CN116377720B - Thermochromic waterproof fabric and preparation method thereof - Google Patents

Thermochromic waterproof fabric and preparation method thereof Download PDF

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CN116377720B
CN116377720B CN202310360720.8A CN202310360720A CN116377720B CN 116377720 B CN116377720 B CN 116377720B CN 202310360720 A CN202310360720 A CN 202310360720A CN 116377720 B CN116377720 B CN 116377720B
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thermochromic
waterproof
agent
color
mixing
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CN116377720A (en
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张旭建
杨静静
孟建国
黄兵
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Risun Polymer International Co ltd
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Risun Polymer International Co ltd
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D06M15/568—Reaction products of isocyanates with polyethers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/80—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with boron or compounds thereof, e.g. borides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/12—Processes in which the treating agent is incorporated in microcapsules
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

The application relates to the technical field of waterproof color-changing fabrics, in particular to a thermochromic waterproof fabric and a preparation method thereof, and the preparation method comprises the following preparation processes: mixing a color former, a color developer and a solvent at a temperature, mixing with tetraethyl orthosilicate in ethanol, and slowly adding into an anionic surfactant aqueous solution to obtain a microcapsule; dispersing the microcapsule and the polyurethane waterproof agent in water to obtain a finishing agent; and finishing and baking the fabric to obtain the thermochromic waterproof fabric. According to the application, the thermochromic material and the waterproof agent are prepared and mixed to be used as a finishing agent to treat the fabric, so that the thermochromic waterproof fabric is obtained; the color change type solar energy collector is colored in a normal temperature environment, when the temperature meets the color change condition, the color change type solar energy collector is quickly changed from color to colorless, when the temperature is reduced, the color change type solar energy collector is quickly cooled and can be changed into color, the color change type solar energy collector can be recycled, the temperature which can possibly cause human body injury can be effectively warned, early warning is achieved, and harm is prevented.

Description

Thermochromic waterproof fabric and preparation method thereof
Technical Field
The application relates to the technical field of waterproof color-changing textiles, in particular to a thermochromic waterproof fabric and a preparation method thereof.
Background
With the development of technology and the increasing of the physical life of people, fabrics with single functions or only basic functions of shielding against cold cannot meet the requirements of human beings, waterproof, flame-retardant, antibacterial and other types of fabrics have been rapidly developed, and some fabrics with early warning functions are being developed. The thermochromic fabric has the function of warning the excessive temperature, and is in line with the development trend of the fabric in order to meet the multifunctional requirement of human beings on the fabric. Therefore, we propose a thermochromic waterproof fabric.
Disclosure of Invention
The application aims to provide a thermochromic waterproof fabric so as to solve the problems in the background technology.
In order to solve the technical problems, the application provides the following technical scheme: the preparation method of the thermochromic waterproof fabric comprises the following preparation processes:
step one, heating the color former, the color developer and the solvent to 60-90 ℃, and stirring and mixing uniformly to obtain a thermochromic material; mixing a thermochromic material and tetraethyl orthosilicate in ethanol to obtain a mixed solution;
step two, taking an anionic surfactant aqueous solution, heating to 80-95 ℃, slowly adding the mixed solution, centrifuging after the addition, and washing to obtain microcapsules;
step three, heating isophorone diisocyanate, polypropylene glycol and hydroxyl silicone oil to react; adding dimethylol butyric acid, glycidol and a catalyst, reacting, adding deionized water and an emulsifying agent under high-speed shearing, mixing and emulsifying to obtain a waterproof agent;
dispersing the microcapsule and the waterproof agent in water to obtain a finishing agent; and finishing and baking the fabric by using the finishing agent to form a film layer, so as to prepare the thermochromic waterproof fabric.
Further, in the first step, the stirring speed is 100-700 rpm, and the stirring is carried out until the system turns from colorless to blue and then turns colorless;
the thermochromic material comprises the following components in percentage by mass: 1 to 5 percent of color former, 5 to 10 percent of color developer and 88 to 95 percent of solvent;
color-developing agents include, but are not limited to, crystal violet lactone, malachite green lactone, cresol red, fuji black, thermosensitive red, thermosensitive green;
color developers include, but are not limited to, bisphenol A, gallate, methylparaben, stearic acid, boric acid;
solvents include, but are not limited to, behenyl alcohol, cetyl alcohol, stearyl alcohol.
Further, in the second step, the anionic surfactant includes, but is not limited to, sodium dodecyl sulfate, octadecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium bromide;
the mass ratio of the thermochromic material to the tetraethyl orthosilicate in the mixed solution is (5-10) (1-5); the ratio of the thermochromic material to the ethanol is 1g to 1mL;
the mass concentration of the anionic surfactant aqueous solution is 1.5-3.0%;
adding the mixed solution into the anionic surfactant water solution at the speed of 1-5 drops/s, and magnetically stirring at the speed of 500-2000 rpm;
the centrifugal process comprises the following steps: centrifuging at 8000-12000 rpm for 1-4 hr;
the washing process comprises the following steps: ethanol, acetone and water are adopted for washing in sequence.
Further, in the third step, the waterproofing agent comprises the following components in mole percent: 2 to 3 parts of isophorone diisocyanate, 0.3 to 0.6 part of polypropylene glycol, 0.3 to 0.6 part of hydroxyl silicone oil, 0.5 to 1.5 parts of dimethylol butyric acid, 0.15 to 0.50 part of glycidol, 0.23 to 0.43 part of emulsifier, and 0.004 to 0.024 part of catalyst dibutyltin dilaurate;
the polypropylene glycol is PPG800 and is sourced from Shanghai Ala Biochemical technology Co., ltd;
the hydroxy silicone oil is hydroxy silicone oil 400, which is derived from Shanghai Ke Raman reagent Co;
the emulsifier is DNS-18; the solids content of the waterproofing agent was 20%.
Further, the third step specifically includes the following processes:
heating isophorone diisocyanate, polypropylene glycol and hydroxyl silicone oil to 85-95 ℃ in a nitrogen atmosphere, and reacting for 2-3 h; the temperature of the system is reduced to 60-85 ℃, and dimethylolbutyric acid is added for reaction for 2-3 h; adding glycidol and catalyst dibutyl tin dilaurate, and continuing the reaction for 50-120 min; cooling to 35-45 ℃, adding triethylamine to neutralize for 1min, adding deionized water and an emulsifying agent to mix and emulsify for 30min under high-speed shearing, and obtaining the waterproof agent.
