CN115559131A - Thermochromic cooling heat-resisting fabric and preparation method thereof - Google Patents

Thermochromic cooling heat-resisting fabric and preparation method thereof Download PDF

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Publication number
CN115559131A
CN115559131A CN202210942779.3A CN202210942779A CN115559131A CN 115559131 A CN115559131 A CN 115559131A CN 202210942779 A CN202210942779 A CN 202210942779A CN 115559131 A CN115559131 A CN 115559131A
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parts
expanded graphite
cooling heat
temperature
alkenyl
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CN115559131B (en
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李华桥
许涛
张勇
丁晓东
方琼
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Zhejiang Shengshan Technology Textile Co ltd
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Zhejiang Shengshan Technology Textile Co ltd
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0015—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using fibres of specified chemical or physical nature, e.g. natural silk
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0063—Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • D06N3/146—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the macromolecular diols used
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
    • D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
    • D06P1/5285—Polyurethanes; Polyurea; Polyguanides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
    • D06P1/642—Compounds containing nitrogen
    • D06P1/6424—Compounds containing isocyanate or isothiocyanate groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/80—Inorganic fibres
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2203/00—Macromolecular materials of the coating layers
    • D06N2203/06—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06N2203/068—Polyurethanes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/06—Properties of the materials having thermal properties
    • D06N2209/065—Insulating

Abstract

The invention relates to the field of functional fabrics, and discloses a thermochromic cooling heat-resistant fabric and a preparation method thereof. The preparation method comprises the following steps: coating the cooling heat-resistant slurry on the surface of the carbon fiber base cloth, and forming a cooling heat-resistant coating on the surface of the carbon fiber base cloth after drying; printing on the surface of the cooling heat-resistant coating by using the temperature-sensitive color-changing printing slurry, and then baking to obtain a temperature-sensitive color-changing cooling heat-resistant fabric; the thermochromic printing paste comprises the following components: reversible thermochromic microcapsules, water-based hyperbranched polyurethane, a curing agent and a solvent. According to the invention, the surface of the carbon fiber base cloth is coated with the cooling heat-resistant slurry, and the temperature-sensitive color-changing printing slurry is used for printing, so that the obtained cloth has the functions of temperature-sensitive color changing, cooling heat resistance and ultraviolet resistance, and the reversible temperature-sensitive color-changing microcapsule has higher bonding fastness in the fabric.

Description

Thermochromic cooling heat-resisting fabric and preparation method thereof
Technical Field
The invention relates to the field of functional fabrics, in particular to a thermochromic cooling heat-resistant fabric and a preparation method thereof.
Background
With the improvement of living standard of people, higher demands are shown on the functionalization and intellectualization of textiles. The thermochromic fabric with the temperature responsiveness can be colorful, integrates functions, fashion and the like, and is popular in the market. At present, temperature-sensing color-changing microcapsules with various colors and color-changing temperatures are widely researched, but most of temperature-sensing color-producing textiles only have the function of temperature sensing color changing, the function is single, and the fabric which can simultaneously realize the functions of temperature sensing color changing, heat resistance, temperature reduction and high ultraviolet resistance under outdoor strong light irradiation, particularly in hot weather with high temperature in summer can play a role of serving multiple purposes.
For example, patent CN201710733599.3 discloses a preparation method of a temperature-change printed fabric, which comprises the following steps: sequentially coating a temperature-changing coating on the fabric grey cloth, softening, shaping and drying; in the process of smearing the temperature-changing paint, the used printing paste comprises reversible temperature-sensing microcapsules, the average diameter of the reversible temperature-sensing microcapsules is between 2 and 7 microns, and the outer walls of the reversible temperature-sensing microcapsules are made of transparent epoxy resin with the thickness of between 0.2 and 0.5 microns. The patent can realize better temperature sensing color changing effect, but cannot realize heat-resisting and temperature-reducing high-ultraviolet-resistance functions.
Disclosure of Invention
In order to solve the technical problem that a fabric which can simultaneously realize temperature sensing and color changing and heat resisting and cooling functions and has high ultraviolet resistance is lacked in the prior art, the invention provides a temperature sensing and color changing cooling heat resisting fabric and a preparation method thereof. According to the invention, the temperature-reducing heat-resisting slurry is coated on the surface of the carbon fiber base fabric, and the temperature-sensing color-changing printing slurry is used for printing, so that the obtained fabric has the functions of temperature sensing color changing, temperature-reducing heat resisting and ultraviolet resisting, and the reversible temperature-sensing color-changing microcapsule has higher bonding fastness in the fabric.
The specific technical scheme of the invention is as follows:
in a first aspect, the invention provides a preparation method of a thermochromic cooling heat-repellent fabric, which comprises the following steps:
(1) Coating the cooling heat-resistant slurry on the surface of the carbon fiber base cloth, and forming a cooling heat-resistant coating on the surface of the carbon fiber base cloth after drying;
(2) Printing on the surface of the cooling heat-resistant coating by adopting the temperature-sensitive color-changing printing slurry, and then baking to obtain a temperature-sensitive color-changing cooling heat-resistant fabric; the thermochromic printing paste comprises the following components: reversible thermochromic microcapsules, water-based hyperbranched polyurethane, a curing agent and a solvent.
