CN111057264A - High-transmittance intelligent liquid crystal dimming film and preparation method thereof - Google Patents
High-transmittance intelligent liquid crystal dimming film and preparation method thereof Download PDFInfo
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- C08J5/18—Manufacture of films or sheets
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
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- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/105—Esters; Ether-esters of monocarboxylic acids with phenols
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- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/28—Glass
Abstract
The invention discloses a high-transmittance intelligent liquid crystal dimming film and a preparation method thereof. The preparation method of the high-transmittance intelligent liquid crystal dimming film comprises the following steps: step S1: fully and uniformly stirring urethane acrylate, biphenyl liquid crystal, spacer particles, a photoinitiator, a surfactant and pentaerythritol ester to obtain a mixed solution; step S2: placing the mixed solution between two conductive films, and rolling to form a thin film; step S3: carrying out first-step ultraviolet irradiation polymerization on the film; step S4: and then, under the condition of applying an electric field to the film, carrying out second-step ultraviolet irradiation polymerization on the film to obtain the intelligent liquid crystal dimming film with high transmittance. The high-transmittance intelligent liquid crystal dimming film disclosed by the invention has better shielding property in an off state and better visual effect in an on state, and is suitable for occasions needing privacy protection, space permeability, safety defense and light regulation.
Description
Technical Field
The invention relates to the technical field of photoelectric materials, in particular to a high-transmittance intelligent liquid crystal dimming film and a preparation method thereof.
Background
The intelligent light adjusting film is an electro-optical functional material capable of realizing light control, and the intelligent light adjusting film technology was invented by Kent university in Texas in the United states in the last 80 th century and authorizes the commercialization amount of American national institute of technology. Subsequently, manufacturers in korea, japan, and the like start to enter the field in the middle of the nineties of the last century, and the manufacturers in china are put into the production field after the intelligent light modulation film comes out for more than ten years, but because the organic synthesis process is slowly developed, the price of liquid crystal and the price of polymer raw materials are high, the produced intelligent light modulation film product is expensive, the market acceptance is low, the development is slow, and the application of the intelligent light modulation film is mainly focused on laboratory research and the application in aerospace and military industry.
In recent years, liquid crystal industry and light-cured material industry are rapidly developed, the manufacturing cost of intelligent light-adjusting film products is gradually reduced, and along with the improvement of national income, consumers not only need to meet basic requirements on the performance of the products, but also pay more attention to the intellectualization and environment protection of the products. The intelligent light adjusting film has controllable light transmittance, is energy-saving and environment-friendly, is widely accepted and applied in the market, the market demand is increased year by year, and the number of domestic manufacturers is gradually increased.
The invention of application No. 201510713822.9 discloses a method for preparing a nano-doped intelligent light modulation film, which comprises the steps of preparing nano metal oxide particle crystal gel by using a hydrothermal method or a solvothermal method synthesis method, mixing the gel nano particles with strong dispersion activity into a prepolymer, adding a small amount of coupling agent, mixing the nano particles with the prepolymer, dispersing the nano particles by using stirring ultrasonic waves to form prepolymer nano sol, mixing the prepolymer nano sol with acrylic ester and nematic liquid crystal, adding a spacer, coating the surface of a PET conductive film by using a roll coating method, and initiating photopolymerization under the ultraviolet light condition to prepare the intelligent light modulation film with excellent electro-optic characteristics. The polymer matrix is subjected to nano modification, so that parameters such as dielectric constant, refractive index and the like of the polymer matrix are changed, the electro-optical performance of the intelligent light adjusting film is improved, the working voltage is 30V, and the light transmittance of the intelligent light adjusting film is about 70%; meanwhile, the nano metal oxide particles synthesized by a hydrothermal or solvent method are dispersed in the polymer matrix, so that the nano particles have good dispersion activity and are not easy to agglomerate, and the uniform dispersion of the nano particles in the polymer matrix is ensured.
The invention of application number 201510377679.0 discloses an intelligent light adjusting film and a preparation method thereof, comprising two transparent conductive ITO film layers and a polymer-liquid crystal mixed functional layer arranged between the two film layers, wherein the polymer-liquid crystal mixed functional layer is prepared from a polymer intermediate, liquid crystal and an accelerant. The intelligent light modulation film has a more reasonable structure by improving the proportion of the polymer liquid crystal mixed liquid, so that the light modulation film achieves a better use effect, and the quality defect caused by the precision problem of a domestic film material is overcome. Through experimental production, the performance index of the intelligent light adjusting film completely meets the quality requirements of the same products at home and abroad, and the cost of the intelligent light adjusting film is reduced by 40-50% compared with the product produced by adopting the imported auxiliary material because the intelligent light adjusting film completely adopts the domestic original auxiliary material; the preparation method of the intelligent light-adjusting film is suitable for production of production lines with stronger automation and higher production efficiency, and achieves the purpose of localization of the intelligent light-adjusting film.
The invention of application No. 201610391093.4 provides an intelligent light adjusting film and its preparation and application. The structure of intelligence membrane of adjusting luminance includes: the vanadium oxide layer with the phase change characteristic is arranged on the substrate; a nano silicon layer or a silicon alloy layer capable of improving the light transmittance of the vanadium oxide layer is compounded on at least one side of the vanadium oxide layer; the substrate is provided with at least one group of composite layers of vanadium oxide layers and nano silicon layers or silicon alloy layers. According to the invention, through the design of the film layer structure and the selection of the film layer material, the nano silicon layer and the vanadium oxide layer are compounded or the silicon alloy layer and the vanadium oxide layer are subjected to heat treatment, so that the mutual diffusion between the nano silicon or the silicon alloy and the vanadium oxide material is realized, and the purposes of improving the visible light transmittance and reducing the phase transition temperature are achieved. The invention has the advantages of simplified process, reduced cost, easy operation, etc.
Disclosure of Invention
The invention provides a preparation method of a high-transmittance intelligent liquid crystal dimming film.