Further, in the fourth step, the finishing agent comprises 50-100 g/L microcapsules and 20-80 g/L waterproof agents;
the finishing process comprises the following steps: two-soaking and two-rolling, wherein the soaking time is 18-23 min, and the rolling residual rate is 70-80%;
the baking process comprises the following steps: pre-baking at 80-90 deg.c for 3-5 min and baking at 110-150 deg.c for 2-4 min.
The fabric is selected from plain full-polyester fabric with gram weight of 78g/m 2 Derived from the company Xuanna textile Co.Ltd.
In the technical scheme, the microcapsule takes three components of the thermochromic material as a core material; the solvent is used as a phase change material to determine the color changing temperature of the thermochromic material; the color former is an electron donor of the thermochromic material, and the color former accepts electrons provided by the color former, so that the thermochromic material system generates color change below the phase transition temperature. Wherein, the oxygen in-OH and S=O in the bisphenol S derivative has hydrogen bond action with spirolactone in the color former, compared with other color former components, the thermochromic material has more stable color development state and sensitivity. The silicon dioxide is used as a shell material of the microcapsule to coat the thermochromic material, so that on one hand, the thermochromic material can be isolated from undesirable substances such as external acid and alkali and the like, and the stability of the thermochromic material is improved; on the other hand, the liquefaction and leakage of the solvent at high temperature can be avoided, the thermochromic material is more convenient to fix on the fabric, and the preparation of the thermochromic waterproof fabric is realized; meanwhile, the use of the shell material silicon dioxide promotes the heat transfer on the prepared film layer, and relieves the hysteresis of the color change of the thermochromic material caused by low thermal conductivity; and the color is transparent and colorless, so that the color of the core material is prevented from being shielded, and the color development capability of the thermochromic material is prevented from being influenced. The ratio of the color former, the color developer, the solvent and the thermochromic material to the tetraethyl orthosilicate is controlled, so that the microcapsule has better color-changing sensitivity. When the content of the color developing agent is low, the color developing capability of the prepared thermochromic material is low, and the color of the change of the thermochromic material is light; when the content of the phase change material is low, the color change performance of the thermochromic material is poor, and the color change time is longer. Along with the increase of the core-shell ratio of the microcapsule, the mass of the core material is continuously increased, the thickness of the shell material is continuously increased, and the change range of the color temperature is gradually increased. In addition, the microcapsule is granular, so that the surface roughness of the prepared film layer is improved to a certain extent, the hydrophobicity of the film layer can be enhanced, and the waterproof performance of the thermochromic waterproof fabric is improved.
After finishing process, the waterproof agent is loaded on the surface of the fabric and permeates into the fabric, and the epoxy group (glycidol) structure in the system is largely opened in the film forming process, so that the crosslinking point of the system is increased, the intermolecular acting force in the system is improved, a three-dimensional network structure is formed, the microcapsules are limited, and the mechanical property of the film layer is improved. The waterproof agent forms a layer of compact reticular film, so that the film layer is not easy to be permeated by moisture, and the waterproof performance of the thermochromic waterproof fabric is improved.
Further, the microcapsule obtained in the second step is subjected to surface modification, and the specific process is as follows:
mixing an ultraviolet absorbent 1130, a fluorosilane coupling agent and a mercaptosilane coupling agent, reacting for 4.0-4.5 hours, adding the mixture into the aqueous dispersion of the microcapsule, and stirring at a high speed for 30-60 min;
filtering at 27-32 deg.c, dispersing into silver nitrate aqua and stirring to react for 5-7 min; centrifuging and washing to obtain the modified microcapsule.
Further, the mass ratio of the microcapsule, the ultraviolet absorber 1130, the fluorosilane coupling agent and the mercaptosilane coupling agent is 100 (1.5-2.0): 2.0-2.5): 3.0-3.5; the concentration of the aqueous dispersion of microcapsules was 50%;
the proportion of the microcapsule and the silver nitrate aqueous solution is 0.4g/100mL; the concentration of the silver nitrate aqueous solution was 0.1M.
Further, the method comprises the steps of, the fluorosilane coupling agent includes, but is not limited to, 4-perfluorotriethoxysilane, 1H, 2H-perfluorodecyl triethoxysilane, 1H, 2H-perfluorododecyl triethoxysilane triethoxy-1H, 2H-tridecafluoro-N-octylsilane, tridecafluorooctyltrimethoxysilane (1H, 2H-perfluoro-tetradecyl) tris (ethoxy) silane, 1H, 2H-heptadecafluorodecyl trimethoxysilane;
mercaptosilane coupling agents include, but are not limited to, mercaptotrimethoxysilane, 3-mercaptopropyl triethoxysilane, mercaptopropyl trimethoxysilane, 11-mercaptoundecyltrimethoxysilane.
In the technical scheme, the thermochromic material contains carbonyl groups, is easy to oxidize and is influenced by ultraviolet rays, and the ultraviolet absorber is utilized to carry out surface modification on the microcapsule, so that the ultraviolet resistance of the thermochromic material can be effectively improved, and the stable color development capability and sensitivity of the thermochromic material can be kept; and meanwhile, ultraviolet light in the subsequent process is prevented from damaging the bonding structure of the thermochromic material, so that the thermochromic material is prevented from being discolored and losing efficacy.
In the surface modification process of the microcapsule, a fluorosilane coupling agent and a mercapto silane coupling agent are also added, so that the water-repellent capacity of the microcapsule can be improved, the stability of a waterproof agent and polyacrylate emulsion system can be improved, and the water-repellent capacity of a prepared film layer can be enhanced; meanwhile, a large number of mercapto groups are introduced on the surface of the microcapsule, the benzotriazole structure in the ultraviolet absorbent 1130 is cooperated, the adsorption of silver ions on the surface of the microcapsule is promoted by the silver nitrate aqueous solution, a supersaturated solution area of the silver ions is formed, when two mercapto groups are condensed to form disulfide bonds, the reduction of the silver ions is realized by the double electrons through the coordination structure of the mercapto groups and the silver ions, the silver simple substance is loaded on the surface of the microcapsule, the benzotriazole structure in the ultraviolet absorbent 1130 is cooperated with fluorine atoms in the fluorosilane coupling agent, the interaction among molecules can be enhanced, the charge transmission is promoted, the reduction and the deposition of the silver ions are promoted, so that nano silver with the particle size below 10nm is formed on the surface of the microcapsule, and the color development capability of the thermochromic material is not influenced. Silver has excellent heat conduction capability, and the silver is loaded on the surface of the microcapsule, so that the heat conduction coefficient of the microcapsule shell material can be greatly improved, the heat transfer to the thermochromic material is promoted, the color change sensitivity of the thermochromic waterproof fabric is further improved, and the color change hysteresis of the thermochromic waterproof fabric is relieved.
