
The preparation raw materials of the composite antifogging agent also comprise an ultraviolet light initiator, and the mass of the ultraviolet light initiator preferably accounts for 1-1.5% of the total mass of the waterborne polyurethane-silica sol composite antifogging agent. After the ultraviolet initiator is added, a cross-linking structure is formed between the hydrophilic polyurethane and the silica sol in the composite antifogging agent under the ultraviolet irradiation condition, so that the wear resistance and the durability of the antifogging effect of the coating can be further improved. In the invention, the ultraviolet initiator is preferably one or more of benzophenone, 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone, 2-hydroxy-methyl phenyl propane-1-one, 1-hydroxycyclohexyl phenyl ketone and methyl o-benzoylbenzoate, and when the ultraviolet initiator comprises a plurality of ultraviolet initiators, the invention has no special requirement on the proportion of each ultraviolet initiator, and the proportion can be any proportion.
The preparation raw materials of the composite antifogging agent provided by the invention preferably further comprise a functional assistant, and the functional assistant preferably comprises one or more of a wetting agent, a dispersing agent, a flatting agent and a defoaming agent. In the invention, the functional auxiliary agent is preferably a wetting agent, a dispersing agent, a leveling agent and an antifoaming agent, and the mass ratios of the wetting agent, the dispersing agent, the leveling agent and the antifoaming agent to the antifogging agent are preferably 0.1-1.5%, 0.1-2.0% and 0-3.0%, more preferably 0.3-1.0%, 0.5-1.0%, 0.2-1.0% and 0.2-2.0%, respectively.
The invention provides a preparation method of the waterborne polyurethane-silica sol composite antifogging agent, which comprises the following steps:
mixing hydrophilic polyurethane containing C ═ C double bonds with a solvent to obtain a polymer dispersion;
and mixing the polymer dispersion, silica sol containing C-C double bonds and an ultraviolet initiator to obtain the waterborne polyurethane-silica sol composite antifogging agent.
The invention mixes hydrophilic polyurethane containing C ═ C double bonds with a solvent to obtain a polymer dispersion. The specific mixing process is not particularly limited, and the hydrophilic polyurethane containing C ═ C double bonds may be uniformly dispersed in a solvent.
After the polymer dispersion is obtained, the polymer dispersion, silica sol containing C ═ C double bonds and an ultraviolet initiator are mixed to obtain the waterborne polyurethane-silica sol composite antifogging agent. The polymer dispersion is preferably mixed with a silica sol containing C ═ C double bonds and then with the uv initiator.
In the present invention, the polymer dispersion and the silica sol containing C ═ C double bonds are preferably mixed in such a manner that: the silica sol containing C ═ C double bonds is added dropwise to the polymer dispersion with stirring. In the invention, the stirring speed is preferably 100-300 r/min, and the dropping speed is preferably 0.5-2.0 mL/min. The invention adopts the dropwise mixing mode to fully mix the polymer dispersoid and the silica sol.
In the present invention, when the raw material for preparing the composite antifogging agent includes a functional adjuvant, the present invention preferably adds the functional adjuvant to the resulting system after the polymer dispersion, the silica sol containing C ═ C double bonds, and the uv initiator are mixed. In the present invention, when the functional additives include a plurality of functional additives, the order of addition of the functional additives is not particularly required.
In the invention, the appearance of the waterborne polyurethane-silica sol composite antifogging agent is yellowish transparent liquid or yellowish semitransparent liquid.
The invention also provides an application of the waterborne polyurethane-silica sol composite antifogging agent prepared by the technical scheme or the waterborne polyurethane-silica sol composite antifogging agent prepared by the preparation method of the technical scheme in antifogging products. In the present invention, the antifogging product preferably includes a mirror, glasses, goggles, various types of lenses, automobile glass, or rearview mirror.
In the present invention, the application preferably comprises the steps of: compounding the waterborne polyurethane-silica solThe antifogging agent is coated on the surface of the substrate to be treated and naturally dried to form a coating. In the present invention, the substrate to be treated preferably comprises glass, polystyrene, PET, PVC or PMMA. In the present invention, the manner of coating preferably includes spraying or wiping; the coating amount is preferably 0.01-0.10 g/cm2。
According to the invention, preferably, after the natural airing, the obtained film layer is subjected to ultraviolet irradiation to obtain the coating film. In the present invention, the power of the ultraviolet irradiation is preferably 2mW/cm2The time of the ultraviolet irradiation is preferably 30 min.