The preparation method of the high-transmittance intelligent liquid crystal dimming film comprises the following steps:
step S1: fully and uniformly stirring urethane acrylate, biphenyl liquid crystal, spacer particles, a photoinitiator, a surfactant and pentaerythritol ester to obtain a mixed solution;
step S2: placing the mixed solution between two conductive films, and rolling to form a thin film;
step S3: carrying out first-step ultraviolet irradiation polymerization on the film;
step S4: and then, under the condition of applying an electric field to the film, carrying out second-step ultraviolet irradiation polymerization on the film to obtain the intelligent liquid crystal dimming film with high transmittance.
Further, the preparation method of the high-transmittance intelligent liquid crystal dimming film comprises the following steps:
step S1: fully and uniformly stirring 20-60 parts by weight of polyurethane acrylate, 30-70 parts by weight of biphenyl liquid crystal, 0.01-2 parts by weight of spacer particles, 0.01-10 parts by weight of photoinitiator, 0.5-3 parts by weight of surfactant and 0.3-3 parts by weight of pentaerythritol ester to obtain a mixed solution;
step S2: placing the mixed solution between two conductive films, wherein the conductive layers of the conductive films are oppositely arranged at the inner sides and face to face, coating the mixed solution in the middle of the conductive films by coating equipment, and rolling to form a thin film;
step S3: carrying out the first-step ultraviolet irradiation polymerization on the film, wherein the ultraviolet intensity is 0.1-1 mw/cm2The ultraviolet irradiation time is 10-60 s, so that the polymerizable monomer in the film system is incompletely polymerized;
step S4: then, under the condition of applying an electric field to the film, the frequency of the electric field is 0.01-10 Hz, the applied voltage is 100-200V, and the film is subjected to a second step of ultraviolet light irradiation polymerization, wherein the intensity of the ultraviolet light is 0.1-1 mw/cm2And the ultraviolet irradiation time is 2-4 minutes, so that the residual polymerizable monomer is completely polymerized to obtain the high-transmittance intelligent liquid crystal dimming film.
The biphenyl liquid crystal used in the present invention may be prepared using a commercially available biphenyl liquid crystal, or may be prepared by referring to a conventional patent or literature.
In the above technical solution, the urethane acrylate may be urethane acrylate in the prior art, or may be hyperbranched urethane acrylate.
Further, the polyurethane acrylate is hyperbranched polyurethane acrylate, and is obtained by using hyperbranched polyester as a central core, firstly performing hydrophilization modification on part of terminal hydroxyl groups of the hyperbranched polyester by using maleic anhydride to obtain a hydrophilic modified substance, and then performing acrylation modification on the rest of the terminal hydroxyl groups by using an addition product of isophorone diisocyanate and hydroxyethyl acrylate.
Further, the preparation process of the hyperbranched polyurethane acrylate comprises the following steps:
(1) adding 8-12 g of isophorone diisocyanate, 4-6 g of hydroxyethyl acrylate and 0.05-0.08 g of dibutyltin dilaurate into a reaction device under the atmosphere of nitrogen, uniformly mixing, heating to 30-35 ℃, and reacting at 30-35 ℃ for 2-4 hours to prepare an addition product of isophorone diisocyanate and hydroxyethyl acrylate;
(2) dissolving 8-12 g of hyperbranched polyester and 4-5 g of maleic anhydride in 30-50 mL of tetrahydrofuran, and fully stirring to form a uniform solution; then adding 0.03-0.06 g of catalyst 4-dimethylaminopyridine, heating to 50-60 ℃, reacting for 3-6 hours at 50-60 ℃, and preparing a hydrophilic modifier by using a mono-esterification reaction between a terminal hydroxyl group of the hyperbranched polyester and an anhydride group of maleic anhydride;
(3) adding an addition product of isophorone diisocyanate and hydroxyethyl acrylate into a hydrophilic modifier, adding 0.08-0.15 g of dibutyltin dilaurate, heating to 70-80 ℃, and reacting at 70-80 ℃ for 4-7 hours to obtain the hyperbranched polyurethane acrylate.
In some embodiments of the invention, the photoinitiator is photoinitiator 1173.
In some technical schemes of the present invention, the photoinitiator is a nanocellulose crystal grafted photoinitiator 1173, and the preparation process is as follows: adding 20-40 g of anhydrous acetone into 0.3-1 g of nano-cellulose crystals, and performing ultrasonic dispersion for 30-50 minutes to obtain a dispersion liquid in which the nano-cellulose crystals are uniformly dispersed in the acetone; adding the dispersion liquid and 6-20 g of isophorone diisocyanate into a reaction device provided with a stirrer, a thermometer and a condenser pipe, adding 0.04-0.1 g of catalyst dibutyltin dilaurate, heating to 40-50 ℃, and carrying out heat preservation reaction for 4 hours at 40-50 ℃; then 6-22 g of photoinitiator 1173 is added, heated to 60-70 ℃, and reacted for 4-7 hours at 60-70 ℃; after the reaction is finished, performing centrifugal separation, and collecting bottom solids; and washing the bottom solid with acetone, and drying at normal temperature in vacuum to obtain the nano cellulose crystal grafted photoinitiator 1173.
Further, the surfactant is polyether modified silicone surfactant, glycoside modified silicone surfactant or polyglycerol modified silicone surfactant.
Further, the surfactant is preferably a polyglycerol-modified silicone surfactant.