In the fourth step, the finishing agent further comprises 2.4-9.6 g/L polyacrylate, 4-16 g/L boron nitride, 1.1-4.4 g/L photoinitiator benzophenone and 0.37-1.47 g/L co-initiator triethylamine.
Further, in the baking process, the pre-baking process is carried out while ultraviolet irradiation is carried out, and the wavelength of ultraviolet light is 300-400 nm.
Further, the polyacrylate is prepared by the following process:
(1) Under the condition of avoiding light, taking deionized water, adding allyl glycinate and 1-hydroxybenzotriazole, mixing and stirring uniformly, adding N-acetyl-L-cysteine, regulating the pH of the system to 4.7-5.2 by using sodium hydroxide solution, and stirring and reacting for 150-200 min; adding absolute ethyl alcohol, carrying out suction filtration, washing and drying to obtain a modified monomer;
(2) Under the protection of light shielding and nitrogen atmosphere, mixing the emulsifier with 1/2 component mass and the deionized water with 1/3 component mass, adding the butyl acrylate with 1/2 component mass, the methyl methacrylate with 1/2 component mass and the modified monomer, performing ultrasonic dispersion for 30-40 min, and stirring for 30-40 min to obtain the pre-emulsion;
mixing the emulsifier of the residual component and deionized water of the residual component, adding butyl acrylate of the residual component, methyl methacrylate of the residual component and sodium bicarbonate solution, mixing, performing ultrasonic dispersion for 30-40 min, heating in a water bath at 45-55 ℃, stirring for 30-40 min, heating to 75-85 ℃, adding 1/2 component mass initiator solution, and reacting for 90-150 min;
slowly adding the pre-emulsion and the initiator solution of the rest components to react for 100-150 min at 75-85 ℃; standing, cooling to room temperature, and sieving with a 200-mesh sieve to obtain polyacrylate.
Further, in the step (1), the mass ratio of the allyl glycinate, the N-acetyl-L-cysteine and the 1-hydroxybenzotriazole is 10 (14.2-15.6) (7.0-10.8);
allyl glycinate and deionized water in a ratio of 1.2g/100mL; the concentration of sodium hydroxide solution was 1M.
Further, in the step (2), the polyacrylate comprises the following mass components: 10 to 13 parts of butyl acrylate, 6.7 to 8.7 parts of methyl methacrylate, 1.8 to 2.3 parts of modified monomer, 0.9 to 1.4 parts of emulsifier, 0.15 to 0.30 part of initiator and 10 to 11 parts of deionized water;
the emulsifier is a mixture of OP-10 and SDS, and the mass ratio is 2:1; the mass concentration of the initiator solution was 2%.
Further, the N-acetyl-L-cysteine in the step (1) is protected by sulfhydryl, and the specific process is as follows:
taking a mixed solution of deionized water and ethanol as a solvent, adding 2-nitrobenzyl mercaptan, slowly adding thiourea, concentrated hydrochloric acid and hydrogen peroxide at the temperature of 0-5 ℃ for reaction for 5 hours;
adding N-acetyl-L-cysteine, slowly adding saturated sodium bicarbonate solution at 0-5 ℃ for reaction for 5-9 h; extracting with dichloromethane, concentrating the organic phase under reduced pressure, drying, and passing through column.
Further, the volume ratio of deionized water to ethanol in the mixed solution is 1:3;
the molar ratio of the 2-nitrobenzyl mercaptan to the thiourea to the N-acetyl-L-cysteine is 10 (12-13) (1.0-1.3);
the volume ratio of the mixed solution to the concentrated hydrochloric acid to the hydrogen peroxide is 100 (5-6);
the mass concentration of the concentrated hydrochloric acid is 36-38%; the mass concentration of hydrogen peroxide was 30%.
Further, the 2-nitrobenzyl mercaptan is prepared by the following process:
dissolving 2-nitrobenzyl bromide in absolute ethyl alcohol, adding thiourea, and carrying out reflux reaction for 4-5 h at 60-65 ℃; centrifuging, taking and washing the precipitate, dissolving in deionized water, adding dichloromethane, adding sodium metabisulfite, carrying out reflux reaction for 10-11 h at 33-37 ℃ under the protection of nitrogen, and passing the organic phase through a column to obtain the 2-nitrobenzyl mercaptan.
Further, the molar ratio of the 2-nitrobenzyl bromide to the thiourea to the sodium metabisulfite is 1 (1.1-1.3) (3.8-4.2);
the proportion of the 2-nitrobenzyl bromide, the absolute ethyl alcohol, the deionized water and the methylene dichloride is 25g to 100mL (50 to 75 mL).
According to the technical scheme, butyl acrylate, methyl methacrylate and a modified monomer are used as raw materials to prepare polyacrylate, so that the toughness of the epoxy end-capped polyurethane waterproof agent after film formation can be improved, and the mechanical property and the waterproof property of the thermochromic waterproof fabric are further improved. The modified monomer is prepared by the reaction of allyl glycinate and N-acetyl-L-cysteine, mercapto is introduced into a polyacrylate system, and in the process after finishing, the mercapto can react with epoxy groups in a waterproof agent under the action of ultraviolet initiation, so that the polyacrylate and polyurethane are grafted and modified, the crosslinking point of the system is further improved, and the improvement of the strength and toughness of a prepared film layer is promoted; and can improve the thermal stability of the film and the adhesion between the film and the fabric. The mercapto group in the polyacrylate system can also form a silver-sulfur covalent bond with the nano silver structure on the surface of the microcapsule, so that the composite strength between the microcapsule and the coating is enhanced, and the anti-deformation and anti-fatigue capabilities of the prepared film layer are further improved.