In the invention, the thickness of the coating film is preferably 1-20 μm, and the appearance of the coating film is a uniform and transparent film.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Mixing 0.03mol of polyethylene glycol PEG-1000, 0.05mol of diphenylmethane-4, 4' -diisocyanate (MDI), 0.005mol of 1, 2-dihydroxy-3-sodium propanesulfonate (DHPA) and 0.005mol of dimethylolbutyric acid (DMBA), adding 30g of solvent N, N-Dimethylformamide (DMF), adding 0.15g of bismuth catalyst (specifically BCAT-E20CX) for catalysis, and carrying out polymerization reaction for 5h at the temperature of 80 ℃ to obtain an-NCO-terminated polyurethane prepolymer; then adding 0.06mol of hydroxyethyl methacrylate and 0.05g of hydroquinone for polymerization inhibition, carrying out polymerization reaction at 85 ℃ for 3h for end capping, and drying at 50 ℃ for 24h after the reaction is finished to obtain hydrophilic polyurethane containing C ═ C double bonds;
mixing 20g of silane coupling agent KH-570 and 10g of ethyl orthosilicate, adjusting the pH value to 3-4 by using 10g of water and 60g of ethanol as solvents through hydrochloric acid, hydrolyzing for 1.5h at room temperature, heating to 60 ℃, and keeping the temperature for 6h to obtain silica sol containing C-C double bonds; the solid content of the silica sol is 30%, and the particle size of the silica sol is 30-80 nm;
mixing the hydrophilic polyurethane containing C ═ C double bonds, ethanol and water in a ratio of 8: 85: 7 to form a transparent polymer dispersion; dropwise adding the silica sol containing the C-C double bond into the polymer dispersion under stirring, wherein the mass ratio of the polymer dispersion to the silica sol containing the C-C double bond is 100: 2;
and then adding 1.5 wt% of ultraviolet initiator 2959 and 0.3 wt% of flatting agent BYK-333 into the obtained system, and uniformly stirring to obtain the waterborne polyurethane-silica sol composite antifogging agent.
The waterborne polyurethane-silica sol composite antifogging agent is a yellowish transparent liquid;
the waterborne polyurethane-silica sol composite antifogging agent is coated on the surface of glass, and the coating amount is 0.02-0.08 g/cm2And naturally drying for 10-30 min (the temperature is 10-20 ℃, and the humidity is 30-65%) to obtain a uniform and transparent coating film.
Example 2
Mixing 0.01mol of polyethylene glycol PEG-1000, 0.01mol of polyethylene glycol PEG-400 and 0.015mol of isophorone diisocyanate (IPDI), adding 20g of solvent N, N-Dimethylformamide (DMF), adding 0.10g of bismuth catalyst (specifically BCAT-E20CX) for catalysis, and carrying out polymerization reaction for 5h at 85 ℃ to obtain-NCO group end-capped polyurethane prepolymer; then 0.02mol of hydroxyethyl methacrylate and 0.05g of hydroquinone are added for polymerization inhibition, and the polymerization reaction is carried out for 3 hours for end capping at the temperature of 85 ℃; cooling to room temperature, dropwise adding 0.002mol of 2- [ (2-aminoethyl) amino ] ethanesulfonic acid sodium salt solution (the solvent is water, the concentration is 50%) within 30min, heating to 40 ℃, performing chain extension reaction for 1h, and introducing hydrophilic groups into waterborne polyurethane molecules; after the reaction is finished, drying for 24h at 50 ℃ to obtain hydrophilic polyurethane containing C ═ C double bonds;
mixing 20g of silane coupling agent KH-570 and 10g of ethyl orthosilicate, adjusting the pH value to 3-4 by using 10g of water and 60g of ethanol as solvents through hydrochloric acid, hydrolyzing for 1.5h at room temperature, heating to 60 ℃, and keeping the temperature for 6h to obtain silica sol containing C-C double bonds; the solid content of the silica sol is 30%, and the particle size of the silica sol is 30-80 nm;
mixing the hydrophilic polyurethane containing C ═ C double bonds, ethanol and water in a ratio of 10: 85: 5 to form a transparent polymer dispersion; dropwise adding the silica sol containing the C-C double bond into the polymer dispersion under stirring, wherein the mass ratio of the polymer dispersion to the silica sol containing the C-C double bond is 100: 5;
and then adding 1 wt% of ultraviolet initiator 2959 and 0.3 wt% of flatting agent BYK-333 into the obtained system, and uniformly stirring to obtain the waterborne polyurethane-silica sol composite antifogging agent.
The waterborne polyurethane-silica sol composite antifogging agent is a yellowish semitransparent liquid;
the waterborne polyurethane-silica sol composite antifogging agent is coated on the surface of glass, and the coating amount is 0.02-0.0.8 g/cm2And naturally drying for 10-25 min (the temperature is 10-20 ℃, and the humidity is 30-65%) to obtain a uniform and transparent coating film.