According to the invention, the reversible thermochromic microcapsule and the adhesive (aqueous hyperbranched polyurethane) are compounded to form the printing slurry, and the patterns are formed on the fabric in a printing mode, so that when the temperature changes, the patterns can show different colors, and the fashion feeling is increased. Meanwhile, the carbon fiber base cloth is adopted, and the cooling heat-resisting coating is arranged on the surface of the carbon fiber base cloth, so that the carbon fiber base cloth has strong reflectivity and absorption performance to ultraviolet rays and visible light, the fabric has a good light-shielding and ultraviolet-resisting effect, and the good cooling heat-resisting effect can be realized by blocking the penetration of the visible light and the ultraviolet rays. Therefore, the fabric has the functions of temperature sensing color change, temperature reduction, heat rejection and high ultraviolet resistance, and can be widely applied to outdoor products such as tents, umbrellas, car covers and the like.
In addition, the invention adopts the water hyperbranched polyurethane as the adhesive in the printing paste, has more active functional groups and higher branching degree, and can improve the bonding fastness of the reversible thermochromic microcapsule on the surface of the cooling heat-resistant coating.
Preferably, in the step (2), the thermochromic printing paste comprises the following components in parts by weight: 10-15 parts of reversible thermochromic microcapsules, 8-20 parts of waterborne hyperbranched polyurethane, 1-1.5 parts of curing agent and 30-60 parts of solvent.
Further, in the step (2), the thermochromic printing paste further comprises the following components in parts by weight: 0.2 to 1.2 portions of thickening agent.
Preferably, in the step (2), the specific process of baking is as follows: pre-baking at 80-90 deg.c for 4-8 min, and baking at 150-160 deg.c for 2-3 min.
Preferably, in step (1), the temperature-reduced heat-rejecting slurry comprises modified expanded graphite; the preparation method of the modified expanded graphite comprises the following steps:
(A) Roasting and puffing expandable graphite to obtain loose and porous expanded graphite;
(B) Respectively grafting alkenyl silane coupling agents on the nano titanium dioxide and the loose and porous expanded graphite to obtain alkenyl nano titanium dioxide and alkenyl expanded graphite;
in the step (B), hydroxyl exists on the nano titanium dioxide and the expanded graphite, and the hydroxyl can react with the alkenyl silane coupling agent, so that alkenyl is grafted on the surface of the nano titanium dioxide, the surface of the expanded graphite and in the pores of the expanded graphite.
(C) Mixing carboxylic acid betaine methyl methacrylate, a polyene group crosslinking agent, an initiator and water, adding alkenyl nano titanium dioxide, and uniformly mixing to obtain a modified solution;
(D) Dispersing alkenyl expanded graphite into the modification solution, fully soaking, filtering and separating out precipitate, and heating and polymerizing the precipitate at 70-80 ℃ for 2-3 h to obtain modified expanded graphite;
in the step (D), in the dipping process, the modification liquid is absorbed into the pore channels of the alkenyl expanded graphite, the modification liquid absorbed in the pore channels is reserved after filtering and separating out precipitates, and the alkenyl in the pores of the alkenyl expanded graphite, the alkenyl on the surface of the alkenyl nano titanium dioxide, the carboxylic acid betaine methyl methacrylate and the polyene-based crosslinking agent are subjected to polymerization reaction under the action of an initiator during heating, so that the super-hydrophilic hydrogel loaded with the nano titanium dioxide is formed in the pores of the expanded graphite.
In the modified expanded graphite prepared by the steps, the expanded graphite can reflect and absorb visible light and ultraviolet light, and the titanium dioxide in the holes can absorb the ultraviolet light, so that the cooling heat-resisting coating has a good light-shielding effect; meanwhile, the cooling heat-resistant coating can have a good cooling heat-resistant effect by blocking penetration of ultraviolet light and visible light and utilizing the loose porous structure of the expanded graphite.
In the step (D), the precipitate is separated by filtration and then polymerized by heating, so that the titanium dioxide is present in the pores of the expanded graphite and is rarely distributed on the surface of the expanded graphite. By adopting the mode, on one hand, the direct contact between the expanded graphite and the polymer matrix in the coating can be avoided, so that the photocatalytic degradation of the polymer matrix can be reduced, and the great reduction of the ultraviolet resistance caused by the falling of a large amount of expanded graphite and titanium dioxide after the fabric is used for a long time can be avoided; on the other hand, the problem that the reversible thermochromic microcapsules fall off due to photocatalytic degradation of the adhesive caused by contact between titanium dioxide and the adhesive in the thermochromic printing can be avoided.
In the process of long-term outdoor use, dust, dirt and the like are easy to adhere and gather on the surface and in the pores of the expanded graphite to cause pore channel filling and blocking, and substances filling and blocking the pore channels are difficult to effectively remove through common rain or water washing, so that the ultraviolet resistance, cooling and heat rejection effects of the modified expanded graphite are reduced after long-term use. Therefore, the invention combines the super-hydrophilic hydrogel on the surface and in the pores of the expanded graphite, and can play the following roles: when the hydrogel is contacted with water (used for keeping out the rain or being washed by water), the hydrogel in the expanded graphite holes can greatly expand in volume after absorbing water by utilizing the characteristic of water absorption swelling of the hydrogel, so that substances filling and blocking the holes are discharged from the holes, and meanwhile, as the polycarboxylic betaine methyl methacrylate hydrogel has super-hydrophilicity and can be completely soaked by water, substances such as dust on the surface of the hydrogel can be promoted to be carried away by the water. By the method, substances filling and blocking the pore passages of the expanded graphite can be effectively removed, so that the cooling heat-repellent coating can still keep better ultraviolet resistance and cooling heat-repellent performance after the fabric is used for a long time. In addition, the hydrogel in the holes can improve the water storage capacity of the expanded graphite pore passage, and the combined water can evaporate to take away part of heat at higher temperature, so that the cooling heat rejection effect of the cooling heat rejection coating is improved.