The thiol on the N-acetyl-L-cysteine is protected by a thiol protecting agent with photosensitive characteristic, so that the thiol is prevented from reacting in the preparation process of polyacrylate, and the existence of the thiol in a polyacrylate system in the subsequent process is ensured; in the finishing agent system, when the pre-baking process is carried out, the thiol at the ortho position of the nitro group in the molecular structure of the sulfhydryl protective agent leaves to generate aldehyde (nitrobenzaldehyde), the aldehyde (nitrobenzaldehyde) is easy to evaporate along with water vapor, the water vapor of the system and the pH value change of the system, disulfide bond formation is blocked, and a large amount of epoxy groups are opened, so that the interaction between the sulfhydryl group in the polyacrylate system, the waterproof agent and the microcapsule is realized.
Further, the boron nitride is modified by a mercaptosilane coupling agent, and specifically comprises the following processes:
taking dimethylbenzene, adding boron nitride and a mercaptosilane coupling agent for dispersion, and condensing and refluxing for reaction; cooling to room temperature, and filtering; placing the mixture in ethanol solution, performing ultrasonic dispersion for 30min, heating to 45-55 ℃, and stirring for 30-90 min; filtering, washing with ethanol solution, and drying.
Further, the mass ratio of the boron nitride to the mercapto silane coupling agent is 100 (2.0-5.0);
the proportion of the boron nitride, the dimethylbenzene and the ethanol solution is 10g:50mL:100mL; the mass concentration of the ethanol solution is 95%;
boron nitride: cubic boron nitride with an average particle size of 8 μm is obtained from Shanghai Jinghai New Material technology Co.
In the technical scheme, the boron nitride has high heat conduction capacity, so that the heat conduction performance of an organic system formed by the waterproof agent and polyacrylate is improved, and the color change performance of the prepared thermochromic waterproof fabric is further improved; after being modified by the sulfhydryl silane coupling agent, the dispersibility of the boron nitride in the finishing agent system is improved, sulfhydryl groups are introduced on the surface of the boron nitride, the interaction between the boron nitride, the waterproof agent and the microcapsules is enhanced, and the color development capability, the waterproof performance and the mechanical performance of the film are improved.
Compared with the prior art, the application has the following beneficial effects:
according to the thermochromic waterproof fabric and the preparation method thereof, the fabric is treated as a finishing agent through the preparation and mixing of the thermochromic material and the waterproof agent, so that the thermochromic waterproof fabric is obtained; the color change type solar energy collector is colored in a normal temperature environment, when the temperature meets the color change condition, the color change type solar energy collector is quickly changed from color to colorless, when the temperature is reduced, the color change type solar energy collector is quickly cooled and can be changed into color, the color change type solar energy collector can be recycled, the temperature which can possibly cause human body injury can be effectively warned, early warning is achieved, and harm is prevented.
Detailed Description
The following description of the technical solutions in the embodiments of the present application will be clearly and completely described, and it is obvious that the described embodiments are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
In the following embodiments, the color former is selected from crystal violet lactone; bisphenol A is selected as the color reagent; selecting a solvent of behenyl alcohol; the ionic surfactant is sodium dodecyl sulfonate; the fluorosilane coupling agent is 1H, 2H-perfluoro decyl triethoxysilane; the mercapto silane coupling agent is 11-mercapto undecyl trimethoxy silane;
the polypropylene glycol is PPG800 and is sourced from Shanghai Ala Biochemical technology Co., ltd; the hydroxy silicone oil is hydroxy silicone oil 400, which is derived from Shanghai Ke Raman reagent Co; the fabric is selected from plain full polyester fabric with gram weight of 78g/m < 2 >, and is derived from Suzhou Xuanna textile Co., ltd; boron nitride: cubic boron nitride with an average particle size of 8 μm is obtained from Shanghai Jinghai New Material technology Co.
The N-acetyl-L-cysteine is protected by sulfhydryl, and the specific process is as follows: taking a mixed solution of 25mL of deionized water and 75mL of ethanol as a solvent, adding 1.0mol of 2-nitrobenzyl mercaptan, slowly adding 1.3mol of thiourea, 5.5mL of concentrated hydrochloric acid (37%) and 5.5mL of hydrogen peroxide (30%) at the temperature of 2 ℃ for reaction for 5h; adding 0.13mol of N-acetyl-L-cysteine, slowly adding saturated sodium bicarbonate solution at the temperature of 2 ℃ for reaction for 7h; extracting with dichloromethane, concentrating the organic phase under reduced pressure, drying, and passing through column.
Wherein, the 2-nitrobenzyl mercaptan is prepared by the following process: 1mol of 2-nitrobenzyl bromide is taken and dissolved in 85.5mL of absolute ethyl alcohol, 1.2mol of thiourea is added, and reflux reaction is carried out for 4.5 hours at 60 ℃; centrifuging, taking and washing the precipitate, dissolving the precipitate in 85.5mL of deionized water, adding 54mL of dichloromethane, adding 4mol of sodium metabisulfite, carrying out reflux reaction for 10h at 35 ℃ under the protection of nitrogen, and passing the organic phase through a column to obtain the 2-nitrobenzyl mercaptan.
