CN115125629B - Textile fiber material with heat storage and temperature regulation functions and preparation method thereof - Google Patents
Textile fiber material with heat storage and temperature regulation functions and preparation method thereof Download PDFInfo
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- CN115125629B CN115125629B CN202211051961.6A CN202211051961A CN115125629B CN 115125629 B CN115125629 B CN 115125629B CN 202211051961 A CN202211051961 A CN 202211051961A CN 115125629 B CN115125629 B CN 115125629B
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/48—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of halogenated hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
Abstract
The invention relates to the technical field and discloses a textile fiber material with heat storage and temperature regulation functions and a preparation method thereof, wherein the textile fiber material comprises the following components: synthesizing an alkenylated phase change functional monomer; the method comprises the following steps of (1) taking an organic-inorganic hybrid material which is in a star-shaped three-dimensional structure and is terminated by a chlorine functional group as an initiator, taking an alkenyl phase-change functional monomer as a polymerization monomer, generating star-shaped solid-supported structure phase-change particles by an atom transfer radical polymerization reaction method, and encapsulating a layer of multi-wall carbon nanotube coating shell with a function of rapidly promoting latent heat storage/release on the star-shaped solid-supported structure phase-change particles to obtain phase-change particles; the textile fiber material with the heat storage and temperature regulation functions is prepared by taking the phase-change particles as a fiber inner core and polyvinylidene fluoride as a fiber shell layer and adopting a coaxial electrostatic spinning method. The invention effectively solves the problem of overflow of the phase change material in the use process of the textile fiber material, and can promote the latent heat of the phase change material to be stored and released more quickly.
Description
Technical Field
The invention relates to the technical field of synthesis of heat-storage temperature-adjustment textile fibers, in particular to a textile fiber material with heat-storage temperature-adjustment functions and a preparation method thereof.
Background
The heat storage temperature regulation fiber is a functional fiber developed by combining the traditional fiber manufacturing technology and the phase change material technology, and the temperature regulation mechanism of the heat storage temperature regulation fiber is mainly that the phase change material inside the heat storage temperature regulation fiber can make an intelligent reaction according to the change of the external environment temperature. When the external environment temperature or the human body temperature is higher than the melting point of the phase-change material, the fiber can absorb heat and store the heat in the fiber, and meanwhile, the phase-change material is converted from a solid state to a liquid state; when the external environment temperature or the human body temperature is lower than the melting point of the phase-change material, the liquid phase-change material can emit the heat stored by the phase-change material, so that the small weather temperature around the fiber is kept relatively stable.
The crystallization temperature of the phase-change material polyethylene glycol monomethyl ether is 26.76 ℃, the crystallization enthalpy is 154.6J/g, the melting temperature is 35.17 ℃, the melting enthalpy is 164.0J/g, the temperature of the phase-change material polyethylene glycol monomethyl ether is comfortable for human body, and the phase-change material polyethylene glycol monomethyl ether can be applied to the preparation of heat-storage temperature-regulating textile fibers.
Researches show that the carbon nano tube can well improve the mechanical property and the heat conducting property of the material, enables latent heat to be stored and released more quickly, and can well improve the mechanical property of the material.
The present invention incorporates the following references: the Master academic thesis of university of compost industry "POSS synthesis and POSS/polymer composite material preparation by ATPR method" discloses the structure and preparation method of octachloropropyl POSS;
the invention provides a method for preparing a heat-storage temperature-regulating textile fiber material, which is used for preparing a textile fiber material with excellent heat-storage temperature-regulating functions.
Disclosure of Invention
Technical problem to be solved
The invention provides a textile fiber material with heat storage and temperature regulation functions and a preparation method thereof, and aims to solve the problem of overflow of a phase change material in the use process of the textile fiber material and provide a solution for promoting the rapid storage and release of latent heat of the phase change material so as to enable the prepared textile fiber to obtain more excellent heat storage and temperature regulation capabilities.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of a textile fiber material with heat storage and temperature regulation functions comprises the following steps:
step1, synthesizing an alkenyl phase-change functional monomer by using polyethylene glycol monomethyl ether as a phase-change material and alkenyl fatty acyl chloride as an activation modifier; preparing an alkenyl multi-walled carbon nanotube by using alkenyl fatty acyl chloride as an activation modifier;
step2, taking an organic-inorganic hybrid material which is in a star-shaped three-dimensional structure and is terminated by a chlorine functional group as an initiator, taking an alkenyl phase-change functional monomer as a polymerization monomer, generating star-shaped solid-supported structure phase-change particles by an atom transfer radical polymerization reaction method, and encapsulating a layer of multi-wall carbon nanotube coating shell with a function of rapidly promoting latent heat storage/release on the star-shaped solid-supported structure phase-change particles to obtain phase-change particles;
and step3, preparing the textile fiber material with the heat storage and temperature regulation functions by using the phase-change particles as fiber inner cores and polyvinylidene fluoride as fiber shell layers and adopting a coaxial electrostatic spinning method.