Further, in the step (A), the temperature for roasting and expanding is 900-1100 ℃ and the time is 20-30 s.
Further, in the step (C), the mass ratio of the carboxylic betaine methyl methacrylate to the water is 1:6-8.
When the content of the carboxylic acid betaine methyl methacrylate in the modified solution is too small, the formed super-hydrophilic hydrogel is insufficient, and substances filling and blocking pores of the expanded graphite are difficult to effectively remove, so that the effect of improving the long-term cooling heat-resisting and ultraviolet-resisting performance of the coating is poor; when the content of the carboxylic acid betaine methyl methacrylate in the modification solution is too high, too much space in the pores of the expanded graphite filled with the super-hydrophilic hydrogel is caused, and adverse effects on the cooling, heat-resisting and ultraviolet-resisting effects of the titanium dioxide and the expanded graphite are further caused.
Further, in the step (C), the mass ratio of the carboxylic betaine methyl methacrylate to the alkenyl nano titanium dioxide is 1.
Further, in the step (C), the mass ratio of the carboxylic betaine methyl methacrylate to the polyene-based crosslinking agent is 1.005 to 0.015.
In step (D), the mass ratio of the alkenylated expanded graphite to the modifying solution is 1:5 to 15.
Preferably, in the step (1), the temperature-reducing heat-resisting slurry comprises the following components in parts by weight: 5-15 parts of modified expanded graphite, 0-5 parts of carbon black powder, 2-4 parts of dispersant, 15-20 parts of matrix polymer, 1-1.8 parts of cross-linking agent and 60-80 parts of solvent.
In a second aspect, the invention provides the thermochromic cooling heat-resisting fabric prepared by the preparation method.
Compared with the prior art, the invention has the following advantages:
(1) According to the invention, the surface of the carbon fiber base cloth is coated with the cooling heat-resistant slurry, and the temperature-sensitive color-changing printing slurry is used for printing, so that the obtained cloth has the functions of temperature-sensitive color change, cooling heat resistance and ultraviolet resistance;
(2) According to the invention, the water-based hyperbranched polyurethane is used as the adhesive in the printing paste, so that the reversible thermochromic microcapsule has higher adhesive fastness in the fabric;
(3) According to the invention, the special modified expanded graphite is used in the cooling heat-resistant coating, so that the titanium dioxide can be prevented from directly contacting with a polymer matrix in the coating, and meanwhile, the super-hydrophilic hydrogel in pores of the expanded graphite can be used for promoting substances filling and blocking the pore channels to fall off when being showered or washed by water, so that the cooling heat-resistant and ultraviolet-resistant performances of the fabric are prevented from being greatly reduced after the fabric is used for a long time;
(4) The special modified expanded graphite is used in the cooling heat-resistant coating, so that direct contact between titanium dioxide and an adhesive in the temperature-sensitive color-changing printing can be avoided, and a large amount of reversible temperature-sensitive color-changing microcapsules can be prevented from falling off after long-term use.
Detailed Description
The present invention will be further described with reference to the following examples.
General examples
A preparation method of a temperature-sensing color-changing cooling heat-resisting fabric comprises the following steps:
(1) Preparing modified expanded graphite:
(A) Roasting and puffing expandable graphite at 900-1100 ℃ for 20-30 s to obtain loose and porous expanded graphite;
(B) Respectively grafting alkenyl silane coupling agents on the nano titanium dioxide and the loose and porous expanded graphite to obtain alkenyl nano titanium dioxide and alkenyl expanded graphite;
(C) Mixing carboxylic betaine methyl methacrylate, a polyenyl crosslinking agent, an initiator and water according to the mass ratio of 1: 0.005-0.015: 6-8, adding alkenyl nano titanium dioxide, wherein the mass ratio of the carboxylic betaine methyl methacrylate to the alkenyl nano titanium dioxide is 1: 0.4-0.6, and uniformly mixing to obtain a modified solution;
(D) Dispersing alkenyl expanded graphite into a modification liquid, wherein the mass ratio of the alkenyl expanded graphite to the modification liquid is 1:5-15, fully soaking, filtering to separate out a precipitate, and heating and polymerizing the precipitate at 70-80 ℃ for 2-3 h to obtain the modified expanded graphite.
(2) Preparing a cooling heat-resisting slurry, wherein the cooling heat-resisting slurry comprises the following components in parts by weight: 5-15 parts of modified expanded graphite, 0-5 parts of carbon black powder, 2-4 parts of dispersant, 15-20 parts of matrix polymer, 1-1.8 parts of cross-linking agent and 60-80 parts of solvent.
(3) Coating the cooling heat-resistant slurry on the surface of the carbon fiber base cloth, and forming a cooling heat-resistant coating on the surface of the carbon fiber base cloth after drying;
(4) Preparing thermochromic printing paste which comprises the following components in parts by weight: 10 to 15 parts of reversible temperature-sensitive color-changing microcapsule, 8 to 20 parts of waterborne hyperbranched polyurethane, 1 to 1.5 parts of curing agent, 0.2 to 1.2 parts of thickening agent and 30 to 60 parts of solvent.
(5) Printing is carried out on the surface of the cooling heat-resisting coating by adopting the temperature-sensing color-changing printing sizing agent, then prebaking is carried out for 4-8 min at the temperature of 80-90 ℃, and then baking is carried out for 2-3 min at the temperature of 150-160 ℃, so as to obtain the temperature-sensing color-changing cooling heat-resisting fabric.