Example 1: the preparation method of the thermochromic waterproof fabric comprises the following preparation processes:
heating 1wt% of a color former, 5wt% of a color former and 94wt% of a solvent to 60 ℃, stirring and mixing uniformly at a stirring speed of 100rpm until the system turns from colorless to blue, and then turning to colorless to obtain a thermochromic material; 50g of thermochromic material and 10g of tetraethyl orthosilicate are mixed in 50mL of ethanol to obtain a mixed solution;
step two, taking 1.5% of anionic surfactant aqueous solution, heating to 80 ℃, slowly adding the mixed solution, adding the mixed solution into the anionic surfactant aqueous solution at a speed of 1 drop/s, and magnetically stirring at a speed of 500 rpm; centrifuging after the addition, and centrifuging at 8000rpm for 1h; sequentially washing with ethanol, acetone and water to obtain microcapsules;
mixing 1.5g of ultraviolet absorbent 1130, 2.0g of fluorosilane coupling agent and 3.0g of mercapto silane coupling agent, reacting for 4 hours, adding into 200mL of 50% microcapsule aqueous dispersion, and stirring at high speed for 30min; filtering at 27 ℃, dispersing into 0.1M silver nitrate water solution, and continuously stirring for reaction for 5min; centrifuging and washing to obtain modified microcapsules; the proportion of the microcapsule and the silver nitrate aqueous solution is 0.4g/100mL, and examples 2-3 are the same;
step three, in a nitrogen atmosphere, heating 2mol of isophorone diisocyanate, 0.3mol of polypropylene glycol and 0.3mol of hydroxyl silicone oil to 85 ℃ for reaction for 2 hours; the temperature of the system is reduced to 60 ℃, 0.5mol of dimethylolbutyric acid is added for reaction for 2 hours; 0.15mol of glycidol and 0.004mol of catalyst dibutyltin dilaurate are added for continuous reaction for 50min; cooling to 35 ℃, adding triethylamine for neutralization for 1min, adding deionized water and 0.23mol of emulsifier DNS-18 under high-speed shearing, and mixing and emulsifying for 30min to obtain the waterproof agent with the solid content of 20%;
taking 833mL of deionized water under the dark condition, adding 10g of allyl glycinate and 7.0g of 1-hydroxybenzotriazole, uniformly mixing and stirring, adding 14.2g of N-acetyl-L-cysteine, regulating the pH of the system to 4.7 by using a 1M sodium hydroxide solution, and stirring for reacting for 150min; adding absolute ethyl alcohol, carrying out suction filtration, washing and drying to obtain a modified monomer;
under the protection of light-shielding and nitrogen atmosphere, mixing 4.5g of emulsifier (the mixture of OP-10 and SDS with the mass ratio of 2:1, the same applies below) and 34g of deionized water, adding 50g of butyl acrylate, 33g of methyl methacrylate and 18g of modified monomer, performing ultrasonic dispersion for 30min, and stirring for 30min to obtain pre-emulsion; mixing 4.5g of emulsifier and 66g of deionized water, adding 50g of butyl acrylate, 34g of methyl methacrylate and sodium bicarbonate solution, mixing, performing ultrasonic dispersion for 30min, heating in a 45 ℃ water bath, stirring for 30min, heating to 75 ℃, adding 15mL of 2% initiator potassium persulfate solution, and reacting for 90min; slowly adding the pre-emulsion and 15mL of 2% initiator solution, and reacting at 75 ℃ for 100min; standing, cooling to room temperature, and sieving with a 200-mesh sieve to obtain polyacrylate;
taking 250mL of dimethylbenzene, adding 50g of boron nitride and 1.0g of mercaptosilane coupling agent for dispersion, condensing and refluxing for reaction; cooling to room temperature, and filtering; placing in 500mL ethanol solution (95%), ultrasonic dispersing for 30min, heating to 45deg.C, and stirring for 30min; filtering, washing with ethanol solution, and drying to obtain modified boron nitride;
dispersing the modified microcapsule and the waterproof agent in water to obtain a finishing agent; the finishing agent comprises 50g/L modified microcapsule, 20g/L waterproof agent, 2.4g/L polyacrylate, 4g/L modified boron nitride, 1.1g/L photoinitiator benzophenone and 0.37g/L co-initiator triethylamine;
the fabric is finished by using the finishing agent, and the finishing process comprises the following steps: two-soaking and two-rolling, wherein the soaking time is 18min, and the rolling residual rate is 70%; baking, wherein the baking process comprises the following steps: pre-baking at 80deg.C for 3min, irradiating with ultraviolet light with wavelength of 365nm and power of 300W; baking at 110 ℃ for 2min to form a film layer, and obtaining the thermochromic waterproof fabric.
Example 2: the preparation method of the thermochromic waterproof fabric comprises the following preparation processes:
heating 3wt% of a color former, 7wt% of a color developer and 90wt% of a solvent to 75 ℃, stirring and mixing uniformly, wherein the stirring speed is 400rpm, and stirring until the system turns from colorless to blue and then turns to colorless, thereby obtaining a thermochromic material; mixing 75g of thermochromic material and 30g of tetraethyl orthosilicate in 75mL of ethanol to obtain a mixed solution;
step two, taking 2.2% of anionic surfactant aqueous solution, heating to 88 ℃, slowly adding the mixed solution, adding the mixed solution into the anionic surfactant aqueous solution at a speed of 3 drops/s, and magnetically stirring the mixed solution at a speed of 1200 rpm; centrifuging at 10000rpm for 2.5h after adding; sequentially washing with ethanol, acetone and water to obtain microcapsules;
mixing 1.8g of ultraviolet absorbent 1130, 2.2g of fluorosilane coupling agent and 3.2g of mercapto silane coupling agent, reacting for 4.2h, adding into 200mL of 50% microcapsule aqueous dispersion, and stirring at high speed for 45min; filtering at 30deg.C, dispersing into 0.1M silver nitrate water solution, and continuously stirring for reaction for 6min; centrifuging and washing to obtain modified microcapsules;
step three, in a nitrogen atmosphere, heating 2.5mol of isophorone diisocyanate, 0.4mol of polypropylene glycol and 0.5mol of hydroxyl silicone oil to 90 ℃ for 2.5 hours; the temperature of the system is reduced to 75 ℃, 1mol of dimethylolbutyric acid is added for reaction for 2.5 hours; 0.3mol of glycidol and 0.014mol of catalyst dibutyltin dilaurate are added to continue the reaction for 85min; cooling to 40 ℃, adding triethylamine for neutralization for 1min, adding deionized water and 0.33mol of emulsifier DNS-18 under high-speed shearing, and mixing and emulsifying for 30min to obtain the waterproof agent with the solid content of 20%;
taking 833mL of deionized water under the dark condition, adding 10g of allyl glycinate and 8.9g of 1-hydroxybenzotriazole, uniformly mixing and stirring, adding 14.9g of N-acetyl-L-cysteine, regulating the pH of the system to 5 by using a 1M sodium hydroxide solution, and stirring and reacting for 175min; adding absolute ethyl alcohol, carrying out suction filtration, washing and drying to obtain a modified monomer;
under the protection of light-shielding and nitrogen atmosphere, mixing 5.5g of emulsifier and 35g of deionized water, adding 57g of butyl acrylate, 38g of methyl methacrylate and 20g of modified monomer, performing ultrasonic dispersion for 35min, and stirring for 35min to obtain a pre-emulsion; mixing 5.5g of emulsifier and 70g of deionized water, adding 58g of butyl acrylate, 39g of methyl methacrylate and sodium bicarbonate solution, mixing, performing ultrasonic dispersion for 35min, heating in a water bath at 50 ℃, stirring for 35min, heating to 80 ℃, adding 55mL of 2% initiator potassium persulfate solution, and reacting for 2h; slowly adding the pre-emulsion and 55mL of initiator solution, and reacting for 2 hours at 80 ℃; standing, cooling to room temperature, and sieving with a 200-mesh sieve to obtain polyacrylate;
taking 250mL of dimethylbenzene, adding 50g of boron nitride and 1.7g of mercaptosilane coupling agent for dispersion, condensing and refluxing for reaction; cooling to room temperature, and filtering; placing in 500mL ethanol solution (95%), performing ultrasonic dispersion for 30min, heating to 50deg.C, and stirring for 1h; filtering, washing with ethanol solution, and drying to obtain modified boron nitride;
dispersing the modified microcapsule and the waterproof agent in water to obtain a finishing agent; the finishing agent comprises 75g/L modified microcapsule, 50g/L waterproof agent, 6g/L polyacrylate, 10g/L modified boron nitride, 2.7g/L photoinitiator benzophenone and 0.9g/L co-initiator triethylamine;
the fabric is finished by using the finishing agent, and the finishing process comprises the following steps: two-soaking and two-rolling, wherein the soaking time is 20min, and the rolling residual rate is 75%; baking, wherein the baking process comprises the following steps: pre-baking at 85deg.C for 4min while irradiating with ultraviolet light with wavelength of 365nm and power of 300W; baking at 130 ℃ for 3min to form a film layer, and obtaining the thermochromic waterproof fabric.