In some technical schemes of the invention, the preparation process of the polyglycerol-modified silicone surfactant is as follows:
(1) weighing 150-180 g of octamethylcyclotetrasiloxane, 100-130 g of polydimethyl hydrosilicon and 15-18 g of hexamethyldisiloxane, adding the octamethylcyclotetrasiloxane, the polydimethyl hydrosilicon and the hexamethyldisiloxane into a reaction device, stirring for 10-30 minutes under the protection of nitrogen, heating to 40-45 ℃, adding 3-6 g of 98 mass percent concentrated sulfuric acid, and then fully stirring for reaction for 30-60 hours; after the reaction is stopped, adding sodium bicarbonate to neutralize excessive acid, finally vacuum-drying at 80-85 ℃ for 2-4 hours, naturally cooling to room temperature, filtering, and taking filtrate to obtain the siloxane;
(2) weighing 80-120 g of allyl glycidyl ether and 130-150 g of diglycerol, adding into a reaction kettle, stirring for 10-20 minutes under the protection of nitrogen, adding 1.2-1.8 g of potassium hydroxide, heating to 90-92 ℃, and stirring for reaction for 1-3 hours; naturally cooling to room temperature, and performing vacuum distillation at room temperature to remove water and low-boiling-point substances to obtain allyl polyglycerol;
(3) 0.1-0.2 mL Karstedt catalyst is fully mixed with 30-35 g of hydrosiloxane to obtain the hydrosiloxane containing the catalyst; adding 130-160 mL of isopropanol into a reaction device under the protection of nitrogen, heating to 80-90 ℃, simultaneously adding hydrosiloxane containing a catalyst and 50-55 g of allyl polyglycerol, and continuously reacting for 2-3 hours at 80-90 ℃; and after the reaction is stopped, naturally cooling to room temperature to obtain the polyglycerol modified organosilicon surfactant.
Further, the spacer is a hollow mesoporous organic silicon microsphere and/or a hollow glass microsphere. Preferably, the spacer is a hollow mesoporous organic silicon microsphere and a hollow glass microsphere in a mass ratio of 1: 1, in a mixture of the components.
The preparation process of the hollow mesoporous organic silicon microsphere comprises the following steps: dispersing 300-600 mg of nano silicon dioxide in 20-40 mL of deionized water, and carrying out ultrasonic treatment for 30-50 minutes to obtain a silicon dioxide dispersion liquid; adding 1-2 g of hexadecyl trimethyl ammonium chloride, 10-20 mu L of triethanolamine and 40-60 mL of deionized water into a reaction device, and stirring for 1-1.5 hours at normal temperature; then adding the nano silicon dioxide dispersion liquid, and stirring for 1-1.5 hours; then adding 0.3-1.2 mL of bis- [3- (triethoxysilyl) propyl ] -tetrasulfide, stirring for 1-2 hours at 70-80 ℃, performing centrifugal separation, and collecting precipitates; washing the precipitate with anhydrous ethanol, and drying at normal temperature; and (3) mixing the dried precipitate in a solid-liquid ratio of 1: (20-40) (g/mL) is dispersed in a sodium carbonate solution with the molar concentration of 0.3-0.9 mol/L, stirred for 1-2 hours at 50-60 ℃, and then centrifuged to collect bottom sediment; washing the bottom precipitate with deionized water, then washing with a sodium chloride methanol solution with the mass fraction of 1-2%, and vacuum-drying at 40-50 ℃ to obtain the hollow mesoporous organic silicon microsphere.
Further, the conductive film is one of a nano silver conductive film, a graphene conductive film, an indium tin oxide film and a polymer conductive film.
The second technical problem to be solved by the invention is to provide an intelligent liquid crystal dimming film with high transmittance.
The high-transmittance intelligent liquid crystal dimming film is processed by using any one of the preparation methods of the high-transmittance intelligent liquid crystal dimming film.
The innovation of the invention is that:
1. the hyperbranched polymer with a special structure and active end groups enriched on the surface of molecules is applied to a curing light modulation film system, and the terminal hydroxyl groups of the hyperbranched polyester are subjected to hydrophilic modification and acrylic acid functional group modification, so that the hyperbranched polyester has dispersing capacity and ultraviolet curing capacity at the same time, and has excellent film forming property, adhesive force, moderate hardness and good stability after film forming.
2. According to the invention, a nano-cellulose grafted photoinitiator is used, and a small molecular photoinitiator 2-hydroxy-2-methyl-1-phenyl acetone is grafted to the surface of nano-cellulose through a chemical reaction, so that a low-mobility, low-toxicity and low-volatility macromolecular photoinitiator is prepared, the photoinitiation efficiency is good, on the other hand, the nano-cellulose has good mechanical properties, can play a role of a reinforcing agent in curing urethane acrylate, has good compatibility with a matrix, and improves the mechanical properties and stability of a cured film.
3. As the curing process is carried out, the polymer network density is continuously increased, the meshes are reduced, the liquid crystal particles are extruded to reduce the size of the liquid crystal particles, the viscosity of the system is also obviously increased, and the occurrence of a phase separation structure is further limited, so that the final phase form of the system is basically set, the subsequent irradiation is only to further cure the polymer matrix, and the formed polymer network structure has uniform gaps. According to the invention, by adding a proper active agent, the gelation degree of a local polymer is reduced, the precipitation of liquid microcrystals is facilitated, larger liquid drops are formed, most of aggregation and precipitation are avoided, and the haze and the transmittance are ensured.
The high-transmittance intelligent liquid crystal dimming film disclosed by the invention has better shielding property, lower parallel light transmittance and high haze in an off state, has better visual effect, higher light transmittance and lower haze in an on state, and is suitable for occasions needing privacy protection, space permeability, safety defense and light regulation, such as high-grade hotel rooms, museums, banks, conference rooms, shop windows and the like.
Detailed Description
The raw materials in the examples are as follows:
in the embodiment, the conductive film is an indium tin oxide film.
The wavelength of the ultraviolet light in the examples is 365 nm.
Isophorone diisocyanate, CAS No.: 4098-71-9.
Hydroxyethyl acrylate, CAS No.: 818-61-1.
Dibutyltin dilaurate, CAS No.: 77-58-7.
Hyperbranched polyesters were prepared according to example 1 of patent application No. 201410579643.6.
Maleic anhydride, CAS No.: 108-31-6.
4-dimethylaminopyridine, CAS No.: 1122-58-3.
Octamethylcyclotetrasiloxane, CAS No.: 556-67-2.
Hexamethyldisiloxane, CAS number: 107-46-0.
Allyl glycidyl ether, CAS No.: 106-92-3.
Diglycerol, CAS No.: 59113-36-9.
Karstedt catalyst, CAS number: 81032-58-8.
In the case where the present invention is not specifically described, the absolute pressure of the vacuum drying is 0.06 MPa.