As a specific embodiment, the specific process of step (B) comprises the following steps: uniformly mixing loose and porous expanded graphite with the mass ratio of 1: 0.1-0.2, 10-20, an alkenyl silane coupling agent and a solvent A, adjusting the pH value to 4-5, reacting at 60-70 ℃ for 2-3 h, and separating out a product to obtain alkenyl expanded graphite; uniformly mixing nano titanium dioxide, an alkenyl silane coupling agent and a solvent B in a mass ratio of 1.15-0.25.
Example 1
Preparing a temperature-sensing color-changing cooling heat-resisting fabric according to the following steps:
(1) Preparing modified expanded graphite:
(A) Heating expandable graphite at 1000 deg.C for 30s to obtain loose and porous expanded graphite;
(B) Adding 2.5 parts by weight of silane coupling agent KH-570 into 250 parts by weight of absolute ethyl alcohol, and stirring and mixing to obtain a coupling agent solution; taking 100 parts of coupling agent solution, adding 8 parts of loose and porous expanded graphite, stirring and dispersing, adjusting the pH to 4, reacting at 65 ℃ for 2.5h, centrifuging, washing and drying to obtain alkenyl expanded graphite; adding 5 parts of nano titanium dioxide into 100 parts of coupling agent solution, performing ultrasonic dispersion, adjusting the pH to 4, reacting at 60 ℃ for 2.5 hours, centrifuging, washing and drying to obtain alkenyl nano titanium dioxide;
(C) Dissolving 10 parts by weight of carboxylic betaine methyl methacrylate and 0.1 part by weight of N, N' -methylene bisacrylamide into 70 parts by weight of water, adding 0.8 part by weight of potassium persulfate, adding 5 parts by weight of alkenyl nano titanium dioxide, and stirring and mixing to obtain a modified solution;
(D) Dispersing 8 parts by weight of alkenyl expanded graphite into 80 parts by weight of modification liquid, carrying out vacuum impregnation for 30min, filtering and separating out precipitate, and carrying out heating polymerization on the precipitate at 70 ℃ for 3h to obtain the modified expanded graphite.
(2) Weighing 15 parts of modified expanded graphite, 4 parts of propylene glycol block polyether, 20 parts of polyether polyol polyurethane resin, 1.8 parts of isocyanate curing agent, 60 parts of N, N-dimethylformamide and 20 parts of dimethylbenzene according to parts by weight, and uniformly mixing to obtain the cooling heat-resisting slurry.
(3) Cooling the heat-resisting slurry at 105g/m 2 The coating amount is coated on the surface of the carbon fiber base cloth, and a cooling heat-resisting coating is formed on the surface of the carbon fiber base cloth after drying;
(4) Weighing 10 parts of reversible thermochromic microcapsules, 15 parts of waterborne hyperbranched polyurethane, 1.1 parts of isocyanate curing agent, 1 part of waterborne polyurethane thickener and 40 parts of water in parts by weight, and uniformly mixing to obtain thermochromic printing paste.
(5) Printing the temperature-sensing color-changing printing slurry on the surface of the cooling heat-resisting coating through rotary screen printing, pre-baking for 5min at 80 ℃, and baking for 2min at 160 ℃ to obtain the temperature-sensing color-changing cooling heat-resisting fabric.
Example 2
Preparing a temperature-sensing color-changing cooling heat-resisting fabric according to the following steps:
(1) Preparing modified expanded graphite:
(A) Heating expandable graphite at 1100 deg.C for 20s to obtain loose and porous expanded graphite;
(B) Adding 2 parts by weight of silane coupling agent KH-570 into 200 parts by weight of absolute ethyl alcohol, and stirring and mixing to obtain a coupling agent solution; taking 80 parts of coupling agent solution, adding 6 parts of loose and porous expanded graphite, stirring and dispersing, adjusting the pH value to 4, reacting for 3 hours at 60 ℃, centrifuging, washing and drying to obtain alkenyl expanded graphite; taking 100 parts of coupling agent solution, adding 6 parts of nano titanium dioxide into the coupling agent solution, carrying out ultrasonic dispersion, adjusting the pH value to 4, reacting for 1.5 hours at 70 ℃, and centrifuging, washing and drying to obtain alkenyl nano titanium dioxide;
(C) Dissolving 10 parts by weight of carboxylic betaine methyl methacrylate and 0.15 part by weight of N, N' -methylene bisacrylamide into 80 parts by weight of water, adding 0.8 part by weight of potassium persulfate, then adding 6 parts by weight of alkenyl nano titanium dioxide, and stirring and mixing to obtain a modified solution;
(D) Dispersing 6 parts by weight of alkenyl expanded graphite into 90 parts by weight of modification liquid, carrying out vacuum impregnation for 40min, filtering and separating out precipitate, and carrying out heating polymerization on the precipitate at 75 ℃ for 2.5h to obtain the modified expanded graphite.
(2) Weighing 10 parts of modified expanded graphite, 2 parts of high-pigment carbon black powder, 2 parts of propylene glycol block polyether, 20 parts of polyether polyol polyurethane resin, 1.5 parts of isocyanate curing agent, 60 parts of N, N-dimethylformamide and 20 parts of polyurethane resin
And uniformly mixing the dimethylbenzene to obtain the cooling heat-resisting slurry.