Example 3: the preparation method of the thermochromic waterproof fabric comprises the following preparation processes:
heating 5wt% of a color former, 7wt% of a color developer and 88wt% of a solvent to 90 ℃, stirring and mixing uniformly, wherein the stirring speed is 700rpm, and stirring until the system turns from colorless to blue and then turns to colorless, thereby obtaining a thermochromic material; mixing 100g of thermochromic material and 50g of tetraethyl orthosilicate in 100mL of ethanol to obtain a mixed solution;
step two, taking 3.0% of anionic surfactant aqueous solution, heating to 95 ℃, slowly adding the mixed solution, adding the mixed solution into the anionic surfactant aqueous solution at a speed of 5 drops/s, and magnetically stirring at a speed of 2000 rpm; centrifuging at 12000rpm for 4h after the addition; sequentially washing with ethanol, acetone and water to obtain microcapsules;
mixing 2.0g of ultraviolet absorbent 1130, 2.5g of fluorosilane coupling agent and 3.5 g of mercapto silane coupling agent, reacting for 4.5h, adding into 200mL of 50% microcapsule aqueous dispersion, and stirring at high speed for 1h; filtering at 32 ℃, dispersing into 0.1M silver nitrate water solution, and continuously stirring for reaction for 7min; centrifuging and washing to obtain modified microcapsules;
step three, in a nitrogen atmosphere, 3mol of isophorone diisocyanate, 0.6mol of polypropylene glycol and 0.6mol of hydroxyl silicone oil are heated to 95 ℃ and reacted for 3 hours; the temperature of the system is reduced to 85 ℃, 1.5mol of dimethylolbutyric acid is added for 3 hours of reaction; 0.50mol of glycidol and 0.024mol of catalyst dibutyltin dilaurate are added for continuous reaction for 2 hours; cooling to 45 ℃, adding triethylamine for neutralization for 1min, adding deionized water and 0.43mol of emulsifier DNS-18 under high-speed shearing, and mixing and emulsifying for 30min to obtain the waterproof agent with the solid content of 20%;
taking 833mL of deionized water under the dark condition, adding 10g of allyl glycinate and 10.8g of 1-hydroxybenzotriazole, uniformly mixing and stirring, adding 15.6g of N-acetyl-L-cysteine, regulating the pH of the system to 5.2 by using a 1M sodium hydroxide solution, and stirring for reacting for 150-200 min; adding absolute ethyl alcohol, carrying out suction filtration, washing and drying to obtain a modified monomer;
under the protection of light-shielding and nitrogen atmosphere, 7g of emulsifier and 37g of deionized water are taken and mixed, 65g of butyl acrylate, 43g of methyl methacrylate and 23g of modified monomer are added, ultrasonic dispersion is carried out for 40min, and stirring is carried out for 40min, thus obtaining pre-emulsion; mixing 7g of emulsifier and 73mL of deionized water, adding 65g of butyl acrylate, 44g of methyl methacrylate and sodium bicarbonate solution, mixing, performing ultrasonic dispersion for 40min, heating in a water bath at 55 ℃, stirring for 40min, heating to 85 ℃, adding 75mL of 2% initiator potassium persulfate solution, and reacting for 150min; slowly adding the pre-emulsion and 75mL of initiator solution, and reacting at 85 ℃ for 150min; standing, cooling to room temperature, and sieving with a 200-mesh sieve to obtain polyacrylate;
taking 250mL of dimethylbenzene, adding 50g of boron nitride and 2.5g of mercaptosilane coupling agent for dispersion, condensing and refluxing for reaction; cooling to room temperature, and filtering; placing in 500mL ethanol solution (95%), ultrasonic dispersing for 30min, heating to 55deg.C, and stirring for 90min; filtering, washing with ethanol solution, and drying to obtain modified boron nitride;
dispersing the modified microcapsule and the waterproof agent in water to obtain a finishing agent; the finishing agent comprises 100g/L modified microcapsule, 80g/L waterproof agent, 9.6g/L polyacrylate, 16g/L modified boron nitride, 4.4g/L photoinitiator benzophenone and 1.47g/L co-initiator triethylamine;
the fabric is finished by using the finishing agent, and the finishing process comprises the following steps: two-soaking and two-rolling, wherein the soaking time is 23min, and the rolling residual rate is 80%; baking, wherein the baking process comprises the following steps: pre-baking at 90deg.C for 5min while irradiating with ultraviolet light with wavelength of 365nm and power of 300W; baking at 150 ℃ for 4min to form a film layer, and obtaining the thermochromic waterproof fabric.