Example 1
The preparation method of the intelligent liquid crystal dimming film with high transmittance comprises the following steps:
step S1: fully and uniformly stirring 30 parts by weight of urethane acrylate, 50 parts by weight of biphenyl liquid crystal (specifically, 4' -allyloxy-4-perfluorooctanoyloxy-biphenyl prepared by using example one of reference patent application No. 201010165461.6), 1.2 parts by weight of hollow glass microspheres (a factory of Baifeng mineral products in Lingshou county, the particle size is 10 micrometers, the wall thickness is 1 micrometer), 1.2 parts by weight of photoinitiator 1173 (chemical name is 2-hydroxy-2-methyl-1-phenyl-1-acetone, CAS number is 7473-98-5), 1 part by weight of polyether modified organosilicon surfactant (prepared by example one of reference patent application No. 201510054047.0), and 0.9 part by weight of pentaerythritol ester (CAS number is 8050-10-0) to obtain a mixed solution;
step S2: placing the mixed solution between two conductive films, wherein the conductive layers of the conductive films are oppositely arranged on the inner sides and face to face, coating the mixed solution in the middle of the conductive films through a manual roller coater, and rolling to form a thin film;
step S3: the film is subjected to the first step of ultraviolet irradiation polymerization, and the intensity of the ultraviolet light is 0.1mw/cm2The ultraviolet irradiation time is 50s, so that the polymerizable monomer in the film system is incompletely polymerized;
step S4: then, under the condition of applying an electric field to the film, the frequency of the electric field is 0.01Hz, the voltage is applied to 160V, and the film is subjected to a second step of ultraviolet light irradiation polymerization, wherein the intensity of the ultraviolet light is 0.5mw/cm2And the ultraviolet irradiation time is 3 minutes, so that the residual polymerizable monomer is completely polymerized to obtain the high-transmittance intelligent liquid crystal dimming film with the thickness of 20 mu m.
The urethane acrylate is prepared by the following specific preparation method according to the first example of the patent application No. 201410830852.3:
(1) adding 222g of isophorone diisocyanate, 1.69g of dibutyltin dilaurate and 0.169g of p-hydroxyanisole into a reaction device, starting stirring, controlling the temperature in a water bath, weighing 116g of hydroxyethyl acrylate, placing the weighed hydroxyethyl acrylate into a constant-pressure dropping funnel, starting dropping, controlling the dropping speed, keeping the temperature for 120 minutes after dropping is finished, and reacting to generate an intermediate product A for later use;
(2) weighing 118g of 5-hydroxy-1, 3-dioxane-2-ketone, placing the weighed 5-hydroxy-1, 3-dioxane-2-ketone into a reaction device, heating the mixture to 50 ℃ at the speed of 2 ℃/min, dropwise adding the intermediate product A obtained in the step (1), controlling the dropwise adding speed to be 0.02g/s, controlling the temperature of a water bath to be 50 ℃, stirring the mixture at a constant temperature after titration, heating the mixture to 80 ℃ for reaction for 60 minutes, measuring the-NCO content, finishing the reaction when the-NCO content is 0, and discharging the product.
Example 2
The preparation method of the intelligent liquid crystal dimming film with high transmittance comprises the following steps:
step S1: fully and uniformly stirring 30 parts by weight of urethane acrylate, 50 parts by weight of biphenyl liquid crystal (specifically, 4' -allyloxy-4-perfluorooctanoyloxy-biphenyl prepared by using example one of reference patent application No. 201010165461.6), 1.2 parts by weight of hollow glass microspheres (a factory of Baifeng mineral products in Lingshou county, the particle size is 10 micrometers, the wall thickness is 1 micrometer), 1.2 parts by weight of photoinitiator 1173 (chemical name is 2-hydroxy-2-methyl-1-phenyl-1-acetone, CAS number is 7473-98-5), 1 part by weight of polyether modified organosilicon surfactant (prepared by example one of reference patent application No. 201510054047.0), and 0.9 part by weight of pentaerythritol ester (CAS number is 8050-10-0) to obtain a mixed solution;
step S2: placing the mixed solution between two conductive films, wherein the conductive layers of the conductive films are oppositely arranged on the inner sides and face to face, coating the mixed solution in the middle of the conductive films through a manual roller coater, and rolling to form a thin film;
step S3: the film is subjected to the first step of ultraviolet irradiation polymerization, and the intensity of the ultraviolet light is 0.1mw/cm2The ultraviolet irradiation time is 50s, so that the polymerizable monomer in the film system is incompletely polymerized;
step S4: then, under the condition of applying an electric field to the film, the frequency of the electric field is 0.01Hz, the voltage is applied to 160V, and the film is subjected to a second step of ultraviolet light irradiation polymerization, wherein the intensity of the ultraviolet light is 0.5mw/cm2And the ultraviolet irradiation time is 3 minutes, so that the residual polymerizable monomer is completely polymerized to obtain the high-transmittance intelligent liquid crystal dimming film with the thickness of 20 mu m.
The polyurethane acrylate is hyperbranched polyurethane acrylate, and the preparation process comprises the following steps:
(1) under the atmosphere of nitrogen, adding 10.18g of isophorone diisocyanate, 5.32g of hydroxyethyl acrylate and 0.075g of dibutyltin dilaurate into a reaction device, uniformly mixing, heating to 35 ℃ at the speed of 2 ℃/min, and reacting for 2.5 hours at the temperature of 35 ℃ to prepare an addition product of isophorone diisocyanate and hydroxyethyl acrylate;
(2) dissolving 10g of hyperbranched polyester and 4.49g of maleic anhydride in 50mL of tetrahydrofuran, and fully stirring to form a uniform solution; then adding 0.056g of catalyst 4-dimethylamino pyridine, heating to 50 ℃ at the speed of 2 ℃/min, reacting for 5 hours at 50 ℃, and preparing a hydrophilic modifier by utilizing the mono-esterification reaction between the terminal hydroxyl of the hyperbranched polyester and the anhydride group of the maleic anhydride;
(3) and adding an addition product of isophorone diisocyanate and hydroxyethyl acrylate into the hydrophilic modifier through a dropping funnel, wherein the dropping speed is 0.1mL/min, adding 0.1g of dibutyltin dilaurate, heating to 70 ℃ at the speed of 2 ℃/min, and reacting for 5 hours at 70 ℃ to obtain the hyperbranched polyurethane acrylate.