(3) Cooling the heat-resisting slurry at 105g/m 2 The coating amount is coated on the surface of the carbon fiber base cloth, and a cooling heat-resisting coating is formed on the surface of the carbon fiber base cloth after drying;
(4) Weighing 10 parts of reversible thermochromic microcapsules, 8 parts of waterborne hyperbranched polyurethane, 1 part of isocyanate curing agent, 0.2 part of waterborne polyurethane thickener and 30 parts of water in parts by weight, and uniformly mixing to obtain thermochromic printing paste.
(5) Printing the temperature-sensing color-changing printing slurry on the surface of the cooling heat-resisting coating through rotary screen printing, pre-baking for 5min at 80 ℃, and baking for 2min at 160 ℃ to obtain the temperature-sensing color-changing cooling heat-resisting fabric.
Example 3
The temperature-sensing color-changing cooling heat-resisting fabric is prepared according to the following steps:
(1) Preparing modified expanded graphite:
(A) Heating expandable graphite at 900 ℃ for 30s to obtain loose and porous expanded graphite;
(B) Adding 2.5 parts by weight of silane coupling agent KH-570 into 250 parts by weight of absolute ethyl alcohol, and stirring and mixing to obtain a coupling agent solution; taking 150 parts of coupling agent solution, adding 10 parts of loose and porous expanded graphite, stirring and dispersing, adjusting the pH value to 5, reacting for 2 hours at 70 ℃, centrifuging, washing and drying to obtain alkenyl expanded graphite; taking 80 parts of coupling agent solution, adding 4 parts of nano titanium dioxide into the coupling agent solution, carrying out ultrasonic dispersion, adjusting the pH value to 5, reacting for 2 hours at 70 ℃, centrifuging, washing and drying to obtain alkenylated nano titanium dioxide;
(C) Dissolving 10 parts by weight of carboxylic betaine methyl methacrylate and 0.05 part by weight of N, N' -methylene bisacrylamide into 60 parts by weight of water, adding 0.5 part by weight of potassium persulfate, adding 4 parts by weight of alkenyl nano titanium dioxide, and stirring and mixing to obtain a modified solution;
(D) Dispersing 10 parts by weight of alkenyl expanded graphite into 70 parts by weight of modification liquid, carrying out vacuum impregnation for 30min, filtering and separating out precipitate, and carrying out heating polymerization on the precipitate at 80 ℃ for 2h to obtain the modified expanded graphite.
(2) Weighing 5 parts of modified expanded graphite, 5 parts of high-pigment carbon black powder, 4 parts of propylene glycol block polyether, 15 parts of polyether polyol polyurethane resin, 1 part of isocyanate curing agent, 45 parts of N, N-dimethylformamide and 15 parts of xylene in parts by weight, and uniformly mixing to obtain the cooling heat-resisting slurry.
(3) Cooling the heat-resisting slurry at 105g/m 2 The coating amount is coated on the surface of the carbon fiber base cloth, and a cooling heat-resisting coating is formed on the surface of the carbon fiber base cloth after drying;
(4) Weighing 15 parts of reversible thermochromic microcapsules, 20 parts of waterborne hyperbranched polyurethane, 1.5 parts of isocyanate curing agent, 1.2 parts of waterborne polyurethane thickener and 60 parts of water in parts by weight, and uniformly mixing to obtain thermochromic printing paste.
(5) Printing the temperature-sensing color-changing printing slurry on the surface of the cooling heat-resisting coating through rotary screen printing, pre-baking for 5min at 80 ℃, and baking for 2min at 160 ℃ to obtain the temperature-sensing color-changing cooling heat-resisting fabric.
Comparative example 1
Preparing a temperature-sensing color-changing cooling heat-resisting fabric according to the following steps:
(1) Preparing modified expanded graphite:
(A) Heating expandable graphite at 1000 deg.C for 30s to obtain loose and porous expanded graphite;
(B) Adding 2.5 parts by weight of silane coupling agent KH-570 into 250 parts by weight of absolute ethyl alcohol, and stirring and mixing to obtain a coupling agent solution; taking 100 parts of coupling agent solution, adding 8 parts of loose and porous expanded graphite, stirring and dispersing, adjusting the pH to 4, reacting at 65 ℃ for 2.5h, centrifuging, washing and drying to obtain alkenyl expanded graphite; taking 100 parts of coupling agent solution, adding 5 parts of nano titanium dioxide into the coupling agent solution, carrying out ultrasonic dispersion, adjusting the pH to 4, reacting for 2.5 hours at 60 ℃, and centrifuging, washing and drying to obtain alkenyl nano titanium dioxide;
(C) Dissolving 10 parts by weight of carboxylic betaine methyl methacrylate and 0.1 part by weight of N, N' -methylene bisacrylamide into 70 parts by weight of water, adding 0.8 part by weight of potassium persulfate, adding 5 parts by weight of alkenyl nano titanium dioxide, and stirring and mixing to obtain a modified solution;
(D) Dispersing 8 parts by weight of alkenyl expanded graphite into 80 parts by weight of modification liquid, vacuum-impregnating for 30min, heating and polymerizing at 70 ℃ for 3h, centrifuging, washing and drying to obtain the modified expanded graphite.
(2) Weighing 15 parts of modified expanded graphite, 4 parts of propylene glycol block polyether, 25 parts of polyether polyol polyurethane resin, 1.8 parts of isocyanate curing agent, 40 parts of N, N-dimethylformamide and 20 parts of xylene in parts by weight, and uniformly mixing to obtain the cooling heat-resisting slurry.