Comparative example 1: a preparation method of a thermochromic waterproof fabric comprises the following steps: the finishing agent comprises 50g/L modified microcapsule, 20g/L waterproof agent, 2.4g/L polyacrylate, 1.1g/L photoinitiator benzophenone and 0.37g/L co-initiator triethylamine; other steps were the same as in example 1 to prepare a thermochromic waterproof fabric.
Comparative example 2: a preparation method of a thermochromic waterproof fabric comprises the following steps: in the second step, the microcapsule modification process comprises the following steps: mixing 1.5g of ultraviolet absorbent 1130, 2.0g of fluorosilane coupling agent and 3.0g of mercapto silane coupling agent, reacting for 4 hours, adding into 200mL of 50% microcapsule aqueous dispersion, and stirring at high speed for 30min; centrifuging and washing to obtain modified microcapsules;
the finishing agent comprises 50g/L modified microcapsule, 20g/L waterproof agent, 2.4g/L polyacrylate, 1.1g/L photoinitiator benzophenone and 0.37g/L co-initiator triethylamine; other steps were the same as in example 1 to prepare a thermochromic waterproof fabric.
Comparative example 3: a preparation method of a thermochromic waterproof fabric comprises the following steps: in the second step, the microcapsule is not modified; the finishing agent comprises 50g/L microcapsule, 20g/L waterproof agent, 2.4g/L polyacrylate, 1.1g/L photoinitiator benzophenone and 0.37g/L co-initiator triethylamine; other steps were the same as in example 1 to prepare a thermochromic waterproof fabric.
Comparative example 4: a preparation method of a thermochromic waterproof fabric comprises the following steps: in the second step, the microcapsule is not modified; in the preparation of the fourth polyacrylate, the modified monomer is replaced by methyl methacrylate with equal mass, modified boron nitride is not added into the finishing agent, and the finishing agent comprises 50g/L microcapsules, 20g/L waterproof agent and 2.4g/L polyacrylate; and step one and step three are the same as in the example 1, and the thermochromic waterproof fabric is prepared.
Comparative example 5: a preparation method of a thermochromic waterproof fabric comprises the following steps: in the second step, the microcapsule is not modified; and step four, the components of polyacrylate and modified boron nitride are not arranged, and the finishing agent comprises 50g/L microcapsules and 20g/L waterproof agent.
Experiment
The thermochromic waterproof fabrics obtained in examples 1 to 3 and comparative examples 1 to 5 were taken to prepare samples, the performances of which were respectively tested and the test results were recorded:
color change performance: controlling the experimental temperature to be 75 ℃, detecting the reflectivity of the sample by using a computer, observing the complete color-changing time of the sample according to the reflectivity, and taking the color-changing time as a color-changing performance index of the sample, wherein the size of the sample is 3cm multiplied by 3cm;
waterproof performance: carrying out water contact angle test on the sample by adopting a contact angle measuring instrument, wherein the size of a water drop is 5 mu L, testing after 30s is stable, and taking an average value after 5 times of measurement at different positions;
adhesion force: detecting the film adhesion force in a sample by taking GB/T9286-1998 as a reference standard;
mechanical properties: and detecting breaking strength of the sample by taking GB/T3923.1 as a reference standard.
From the data in the above table, the following conclusions can be clearly drawn:
the thermochromic waterproof fabrics obtained in examples 1 to 3 were compared with those obtained in comparative examples 1 to 5, and the detection results revealed,
compared with the comparative examples, the thermochromic waterproof fabrics obtained in examples 1-3 have higher water contact angle, breaking strength data, lower color change time and adhesion grade data, which fully demonstrate that the application realizes the improvement of the color change performance, the waterproof performance, the film adhesion and the mechanical performance of the prepared thermochromic waterproof fabrics.
The finish of comparative example 1 was not provided with component modified boron nitride as compared to example 1; the microcapsules in comparative example 2 were not nanosilver loaded and the finish was not provided with component modified boron nitride; the microcapsules in comparative example 3 were not modified and the finish was not provided with component modified boron nitride; the finishing agent component in comparative example 4 is a microcapsule, polyacrylate and a water repellent, and the polyacrylate replaces the modified monomer with methyl methacrylate of equal mass; the finishing agent component in comparative example 4 is a microcapsule and a waterproofing agent; the thermochromic waterproof fabrics obtained in comparative examples 1 to 5 were deteriorated in water contact angle, breaking strength data, and discoloration time, and adhesion grade data. The arrangement of the finishing agent component and the process of the application can promote the improvement of the color changing performance, the waterproof performance, the film adhesion and the mechanical performance of the thermochromic waterproof fabric.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process method article or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process method article or apparatus.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present application, and the present application is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present application has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.

Claims (9)

1. A preparation method of thermochromic waterproof fabric is characterized by comprising the following steps: the preparation method comprises the following preparation processes:
step one, heating the color former, the color developer and the solvent to 60-90 ℃, and stirring and mixing uniformly to obtain a thermochromic material; mixing a thermochromic material and tetraethyl orthosilicate in ethanol to obtain a mixed solution;
step two, taking an anionic surfactant aqueous solution, heating to 80-95 ℃, slowly adding the mixed solution, centrifuging after the addition, and washing to obtain microcapsules;
step three, heating isophorone diisocyanate, polypropylene glycol and hydroxyl silicone oil to react; adding dimethylol butyric acid, glycidol and a catalyst, reacting, adding deionized water and an emulsifying agent under high-speed shearing, mixing and emulsifying to obtain a waterproof agent;
dispersing the microcapsule and the waterproof agent in water to obtain a finishing agent; finishing and baking the fabric by using a finishing agent to form a film layer, so as to prepare the thermochromic waterproof fabric;
the microcapsule obtained in the second step is subjected to surface modification, and the specific process is as follows:
mixing an ultraviolet absorbent 1130, a fluorosilane coupling agent and a mercaptosilane coupling agent, reacting for 4.0-4.5 hours, adding the mixture into an aqueous dispersion of the microcapsule, stirring at a high speed for 30-60 min, and filtering;
dispersing the mixture into a silver nitrate aqueous solution at the temperature of 27-32 ℃ and continuously stirring the mixture for reaction for 5-7 min; centrifuging and washing to obtain the modified microcapsule.