Example 3
The preparation method of the intelligent liquid crystal dimming film with high transmittance comprises the following steps:
step S1: fully and uniformly stirring 30 parts by weight of urethane acrylate, 50 parts by weight of biphenyl liquid crystal (specifically, 4' -allyloxy-4-perfluorooctanoyloxy-biphenyl prepared by using example one of reference patent application No. 201010165461.6), 1.2 parts by weight of hollow glass microspheres (particle size 10 micrometers, wall thickness 1 micrometers, in a factory, guohou county, baifeng mineral product processing factory), 3 parts by weight of photoinitiator, 1 part by weight of polyether modified organosilicon surfactant (prepared by using example one of reference patent application No. 201510054047.0), and 0.9 part by weight of pentaerythritol ester (CAS No. 8050-10-0) to obtain a mixed solution;
step S2: placing the mixed solution between two conductive films, wherein the conductive layers of the conductive films are oppositely arranged on the inner sides and face to face, coating the mixed solution in the middle of the conductive films through a manual roller coater, and rolling to form a thin film;
step S3: the film is subjected to the first step of ultraviolet irradiation polymerization, and the intensity of the ultraviolet light is 0.1mw/cm2The ultraviolet irradiation time is 50s, so that the polymerizable monomer in the film system is incompletely polymerized;
step S4: then, under the condition of applying an electric field to the film, the frequency of the electric field is 0.01Hz, the voltage is applied to 160V, and the film is subjected to a second step of ultraviolet light irradiation polymerization, wherein the intensity of the ultraviolet light is 0.5mw/cm2And the ultraviolet irradiation time is 3 minutes, so that the residual polymerizable monomer is completely polymerized to obtain the high-transmittance intelligent liquid crystal dimming film with the thickness of 20 mu m.
The polyurethane acrylate was hyperbranched polyurethane acrylate and the preparation procedure was the same as in example 2.
The photoinitiator is a nano-cellulose crystal grafted photoinitiator 1173, and the preparation process comprises the following steps: adding 30g of anhydrous acetone into 0.5g of nano-cellulose crystals (Shanghai New Material particle, Ltd., width 4-10 nm, length 50-100 nm) and performing ultrasonic dispersion for 30 minutes under the conditions of ultrasonic power 300W and ultrasonic frequency 25kHz to obtain a dispersion liquid in which the nano-cellulose crystals are uniformly dispersed in the acetone; adding the dispersion and 10g of isophorone diisocyanate into a reaction device provided with a stirrer, a thermometer and a condenser pipe; adding 0.06g of catalyst dibutyltin dilaurate, heating to 50 ℃ at the speed of 2 ℃/minute, and carrying out heat preservation reaction at 50 ℃ for 4 hours; then 11g of photoinitiator 1173 is added, heated to 60 ℃ at the speed of 2 ℃/minute and reacted for 5 hours at 60 ℃; after the reaction is finished, centrifuging for 30 minutes at 4000 revolutions per minute, and collecting a bottom solid; and (3) washing the bottom solid with acetone with the weight 50 times of that of the bottom solid, and drying the bottom solid in vacuum at normal temperature to obtain the nano cellulose crystal grafted photoinitiator 1173.
Example 4
The preparation method of the intelligent liquid crystal dimming film with high transmittance comprises the following steps:
step S1: fully and uniformly stirring 30 parts by weight of urethane acrylate, 50 parts by weight of biphenyl liquid crystal (specifically, 4' -allyloxy-4-perfluorooctanoyloxy-biphenyl prepared by using example one of reference patent application No. 201010165461.6), 1.2 parts by weight of hollow glass microspheres (particle size 10 mu m, wall thickness 1 mu m, manufactured by a Baifeng mineral processing factory in Lingshou county), 3 parts by weight of photoinitiator, 1 part by weight of glycosyl modified organosilicon surfactant (prepared by using example two of reference patent application No. 201310746590.8), and 0.9 part by weight of pentaerythritol ester (CAS No. 8050-10-0) to obtain a mixed solution;
step S2: placing the mixed solution between two conductive films, wherein the conductive layers of the conductive films are oppositely arranged on the inner sides and face to face, coating the mixed solution in the middle of the conductive films through a manual roller coater, and rolling to form a thin film;
step S3: the film is subjected to the first step of ultraviolet irradiation polymerization, and the intensity of the ultraviolet light is 0.1mw/cm2The ultraviolet irradiation time is 50s, so that the polymerizable monomer in the film system is incompletely polymerized;
step S4: then, under the condition of applying an electric field to the film, the frequency of the electric field is 0.01Hz, the voltage is applied to 160V, and the film is subjected to a second step of ultraviolet light irradiation polymerization, wherein the intensity of the ultraviolet light is 0.5mw/cm2Ultraviolet irradiation time of 3 minutesSo that the residual polymerizable monomer is completely polymerized to obtain the intelligent liquid crystal dimming film with the high transmittance and the thickness of 20 mu m.
The polyurethane acrylate was hyperbranched polyurethane acrylate and the preparation procedure was the same as in example 2.
The photoinitiator is a nano-cellulose crystal grafted photoinitiator 1173, and the preparation process is the same as that of example 3.