(3) Cooling the heat-resisting slurry at 105g/m 2 The coating amount is coated on the surface of the carbon fiber base cloth, and a cooling heat-resisting coating is formed on the surface of the carbon fiber base cloth after drying;
(4) Weighing 10 parts of reversible thermochromic microcapsules, 15 parts of waterborne hyperbranched polyurethane, 1.1 parts of isocyanate curing agent, 1 part of waterborne polyurethane thickener and 40 parts of water in parts by weight, and uniformly mixing to obtain thermochromic printing paste.
(5) Printing the temperature-sensing color-changing printing slurry on the surface of the cooling heat-resisting coating through rotary screen printing, pre-baking for 5min at 80 ℃, and baking for 2min at 160 ℃ to obtain the temperature-sensing color-changing cooling heat-resisting fabric.
Comparative example 2
Preparing a temperature-sensing color-changing cooling heat-resisting fabric according to the following steps:
(1) Preparing modified expanded graphite:
(A) Heating expandable graphite at 1000 deg.C for 30s to obtain loose and porous expanded graphite;
(B) Adding 2.5 parts by weight of silane coupling agent KH-570 into 250 parts by weight of absolute ethyl alcohol, and stirring and mixing to obtain a coupling agent solution; taking 100 parts of coupling agent solution, adding 8 parts of loose and porous expanded graphite, stirring and dispersing, adjusting the pH to 4, reacting at 65 ℃ for 2.5h, centrifuging, washing and drying to obtain alkenyl expanded graphite; adding 5 parts of nano titanium dioxide into 100 parts of coupling agent solution, performing ultrasonic dispersion, adjusting the pH to 4, reacting at 60 ℃ for 2.5 hours, centrifuging, washing and drying to obtain alkenyl nano titanium dioxide;
(C) Adding 5 parts by weight of alkenyl nano titanium dioxide into 70 parts by weight of water, and stirring and mixing to obtain a modified solution;
(D) Dispersing 7 parts by weight of alkenyl expanded graphite into 70 parts by weight of modification liquid, carrying out vacuum impregnation for 30min, filtering and separating out a precipitate, and heating the precipitate at 70 ℃ for 3h to obtain the modified expanded graphite.
(2) Weighing 15 parts of modified expanded graphite, 4 parts of propylene glycol block polyether, 25 parts of polyether polyol polyurethane resin, 1.8 parts of isocyanate curing agent, 40 parts of N, N-dimethylformamide and 20 parts of xylene in parts by weight, and uniformly mixing to obtain the cooling heat-resisting slurry.
(3) Cooling the heat-resisting slurry at 105g/m 2 The coating amount of (3) is applied to the surface of the carbon fiber base cloth,forming a cooling heat-resisting coating on the surface of the carbon fiber base cloth after drying;
(4) Weighing 10 parts of reversible thermochromic microcapsules, 15 parts of waterborne hyperbranched polyurethane, 1.1 parts of isocyanate curing agent, 1 part of waterborne polyurethane thickener and 40 parts of water in parts by weight, and uniformly mixing to obtain thermochromic printing paste.
(5) Printing the temperature-sensing color-changing printing slurry on the surface of the cooling heat-resisting coating through rotary screen printing, pre-baking for 5min at 80 ℃, and baking for 2min at 160 ℃ to obtain the temperature-sensing color-changing cooling heat-resisting fabric.
Comparative example 3
Preparing a temperature-sensing color-changing cooling heat-resisting fabric according to the following steps:
(1) Preparing modified expanded graphite:
(A) Heating expandable graphite at 1100 deg.C for 20s to obtain loose and porous expanded graphite;
(B) Adding 2 parts by weight of silane coupling agent KH-570 into 200 parts by weight of absolute ethyl alcohol, and stirring and mixing to obtain a coupling agent solution; taking 80 parts of coupling agent solution, adding 6 parts of loose and porous expanded graphite, stirring and dispersing, adjusting the pH value to 4, reacting for 3 hours at 60 ℃, centrifuging, washing and drying to obtain alkenyl expanded graphite; adding 6 parts of nano titanium dioxide into 100 parts of coupling agent solution, performing ultrasonic dispersion, adjusting the pH to 4, reacting at 70 ℃ for 1.5h, centrifuging, washing and drying to obtain alkenyl nano titanium dioxide;
(C) Dissolving 10 parts by weight of carboxylic betaine methyl methacrylate and 0.15 part by weight of N, N' -methylene bisacrylamide into 120 parts by weight of water, adding 0.8 part by weight of potassium persulfate, then adding 6 parts by weight of alkenyl nano titanium dioxide, and stirring and mixing to obtain a modified solution;
(D) Dispersing 6 parts by weight of alkenyl expanded graphite into 90 parts by weight of modification liquid, carrying out vacuum impregnation for 40min, filtering and separating out precipitate, and carrying out heating polymerization on the precipitate at 75 ℃ for 2.5h to obtain the modified expanded graphite.
(2) Weighing 10 parts of modified expanded graphite, 2 parts of high-pigment carbon black powder, 2 parts of propylene glycol block polyether, 20 parts of polyether polyol polyurethane resin, 1.5 parts of isocyanate curing agent, 40 parts of N, N-dimethylformamide and 20 parts of polyurethane resin
And uniformly mixing the dimethylbenzene to obtain the cooling heat-resisting slurry.
(3) Cooling the heat-resisting slurry at 105g/m 2 The coating amount is coated on the surface of the carbon fiber base cloth, and a cooling heat-resisting coating is formed on the surface of the carbon fiber base cloth after drying;
(4) Weighing 10 parts of reversible thermochromic microcapsules, 8 parts of waterborne hyperbranched polyurethane, 1 part of isocyanate curing agent, 0.2 part of waterborne polyurethane thickener and 30 parts of water in parts by weight, and uniformly mixing to obtain thermochromic printing paste.