Test example 1
FIG. 1 is a schematic diagram of the film-forming and anti-fogging mechanism of the waterborne polyurethane-silica sol composite anti-fogging agent provided by the invention, and it can be seen from FIG. 1 that as the solvent volatilizes, physical entanglement is formed among polyurethane-silica sol latex particles, and finally a complete polymer film is formed; since the hydrophilic polyurethane containing C ═ C double bonds contains ionic hydrophilic groups and nonionic hydrophilic segments, water vapor can rapidly come into contact with the coating film and rapidly spread on the film surface, and in this way, the generation of small water droplets is prevented, thereby obtaining the anti-fogging effect.
Test example 2
Dropwise adding the waterborne polyurethane-silica sol composite antifogging agent prepared in the embodiment 1 of the invention on the surface of a base material, fully and uniformly wetting the base material, and drying at normal temperature to obtain a coating film, wherein the detection results of the transparency and the cotton gauze wiping resistance of the coating film are shown in fig. 2;
wherein, the transparency is shown in the uppermost graph in fig. 2, the transparency of the glass and polystyrene (PSt) substrate coated with the composite antifogging agent has no obvious influence, and characters below the substrate are clearly visible;
the wear resistance was measured by wiping with cotton gauze, using a friction tester, and the information and the measurement results are shown in table 1.
TABLE 1 abrasion resistance test results
Numbering 1# 2#
Base material Glass Polystyrene
Load bearing 500g 100g
Number of rubs 1200 times, no coating film is abnormal 500 times, no coating film is abnormal
Post-friction antifogging effect No abnormality No abnormality
As can be seen from Table 1, the coating film formed by the waterborne polyurethane-silica sol composite antifogging agent provided by the invention has good wear resistance.
Test example 3
Coating the waterborne polyurethane-silica sol composite antifogging agent prepared in the embodiment 2 on the surface of PSt, wherein the coating amount is 0.45-0.55 g, and airing at normal temperature to obtain a coating film which is marked as a sample which is not cured by UV;
placing the sample which is not cured by UV under ultraviolet irradiation for 30min, wherein the power of the ultraviolet irradiation is 2mW/cm2Marking the obtained coating film as a UV cured sample;
the un-cured sample and the UV-cured sample were placed over water vapor at 60 ℃ respectively, and the change of the initial stage of water vapor exposure (within 30 s) and the surface fogging were observed, and the detection results are shown in table 2 and fig. 3:
TABLE 2 antifogging Property test results
Figure BDA0002526447220000131
As can be seen from Table 2 and FIG. 3, the samples which are not cured by UV have good antifogging effect in the initial stage (within 30 s) of contacting with water vapor, have no fog on the surface, have no water drops, and are uniform and transparent; after 3min, large water drops appear, no fog exists, and when the state is kept to be close to 60min, fog spots appear and are continuously expanded; after 90min, the area of 1/3 shows a fog point; the UV-cured sample has water drops on the surface in the initial stage (within 30 s) of contacting with water vapor and can be rapidly spread, the initial antifogging effect is reduced compared with that of a coating before curing, and the molecular chain movement range is limited because the molecules form a cross-linked network after curing; large liquid drops are formed on the surface of the inner film within 10min to 4h, no fog exists, and the state is maintained to be close to about 5h, and then a fog point appears and is continuously expanded; after 6h, the area of 1/3 shows fog spots; the transparency of the coating film is good after the coating film is fully wetted; compared with the coating before UV curing, the duration of the anti-fogging effect is obviously prolonged.