2. The method for preparing the thermochromic waterproof fabric according to claim 1, which is characterized in that: in the first step, the thermochromic material comprises the following components in percentage by mass: 1 to 5 percent of color former, 5 to 10 percent of color developer and 88 to 95 percent of solvent; the mass ratio of the thermochromic material to the tetraethyl orthosilicate is (5-10) to (1-5).
3. The method for preparing the thermochromic waterproof fabric according to claim 1, which is characterized in that: in the third step, the waterproof agent comprises the following components in mole percent: 2 to 3 parts of isophorone diisocyanate, 0.3 to 0.6 part of polypropylene glycol, 0.3 to 0.6 part of hydroxyl silicone oil, 0.5 to 1.5 parts of dimethylol butyric acid, 0.15 to 0.50 part of glycidol, 0.23 to 0.43 part of emulsifier and 0.004 to 0.024 part of catalyst dibutyl tin dilaurate.
4. The method for preparing the thermochromic waterproof fabric according to claim 1, which is characterized in that: in the fourth step, the finishing agent comprises 50-100 g/L microcapsules and 20-80 g/L waterproof agent;
the finishing process comprises the following steps: two-soaking and two-rolling, wherein the soaking time is 18-23 min, and the rolling residual rate is 70-80%;
the baking process comprises the following steps: pre-baking for 3-5 min at 80-90 ℃; baking at 110-150 deg.c for 2-4 min.
5. The method for preparing the thermochromic waterproof fabric according to claim 1, which is characterized in that: the mass ratio of the microcapsule to the ultraviolet absorbent 1130 to the fluorosilane coupling agent to the mercaptosilane coupling agent is 100 (1.5-2.0) (2.0-2.5) (3.0-3.5).
6. The method for preparing the thermochromic waterproof fabric according to claim 1, which is characterized in that: in the fourth step, the finishing agent also comprises 2.4-9.6 g/L polyacrylate, 4-16 g/L boron nitride, 1.1-4.4 g/L photoinitiator benzophenone and 0.37-1.47 g/L auxiliary initiator triethylamine;
in the baking process, ultraviolet irradiation is carried out while prebaking, and the wavelength of ultraviolet light is 300-400 nm.
7. The method for preparing the thermochromic waterproof fabric according to claim 6, wherein the method comprises the following steps: the polyacrylate is prepared by the following process:
(1) Under the condition of avoiding light, taking deionized water, adding allyl glycinate and 1-hydroxybenzotriazole, mixing and stirring uniformly, adding N-acetyl-L-cysteine, regulating the pH of a system to 4.7-5.2 by using sodium hydroxide solution, and stirring and reacting for 150-200 min to obtain a modified monomer;
(2) Under the protection of light shielding and nitrogen atmosphere, mixing the emulsifier with 1/2 component mass and the deionized water with 1/3 component mass, adding the butyl acrylate with 1/2 component mass, the methyl methacrylate with 1/2 component mass and the modified monomer, performing ultrasonic dispersion for 30-40 min, and stirring for 30-40 min to obtain the pre-emulsion;
mixing the emulsifier of the residual component and deionized water of the residual component, adding butyl acrylate of the residual component, methyl methacrylate of the residual component and sodium bicarbonate solution, mixing, performing ultrasonic dispersion for 30-40 min, heating in a water bath at 45-55 ℃, stirring for 30-40 min, heating to 75-85 ℃, adding 1/2 component mass initiator solution, and reacting for 90-150 min;
slowly adding the pre-emulsion and the initiator solution of the rest components to react for 100-150 min at 75-85 ℃; standing, cooling to room temperature, and sieving with a 200-mesh sieve to obtain polyacrylate;
the N-acetyl-L-cysteine in the step (1) is protected by sulfhydryl, and the specific process is as follows:
taking a mixed solution of deionized water and ethanol as a solvent, adding 2-nitrobenzyl mercaptan, slowly adding thiourea, concentrated hydrochloric acid and hydrogen peroxide at the temperature of 0-5 ℃ for reaction for 5 hours;
adding N-acetyl-L-cysteine, slowly adding saturated sodium bicarbonate solution at 0-5 ℃ for reaction for 5-9 h; extracting with dichloromethane, concentrating the organic phase under reduced pressure, drying, and passing through column.
8. The method for preparing the thermochromic waterproof fabric according to claim 7, wherein the method comprises the following steps: the mass ratio of the glycin allyl ester to the N-acetyl-L-cysteine to the 1-hydroxybenzotriazole is 10 (14.2-15.6) to 7.0-10.8;
the polyacrylate comprises the following components in parts by mass: 10 to 13 parts of butyl acrylate, 6.7 to 8.7 parts of methyl methacrylate, 1.8 to 2.3 parts of modified monomer, 0.9 to 1.4 parts of emulsifier, 0.15 to 0.30 part of initiator and 10 to 11 parts of deionized water.
9. A thermochromic waterproof fabric prepared by the preparation method according to any one of claims 1 to 8.
CN202310360720.8A 2023-04-06 2023-04-06 Thermochromic waterproof fabric and preparation method thereof Active CN116377720B (en)

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CN105255348A (en) * 2015-10-13 2016-01-20 厦门大学 One-component transparent waterborne polyurethane emulsion waterproof paint and preparation method thereof
CN113201806A (en) * 2021-04-15 2021-08-03 王香玉 Thermochromic fabric based on carbon fibers and preparation method thereof
CN114316912A (en) * 2020-10-09 2022-04-12 天津工业大学 Preparation method of reversible thermochromic phase-change energy-storage microcapsule with hydrophobic surface
CN114525124A (en) * 2022-01-25 2022-05-24 武汉中科先进技术研究院有限公司 Thermochromic microcapsule coated with silicon dioxide wall material and preparation method thereof
CN115182170A (en) * 2022-08-17 2022-10-14 曾莲凤 Thermosensitive color-changing fiber and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105255348A (en) * 2015-10-13 2016-01-20 厦门大学 One-component transparent waterborne polyurethane emulsion waterproof paint and preparation method thereof
CN114316912A (en) * 2020-10-09 2022-04-12 天津工业大学 Preparation method of reversible thermochromic phase-change energy-storage microcapsule with hydrophobic surface
CN113201806A (en) * 2021-04-15 2021-08-03 王香玉 Thermochromic fabric based on carbon fibers and preparation method thereof
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