(5) Printing the temperature-sensing color-changing printing slurry on the surface of the cooling heat-resisting coating through rotary screen printing, pre-baking for 5min at 80 ℃, and baking for 2min at 160 ℃ to obtain the temperature-sensing color-changing cooling heat-resisting fabric.
Comparative example 4
The temperature-sensing color-changing cooling heat-resisting fabric is prepared according to the following steps:
(1) Preparing modified expanded graphite:
(A) Heating expandable graphite at 900 ℃ for 30s to obtain loose and porous expanded graphite;
(B) Adding 2.5 parts by weight of silane coupling agent KH-570 into 250 parts by weight of absolute ethyl alcohol, and stirring and mixing to obtain a coupling agent solution; taking 150 parts of coupling agent solution, adding 10 parts of loose and porous expanded graphite, stirring and dispersing, adjusting the pH value to 5, reacting for 2 hours at 70 ℃, centrifuging, washing and drying to obtain alkenyl expanded graphite; adding 4 parts of nano titanium dioxide into 80 parts of coupling agent solution, performing ultrasonic dispersion, adjusting the pH to 5, reacting at 70 ℃ for 2 hours, centrifuging, washing and drying to obtain alkenyl nano titanium dioxide;
(C) Dissolving 10 parts by weight of carboxylic betaine methyl methacrylate and 0.05 part by weight of N, N' -methylene bisacrylamide into 25 parts by weight of water, adding 0.5 part by weight of potassium persulfate, adding 4 parts by weight of alkenyl nano titanium dioxide, and stirring and mixing to obtain a modified solution;
(D) Dispersing 10 parts by weight of alkenyl expanded graphite into 70 parts by weight of modification liquid, carrying out vacuum impregnation for 30min, filtering and separating out precipitate, and carrying out heating polymerization on the precipitate at 80 ℃ for 2h to obtain the modified expanded graphite.
(2) Weighing 5 parts of modified expanded graphite, 5 parts of high-pigment carbon black powder, 4 parts of propylene glycol block polyether, 15 parts of polyether polyol polyurethane resin, 1 part of isocyanate curing agent, 40 parts of N, N-dimethylformamide and 20 parts of xylene in parts by weight, and uniformly mixing to obtain the cooling heat-resisting slurry.
(3) Cooling the heat-resisting slurry at 105g/m 2 The coating amount is coated on the surface of the carbon fiber base cloth, and a cooling heat-resisting coating is formed on the surface of the carbon fiber base cloth after drying;
(4) Weighing 15 parts of reversible thermochromic microcapsules, 20 parts of aqueous hyperbranched polyurethane, 1.5 parts of isocyanate curing agent, 1.2 parts of aqueous polyurethane thickener and 60 parts of water in parts by weight, and uniformly mixing to obtain thermochromic printing paste.
(5) Printing the temperature-sensing color-changing printing slurry on the surface of the cooling heat-resisting coating through rotary screen printing, pre-baking for 5min at 80 ℃, and baking for 2min at 160 ℃ to obtain the temperature-sensing color-changing cooling heat-resisting fabric.
Test example 1
The fabrics obtained in examples 1 to 3 and comparative examples 1 to 4 were made into sunshade umbrellas. The cooling heat-rejecting performance, the ultraviolet resistance and the friction color fastness of the sunshade are detected, and after the sunshade is used for a period of time in an outdoor simulation mode, the cooling heat-rejecting performance, the ultraviolet resistance and the friction color fastness are detected again. The detection method of the cooling heat-resisting property, the ultraviolet-resisting property and the rubbing color fastness and the outdoor simulation use method are as follows:
(1) Ultraviolet resistance: representing by using a UPF value;
(2) Cooling heat repellency: after the sunshade umbrella is unfolded and placed for 30min under the sunlight, the temperature outside the sunshade umbrella and in the sunshade umbrella (the position 15cm away from the sunshade surface at the center under the sunshade umbrella) is detected, and Wen Chalv is calculated according to Wen Chalv = (the temperature outside the sunshade-the temperature inside the sunshade)/the temperature outside the sunshade by 100 percent; testing for 3 times, and taking the average value of the temperature difference rate;
(3) Color fastness to rubbing: testing the dry rubbing color fastness by adopting a method in GB/T3920-2008 textile color fastness test rubbing color fastness;
(4) Outdoor simulation use: the sunshade umbrella is erected and fixed outdoors at the time of 10-15 days per day from 7 months to 26 months at 2021 in Hangzhou, and is showered by water every 15 days, wherein the time is from 7 months to 8 months and 26 days.
The detection results of the ultraviolet resistance, the cooling heat rejection performance and the rubbing color fastness are respectively shown in tables 1-3.
TABLE 1 UV resistance Properties
Figure BDA0003786404880000111
TABLE 2 temperature drop Heat repellency
Figure BDA0003786404880000112
TABLE 3 color fastness to rubbing
Figure BDA0003786404880000113
Analyzing the data in tables 1 to 3, it can be seen that:
(1) Compared with comparative example 1, example 1 has better ultraviolet resistance and no obvious reduction of color fastness to rubbing after long-term use. The reason is that: in the process of preparing the modified expanded graphite, in example 1, after the expanded graphite is dipped in the modification solution, the precipitate is filtered and separated firstly, and then the precipitate is subjected to heating polymerization, so that titanium dioxide can be present in the pore channels of the expanded graphite and is rarely distributed on the surface of the expanded graphite, and the titanium dioxide is prevented from being directly contacted with a polymer matrix in the coating and an adhesive in the thermochromic printing, and further, the expanded graphite and the titanium dioxide in the coating are prevented from falling off greatly after long-term use, and reversible thermochromic microcapsules in the printing are prevented from falling off greatly; in contrast to comparative example 1, the polymerization reaction was directly carried out in the modification solution without filtration, and much titanium dioxide was distributed on the surface of the modified expanded graphite.