Example 5
The preparation method of the intelligent liquid crystal dimming film with high transmittance comprises the following steps:
step S1: fully and uniformly stirring 30 parts by weight of urethane acrylate, 50 parts by weight of biphenyl liquid crystal (specifically, 50 parts by weight of 4' -allyloxy-4-perfluorooctanoyloxy-biphenyl prepared in example one of reference patent application No. 201010165461.6), 1.2 parts by weight of hollow glass microspheres (a factory of Baifeng mineral products in Lingshou county, the particle size is 10 micrometers, the wall thickness is 1 micrometer), 3 parts by weight of photoinitiator, 1 part by weight of polyglycerol-modified organosilicon surfactant and 0.9 part by weight of pentaerythritol ester (CAS number 8050-10-0) to obtain a mixed solution;
step S2: placing the mixed solution between two conductive films, wherein the conductive layers of the conductive films are oppositely arranged on the inner sides and face to face, coating the mixed solution in the middle of the conductive films through a manual roller coater, and rolling to form a thin film;
step S3: the film is subjected to the first step of ultraviolet irradiation polymerization, and the intensity of the ultraviolet light is 0.1mw/cm2The ultraviolet irradiation time is 50s, so that the polymerizable monomer in the film system is incompletely polymerized;
step S4: then, under the condition of applying an electric field to the film, the frequency of the electric field is 0.01Hz, the voltage is applied to 160V, and the film is subjected to a second step of ultraviolet light irradiation polymerization, wherein the intensity of the ultraviolet light is 0.5mw/cm2And the ultraviolet irradiation time is 3 minutes, so that the residual polymerizable monomer is completely polymerized to obtain the high-transmittance intelligent liquid crystal dimming film with the thickness of 20 mu m.
The polyurethane acrylate was hyperbranched polyurethane acrylate and the preparation procedure was the same as in example 2.
The photoinitiator is a nano-cellulose crystal grafted photoinitiator 1173, and the preparation process is the same as that of example 3.
The preparation process of the polyglycerol modified organosilicon surfactant comprises the following steps:
(1) 178g of octamethylcyclotetrasiloxane, 120g of polydimethylsiloxy (hydrogen mass ratio in hydrogen-containing silicone oil is 1.66 wt%), 16.2g of hexamethyldisiloxane are weighed and added into a reaction device, stirred for 30 minutes at 300 revolutions per minute under the protection of nitrogen, then heated to 45 ℃ at the speed of 2 ℃/minute, 4g of concentrated sulfuric acid with the mass fraction of 98% is added, and then fully stirred and reacted for 50 hours; after the reaction is stopped, adding sodium bicarbonate to neutralize excessive acid, finally performing vacuum drying at 85 ℃ for 2 hours, naturally cooling to room temperature, filtering by using 200-mesh filter cloth, and taking filtrate to obtain the siloxane;
(2) weighing 100g of allyl glycidyl ether and 140g of diglycerol, adding the allyl glycidyl ether and the diglycerol into a reaction kettle, stirring the mixture for 15 minutes at 300 revolutions per minute under the protection of nitrogen, then adding 1.6g of potassium hydroxide, heating the mixture to 92 ℃ at the speed of 2 ℃/minute, and stirring the mixture to react for 3 hours; naturally cooling to room temperature, and performing vacuum distillation at room temperature to remove water and low-boiling-point substances to obtain allyl polyglycerol;
(3) 0.1mL Karstedt catalyst is fully mixed with 31.5g of hydrosiloxane in advance to obtain the hydrosiloxane containing the catalyst; under the protection of nitrogen, 145mL of isopropanol is added into a reaction device, the temperature is raised to 85 ℃ at the speed of 2 ℃/min, meanwhile, hydrosiloxane containing a catalyst and 52g of allyl polyglycerol are added, and the reaction is continued for 3 hours at 85 ℃; and after the reaction is stopped, naturally cooling to room temperature to obtain the polyglycerol modified organosilicon surfactant.
Example 6
The preparation method of the intelligent liquid crystal dimming film with high transmittance comprises the following steps:
step S1: fully and uniformly stirring 30 parts by weight of urethane acrylate, 50 parts by weight of biphenyl liquid crystal (specifically, 50 parts by weight of 4' -allyloxy-4-perfluorooctanoyloxy-biphenyl prepared by using example one of reference patent application No. 201010165461.6), 1.2 parts by weight of hollow mesoporous organic silicon microspheres, 3 parts by weight of photoinitiator, 1 part by weight of polyglycerol-modified organic silicon surfactant and 0.9 part by weight of pentaerythritol ester (CAS No. 8050-10-0) to obtain a mixed solution;
step S2: placing the mixed solution between two conductive films, wherein the conductive layers of the conductive films are oppositely arranged on the inner sides and face to face, coating the mixed solution in the middle of the conductive films through a manual roller coater, and rolling to form a thin film;
step S3: the film is subjected to the first step of ultraviolet irradiation polymerization, and the intensity of the ultraviolet light is 0.1mw/cm2The ultraviolet irradiation time is 50s, so that the polymerizable monomer in the film system is incompletely polymerized;
step S4: then, under the condition of applying an electric field to the film, the frequency of the electric field is 0.01Hz, the voltage is applied to 160V, and the film is subjected to a second step of ultraviolet light irradiation polymerization, wherein the intensity of the ultraviolet light is 0.5mw/cm2And the ultraviolet irradiation time is 3 minutes, so that the residual polymerizable monomer is completely polymerized to obtain the high-transmittance intelligent liquid crystal dimming film with the thickness of 20 mu m.
The polyurethane acrylate was hyperbranched polyurethane acrylate and the preparation procedure was the same as in example 2.
The photoinitiator is a nano-cellulose crystal grafted photoinitiator 1173, and the preparation process is the same as that of example 3.
The preparation process of the hollow mesoporous organic silicon microsphere comprises the following steps: dispersing 500mg of nano silicon dioxide (particle size of 15-30 nm, produced by Hangzhou Wanjing New Material Co., Ltd.) in 30mL of deionized water, and performing ultrasonic treatment for 30 minutes under the conditions of ultrasonic power of 300W and ultrasonic frequency of 25kHz to obtain silicon dioxide dispersion liquid; 1.1g of cetyltrimethylammonium chloride (CAS number: 112-02-7), 18. mu.L of triethanolamine (CAS number: 102-71-6) and 45mL of deionized water are added into a reaction device, and stirred for 1.5 hours at normal temperature; then adding the nano silicon dioxide dispersion liquid, and stirring for 1.5 hours; then 0.9mL of bis- [3- (triethoxysilyl) propyl ] -tetrasulfide (CAS number: 40372-72-3) was added, and after stirring at 80 ℃ for 1 hour, the mixture was centrifuged at 4000 rpm for 30 minutes, and the precipitate was collected; washing the precipitate with 50 times of anhydrous ethanol, and drying at room temperature for 12 hr; and (3) mixing the dried precipitate in a solid-liquid ratio of 1: 30(g/mL) is dispersed in a sodium carbonate solution with the molar concentration of 0.3mol/L, stirred for 1 hour at 50 ℃, centrifuged for 30 minutes at 4000 revolutions/minute, and bottom sediment is collected; washing the bottom precipitate with deionized water 100 times the weight of the bottom precipitate, then washing with sodium chloride methanol solution 20 times the weight of the bottom precipitate and having a mass fraction of 1%, and vacuum-drying at 40 ℃ for 12 hours to obtain the hollow mesoporous organosilicon microsphere.