FIG. 4 is a diagram showing the antifogging effect of the waterborne polyurethane-silica sol composite antifogging agent prepared in example 2 on glass and glasses; the specific test method comprises the following steps: the composite antifogging agent is evenly coated on the surface of the base material in a wiping mode, naturally dried and then placed above a water bath at 60 ℃, and the fogging phenomenon is observed. As can be seen from FIG. 4, the antifogging effect of the lens and glass coated with the antifogging agent is obvious, and the lens and glass are kept in a transparent state; the uncoated portions showed significant water beading and significantly affected the transparency of the substrate.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (6)

1. A water polyurethane-silica sol composite antifogging agent is prepared from hydrophilic polyurethane containing C ═ C double bonds, silica sol containing C ═ C double bonds, ultraviolet initiator and solvent; the mass ratio of the hydrophilic polyurethane containing C ═ C double bonds, the silica sol containing C ═ C double bonds and the solvent is 8-10: 0.5-5: 80-95; the solid content of the silica sol containing C ═ C double bonds is 20-50%;
the preparation method of the hydrophilic polyurethane containing the C ═ C double bond comprises the following steps:
mixing polyethylene glycol, diisocyanate and a first hydrophilic chain extender in an organic solvent, and carrying out a first polymerization reaction under the action of a catalyst to obtain a-NCO-group-terminated polyurethane prepolymer;
mixing the-NCO-group-terminated polyurethane prepolymer, an acrylate monomer containing C-C double bonds and a polymerization inhibitor, and carrying out a second polymerization reaction to obtain hydrophilic polyurethane containing C-C double bonds;
mixing polyethylene glycol and diisocyanate in an organic solvent, and carrying out a third polymerization reaction under the action of a catalyst to obtain a-NCO-group-terminated polyurethane prepolymer;
mixing the-NCO-group-terminated polyurethane prepolymer, an acrylate monomer containing C-C double bonds and a polymerization inhibitor, and carrying out a fourth polymerization reaction to obtain polyurethane containing C-C double bonds;
mixing the polyurethane containing the C-C double bond with a second hydrophilic chain extender, and carrying out chain extension reaction to obtain hydrophilic polyurethane containing the C-C double bond;
the polyethylene glycol is one or more of PEG-300, PEG-400, PEG-800, PEG-1000, PEG-2000 and PEG-4000;
the diisocyanate is one or more of isophorone diisocyanate, 1, 6-hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane-4, 4' -diisocyanate and 4, 4-dicyclohexylmethane diisocyanate;
the first hydrophilic chain extender is one or more of dimethylolpropionic acid, dimethylolbutyric acid and 1, 2-dihydroxy-3-sodium propane sulfonate;
the second hydrophilic chain extender is 2- [ (2-aminoethyl) amino ] ethanesulfonic acid sodium salt;
the organic solvent is acetone, ethyl acetate or N, N-dimethylformamide;
the catalyst is dibutyltin dilaurate, stannous octoate, 1, 4-dimethyl piperazine or an organic bismuth catalyst;
the acrylic ester monomer containing C ═ C double bonds is one or more of hydroxyethyl methacrylate, hydroxyethyl acrylate and hydroxypropyl acrylate;
the polymerization inhibitor is hydroquinone or p-benzoquinone;
the temperature of the first polymerization reaction and the temperature of the third polymerization reaction are 75-100 ℃ independently, and the time of the first polymerization reaction and the time of the third polymerization reaction are 3-6 h independently;
the temperature of the second polymerization reaction and the temperature of the fourth polymerization reaction are 75-100 ℃ independently, and the time of the second polymerization reaction and the time of the fourth polymerization reaction are 2-5 h independently;
the temperature of the chain extension reaction is 30-45 ℃; the time of the chain extension reaction is 0.5-1.5 h;
the preparation method of the silica sol containing C ═ C double bonds comprises the following steps:
dissolving a silane coupling agent containing C ═ C double bonds and tetraethoxysilane in an aqueous solvent, adjusting the pH value to 3-4, and carrying out hydrolysis reaction to obtain silica sol containing C ═ C double bonds.
2. The waterborne polyurethane-silica sol composite antifogging agent according to claim 1, wherein the mass of the ultraviolet initiator accounts for 1-1.5% of the total mass of the waterborne polyurethane-silica sol composite antifogging agent.
3. The preparation method of the waterborne polyurethane-silica sol composite antifogging agent of any one of claims 1 to 2, comprising the following steps:
mixing hydrophilic polyurethane containing C ═ C double bonds with a solvent to obtain a polymer dispersion;
and mixing the polymer dispersion, silica sol containing C-C double bonds and an ultraviolet initiator to obtain the waterborne polyurethane-silica sol composite antifogging agent.
4. The application of the waterborne polyurethane-silica sol composite antifogging agent prepared according to any one of claims 1 to 2 or the waterborne polyurethane-silica sol composite antifogging agent prepared according to the preparation method of claim 3 in antifogging products.
5. Use according to claim 4, characterized in that it comprises the following steps: and coating the waterborne polyurethane-silica sol composite antifogging agent on the surface of a substrate to be treated, and naturally airing to form a coating.
6. The use of claim 4, wherein after the natural drying, the method further comprises subjecting the obtained film layer to ultraviolet irradiation to obtain a coating film.
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CN113999599B (en) * 2021-10-11 2022-05-24 华南理工大学 Waterborne polyurethane-silica sol antifogging coating and preparation method and application thereof
CN114989366A (en) * 2022-06-16 2022-09-02 浙江材华科技有限公司 Waterborne polyurethane resin composition and preparation method thereof
CN115286834B (en) * 2022-07-27 2023-10-24 安徽禾臣新材料有限公司 Wear-resistant oil-proof protective film and preparation method thereof
CN115678328A (en) * 2022-11-04 2023-02-03 江南大学 Preparation method of UV-cured super-hydrophilic anti-fog coating containing sodium sulfonate compound
CN116239948B (en) * 2022-12-27 2024-01-02 江苏汇鼎光学眼镜有限公司 Super-water-resistant lens and preparation method thereof

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