(2) Compared with comparative example 2, example 1 has better ultraviolet resistance and temperature reduction heat rejection performance after long-term use. The reason is that: when the fabric is flushed with water, the hydrogel in the pores of the expanded graphite can greatly expand in volume after absorbing water by utilizing the characteristic of water absorption swelling of the hydrogel, so that substances filling and blocking the pores are discharged from the pores, and meanwhile, as the polycarboxylic betaine methyl methacrylate hydrogel has super-hydrophilicity and can be completely soaked by water, substances such as dust on the surface of the hydrogel can be promoted to be separated by the water, the substances filling and blocking the pores of the expanded graphite can be effectively removed by the way, so that the cooling heat rejection coating can still keep good ultraviolet resistance and cooling heat rejection performance after the fabric is used for a long time; in addition, the hydrogel in the holes can improve the water storage capacity of the expanded graphite pore passage, and the combined water can evaporate to take away part of heat at higher temperature, so that the cooling heat rejection effect of the cooling heat rejection coating is improved.
(4) Comparative example 3 has inferior uv resistance and temperature drop heat repellency after long-term use compared to example 2. The reason is that: in the process of preparing the modified expanded graphite, the content of the carboxylic acid betaine methyl methacrylate in the modified liquid is too small, so that the formed super-hydrophilic hydrogel is insufficient, and substances for filling and blocking pores of the expanded graphite are difficult to effectively remove, so that the effect of improving the long-term cooling heat-resisting and ultraviolet-resisting performance of the coating is poor.
(5) Comparative example 4 has inferior uv and temperature drop heat rejection compared to example 3. The reason is that: in the process of preparing the modified expanded graphite, the content of the carboxylic acid betaine methyl methacrylate in the modification solution is too high, so that too much space is filled in pores of the expanded graphite by the super-hydrophilic hydrogel, and the cooling, heat-resisting and ultraviolet-resisting effects of the titanium dioxide and the expanded graphite are adversely affected.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.

Claims (10)

1. A preparation method of a temperature-sensing color-changing cooling heat-resisting fabric is characterized by comprising the following steps:
(1) Coating the cooling heat-resistant slurry on the surface of the carbon fiber base cloth, and forming a cooling heat-resistant coating on the surface of the carbon fiber base cloth after drying;
(2) Printing on the surface of the cooling heat-resistant coating by using the temperature-sensitive color-changing printing slurry, and then baking to obtain a temperature-sensitive color-changing cooling heat-resistant fabric; the thermochromic printing paste comprises the following components: reversible thermochromic microcapsules, water-based hyperbranched polyurethane, a curing agent and a solvent.
2. The preparation method according to claim 1, wherein in the step (2), the thermochromic printing paste comprises the following components in parts by weight: 10-15 parts of reversible thermochromic microcapsules, 8-20 parts of waterborne hyperbranched polyurethane, 1-1.5 parts of a curing agent and 30-60 parts of a solvent.
3. The preparation method according to claim 2, wherein in the step (2), the thermochromic printing paste further comprises the following components in parts by weight: 0.2 to 1.2 portions of thickening agent.
4. The method according to claim 1, wherein in the step (2), the baking is performed by the following steps: baking at 80 to 90 ℃ for 4 to 8min, and baking at 150 to 160 ℃ for 2 to 3min.
5. The method of claim 1, wherein in step (1), the reduced temperature heat rejection slurry comprises modified expanded graphite; the preparation method of the modified expanded graphite comprises the following steps:
(A) Roasting and puffing expandable graphite to obtain loose and porous expanded graphite;
(B) Respectively grafting alkenyl silane coupling agents on the nano titanium dioxide and the loose and porous expanded graphite to obtain alkenyl nano titanium dioxide and alkenyl expanded graphite;
(C) Mixing carboxylic acid betaine methyl methacrylate, a polyene group crosslinking agent, an initiator and water, adding alkenyl nano titanium dioxide, and uniformly mixing to obtain a modified solution;
(D) Dispersing alkenyl expanded graphite into the modification liquid, fully soaking, filtering to separate out a precipitate, and heating and polymerizing the precipitate at the temperature of 70-80 ℃ for 2-3h to obtain the modified expanded graphite.
6. The process according to claim 5, wherein in the step (A), the temperature of the baking and puffing is 900 to 1100 ℃ for 20 to 30s.
7. The method according to claim 5, wherein in the step (C), the mass ratio of the carboxylic betaine methyl methacrylate to the water is 1.
8. The preparation method according to claim 5 or 7, wherein in the step (D), the mass ratio of the alkenyl expanded graphite to the modification liquid is 1.
9. The preparation method according to claim 5, wherein in the step (1), the temperature-reducing heat-resisting slurry comprises the following components in parts by weight: 5-15 parts of modified expanded graphite, 3238 parts of carbon black powder, 3238 parts of dispersing agent, 3262 parts of dispersing agent, 15-20 parts of matrix polymer, 1-1.8 parts of cross-linking agent and 60-80 parts of solvent.
10. The thermochromic cooling heat-repellent fabric prepared by the preparation method of any one of claims 1~9.
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