Example 7
The preparation method of the intelligent liquid crystal dimming film with high transmittance comprises the following steps:
step S1: fully and uniformly stirring 30 parts by weight of urethane acrylate, 50 parts by weight of biphenyl liquid crystal (specifically using 4 '-allyloxy-4-perfluorooctanoyloxy-biphenyl prepared in example one of reference patent application No. 201010165461.6), 0.6 part by weight of hollow glass microspheres (prepared in manufacturer's guohong county processing factory, particle size 10 micrometers, wall thickness 1 micrometer), 0.6 part by weight of hollow mesoporous organic silicon microspheres (prepared in the same way as in example 6), 3 parts by weight of photoinitiator, 1 part by weight of polyglycerol-modified organic silicon surfactant and 0.9 part by weight of pentaerythritol ester (CAS No. 8050-10-0) to obtain a mixed solution;
step S2: placing the mixed solution between two conductive films, wherein the conductive layers of the conductive films are oppositely arranged on the inner sides and face to face, coating the mixed solution in the middle of the conductive films through a manual roller coater, and rolling to form a thin film;
step S3: the film is subjected to the first step of ultraviolet irradiation polymerization, and the intensity of the ultraviolet light is 0.1mw/cm2The ultraviolet irradiation time is 50s, so that the polymerizable monomer in the film system is incompletely polymerized;
step S4: then, under the condition of applying an electric field to the film, the frequency of the electric field is 0.01Hz, the voltage is applied to 160V, and the film is subjected to a second step of ultraviolet light irradiation polymerization, wherein the intensity of the ultraviolet light is 0.5mw/cm2And the ultraviolet irradiation time is 3 minutes, so that the residual polymerizable monomer is completely polymerized to obtain the high-transmittance intelligent liquid crystal dimming film with the thickness of 20 mu m.
The polyurethane acrylate was hyperbranched polyurethane acrylate and the preparation procedure was the same as in example 2.
The photoinitiator is a nano-cellulose crystal grafted photoinitiator 1173, and the preparation process is the same as that of example 3.
Test example 1
The high-transmittance intelligent liquid crystal dimming films of the embodiments 1 to 7 are subjected to a parallel light transmittance instrument test: and (3) testing the parallel light transmittance data of the intelligent liquid crystal dimming film with high transmittance under different voltages by using a parallel light transmittance instrument (DRTC-81).
The specific test results are shown in table 1.
Table 1 high transmittance intelligent liquid crystal dimming film visible light transmittance test table%
Test example 2
The turbidity test was performed on the intelligent liquid crystal dimming films with high transmittance of examples 1 to 7: haze data were measured with a haze meter (COH400) at various voltages.
The specific test results are shown in table 2.
Table 2 haze test table of high transmittance intelligent liquid crystal dimming film%
From the above data, it can be seen that the surfactant was screened in examples 3 to 5, and when the polyglycerol-modified silicone surfactant was used in example 5, the on-state transmittance of the light-adjusting film was significantly increased, presumably because the addition of the surfactant affected the degree of gelation and dispersion of the polymer. Compared with other surfactants such as a polyglycerol modified organic silicon surfactant, a polyether modified organic silicon surfactant and the like, the polyglycerol chain with hydrophilicity is connected on the linear siloxane framework, so that the polyglycerol modified organic silicon surfactant has lower critical micelle concentration and lower surface tension, and most of liquid crystal is prevented from being aggregated and separated out, so that the on-state transmittance of the light modulation film is improved while the off-state shielding property and the on-state viewing effect are ensured.
Test example 3
The mixture obtained in step 1 of examples 1 to 7 was applied to a galvanized iron sheet (5 cm. times.12 cm) cleaned by wiping with absolute ethanol and acetone and an inorganic glass sheet (0.3 cm. times.9 cm. times.12 cm) substrate, and the substrate was passed through a 50 th padVacuum drying at room temperature, dehydrating, and ultraviolet curing with a box-type ultraviolet curing machine at an ultraviolet intensity of 300mW/cm2And curing for 30s to obtain an ultraviolet curing film, and performing mechanical test on the performance of the ultraviolet curing film:
(1) hardness of the swing rod: inorganic glass is taken as a base material, and a swing rod type paint film hardness tester is used for testing according to GB 1730-2007;
(2) impact strength: the tinplate is taken as a base material, and a paint film impactor is used for testing according to GB 1732 + 1993;
(3) flexibility: taking tinplate as a base material, and testing by a cylindrical bending tester according to GB 6742 and 2007;
(4) adhesion force: the tinplate is taken as a base material, a paint film cross-section instrument is used, and the test is carried out according to GB 1720-1988.
(5) Mechanical properties: the tinplate is taken as a base material, and the tensile rate is 50mm/min according to the GB/T528-92 test.
The specific test results are shown in table 3.
Table 3 high transmittance intelligent liquid crystal dimming film mechanical property test table%
As can be seen from table 3, in example 2, hyperbranched urethane acrylate is used to replace conventional urethane acrylate, so that the cured film has more excellent mechanical properties, and both flexibility and hardness are achieved, thereby solving the problems of insufficient crosslinking density and poor mechanical properties of the conventional cured film. Presumably, the reason for this is that carbon-carbon double bonds and hydrophilic groups are introduced into the urethane acrylate structure, and the hydrophilic groups are introduced into the soft segment, so that the degree of freedom of movement of the soft segment is relatively high, and the hydrophilic groups are favorably distributed on the particle surface, and the obtained dispersion has relatively small particle size and relatively good dispersion performance. In the embodiment 3, a nano-cellulose grafted photoinitiator is used, and a small-molecular photoinitiator 2-hydroxy-2-methyl-1-phenyl acetone is grafted to the surface of nano-cellulose through a chemical reaction to prepare a low-mobility, low-toxicity and low-volatility macromolecular photoinitiator, wherein the photoinitiation efficiency is good, and on the other hand, the nano-cellulose has good mechanical properties, can play a role of a reinforcing agent in curing urethane acrylate, has good compatibility with a matrix, and improves the mechanical properties and stability of a cured film.
It should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art will be able to make the description as a whole, and the embodiments may be appropriately combined to form other embodiments as will be appreciated by those skilled in the art.
Claims (10)
1. The preparation method of the intelligent liquid crystal dimming film with high transmittance is characterized by comprising the following steps:
step S1: fully and uniformly stirring 20-60 parts by weight of polyurethane acrylate, 30-70 parts by weight of biphenyl liquid crystal, 0.01-2 parts by weight of spacer particles, 0.01-10 parts by weight of photoinitiator, 0.5-3 parts by weight of surfactant and 0.3-3 parts by weight of pentaerythritol ester to obtain a mixed solution;
step S2: placing the mixed solution between two conductive films, wherein the conductive layers of the conductive films are oppositely arranged at the inner sides and face to face, coating the mixed solution in the middle of the conductive films by coating equipment, and rolling to form a thin film;
step S3: carrying out the first-step ultraviolet irradiation polymerization on the film, wherein the ultraviolet intensity is 0.1-1 mw/cm2The ultraviolet irradiation time is 10-60 s, so that the polymerizable monomer in the film system is incompletely polymerized;
step S4: then, under the condition of applying an electric field to the film, the frequency of the electric field is 0.01-10 Hz, the applied voltage is 100-200V, and the film is subjected to a second step of ultraviolet light irradiation polymerization, wherein the intensity of the ultraviolet light is 0.1-1 mw/cm2And the ultraviolet irradiation time is 2-4 minutes, so that the residual polymerizable monomer is completely polymerized to obtain the high-transmittance intelligent liquid crystal dimming film.
2. The method for preparing the high-transmittance intelligent liquid crystal dimming film according to claim 1, wherein the polyurethane acrylate is hyperbranched polyurethane acrylate, and is obtained by using hyperbranched polyester as a central core, firstly performing hydrophilic modification on a part of terminal hydroxyl groups of the hyperbranched polyester by using maleic anhydride to obtain a hydrophilic modified substance, and then performing acrylic modification on the remaining terminal hydroxyl groups by using an addition product of isophorone diisocyanate and hydroxyethyl acrylate.
3. The method for preparing the intelligent high-transmittance liquid crystal dimming film according to claim 2, wherein the hyperbranched urethane acrylate is prepared by the following steps:
(1) adding 8-12 g of isophorone diisocyanate, 4-6 g of hydroxyethyl acrylate and 0.05-0.08 g of dibutyltin dilaurate into a reaction device under the atmosphere of nitrogen, uniformly mixing, heating to 30-35 ℃, and reacting at 30-35 ℃ for 2-4 hours to prepare an addition product of isophorone diisocyanate and hydroxyethyl acrylate;
(2) dissolving 8-12 g of hyperbranched polyester and 4-5 g of maleic anhydride in 30-50 mL of tetrahydrofuran, and fully stirring to form a uniform solution; then adding 0.03-0.06 g of catalyst 4-dimethylaminopyridine, heating to 50-60 ℃, reacting for 3-6 hours at 50-60 ℃, and preparing a hydrophilic modifier by using a mono-esterification reaction between a terminal hydroxyl group of the hyperbranched polyester and an anhydride group of maleic anhydride;
(3) adding an addition product of isophorone diisocyanate and hydroxyethyl acrylate into a hydrophilic modifier, adding 0.08-0.15 g of dibutyltin dilaurate, heating to 70-80 ℃, and reacting at 70-80 ℃ for 4-7 hours to obtain the hyperbranched polyurethane acrylate.
4. The method of claim 1, wherein the photoinitiator is photoinitiator 1173.
5. The method for preparing the intelligent high-transmittance liquid crystal dimming film according to claim 1, wherein the photoinitiator is a nanocellulose crystal grafting photoinitiator 1173, and the preparation process comprises: adding 20-40 g of anhydrous acetone into 0.3-1 g of nano-cellulose crystals, and performing ultrasonic dispersion for 30-50 minutes to obtain a dispersion liquid in which the nano-cellulose crystals are uniformly dispersed in the acetone; adding the dispersion liquid and 6-20 g of isophorone diisocyanate into a reaction device provided with a stirrer, a thermometer and a condenser pipe, adding 0.04-0.1 g of catalyst dibutyltin dilaurate, heating to 40-50 ℃, and carrying out heat preservation reaction for 4 hours at 40-50 ℃; then 6-22 g of photoinitiator 1173 is added, heated to 60-70 ℃, and reacted for 4-7 hours at 60-70 ℃; after the reaction is finished, performing centrifugal separation, and collecting bottom solids; and washing the bottom solid with acetone, and drying at normal temperature in vacuum to obtain the nano cellulose crystal grafted photoinitiator 1173.
6. The method of claim 1, wherein the surfactant is a polyether modified silicone surfactant, a glycoside modified silicone surfactant, or a polyglycerol modified silicone surfactant.
7. The method of claim 6, wherein the surfactant is a polyglycerol-modified silicone surfactant.
8. The method of claim 1, wherein the spacer particles are hollow mesoporous silicone microspheres and/or hollow glass microspheres.
9. The method of claim 1, wherein the conductive film is one of a nano silver conductive film, a graphene conductive film, an indium tin oxide film, and a polymer conductive film.
10. A high-transmittance intelligent liquid crystal light-adjusting film, characterized by being produced by the production method for a high-transmittance intelligent liquid crystal light-adjusting film according to any one of claims 1 to 9.
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