Preferably, in step2, the phase-change particles are synthesized by a method that alkenyl multi-wall carbon nanotubes are grafted on a phase-change polymer main chain in a polymer block manner to form a coating shell.
Preferably, in step2, the phase-change particles are synthesized by a method that alkenyl multi-wall carbon nanotubes are grafted to the end of a phase-change polymer in an initiator-terminated manner to form a coating shell.
Preferably, in step2, the phase-change particles are synthesized by a method that alkenyl multi-wall carbon nanotubes are grafted on a main chain of a phase-change polymer in a polymer block mode, and then grafted on the end of the phase-change polymer in an initiator end-capping mode to form a double-layer coating shell.
Preferably, the alkenyl fatty acyl chloride activation modifier is one or a combination of more of acryloyl chloride, methacryloyl chloride, 5-hexenoyl chloride and undecylenoyl chloride.
Preferably, in step3, the flow rate of the shell layer is controlled to be 0.07-0.09mm/min and the flow rate of the core layer is controlled to be 0.008-0.011mm/min during electrostatic spinning, and the spinning fiber is obtained through spinning.
Preferably, in step3, the spinning fiber is hot-pressed under the technological parameters of the hot-pressing temperature of 140-180 ℃, the hot-pressing time of 10-30s and the hot-pressing pressure of 0.1-0.2 MPa.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the invention comprises the following steps: the method comprises the following steps of (1) carrying out esterification reaction on a hydroxyl functional group of a phase-change material (polyethylene glycol monomethyl ether) and an acyl chloride functional group of alkenyl fatty acyl chloride, opening the hydroxyl functional group, and generating an ester bond to obtain an alkenyl phase-change functional monomer;
preparing a hydroxylated multi-wall carbon nano tube, and performing esterification reaction on a hydroxyl functional group of the hydroxylated multi-wall carbon nano tube and an acyl chloride functional group of alkenyl fatty acyl chloride to obtain the alkenyl multi-wall carbon nano tube;
octa-chloropropyl POSS is used as an initiator, an alkenyl phase change functional monomer is used as a polymerization monomer, star-shaped solid-supported structure phase change particles are generated by an atom transfer radical polymerization reaction method, and a multi-wall carbon nanotube coating shell with a function of rapidly promoting latent heat storage/release is packaged on the star-shaped solid-supported structure phase change particles to obtain phase change particles;
preparing a textile fiber material by taking the phase-change particles as a fiber inner core and polyvinylidene fluoride as a fiber shell layer by adopting an electrostatic spinning method;
the star-shaped solid-supported structure phase change particles are fixedly coated inside the multi-walled carbon nano tube by activating and modifying alkenyl of the phase change material (polyethylene glycol monomethyl ether) and taking chemical modification of an atom transfer radical polymerization method as a means, so that the fixing effect of the star-shaped solid-supported structure phase change particles is remarkably improved, and the problem of overflow of the phase change material in the use process of the textile fiber material is effectively solved;
the multi-walled carbon nanotube is grafted on the main chain of the phase-change polymer in a polymer block mode and then grafted on the end part of the phase-change polymer in a POSS (polyhedral oligomeric silsesquioxane) end-capping reagent mode to form a structure with a double-layer coating shell, and the structure design can promote the latent heat of the phase-change material to be stored and released more quickly through the excellent heat conduction capacity of the multi-walled carbon nanotube so as to obtain more excellent heat storage and temperature regulation capacity;
as the length of the fatty chain in the alkenylated fatty acid chloride activation modifier increases, its melting temperature gradually increases, and the melting temperature of the methyl branch contained under the same condition of the fatty chain is lower.
Detailed Description
Example 1-1:
synthesizing an alkenyl phase-change functional monomer P1 (polyethylene glycol monomethyl ether is used as a phase-change monomer, and acryloyl chloride is used as an activation modifier):
dissolving 240mg of polyethylene glycol monomethyl ether in 20mL of dichloromethane in a 100mL single-neck flask, adding 505mg of triethylamine acid-binding agent and 0.2mg of hydroquinone polymerization inhibitor, slowly dropwise adding 181mg of acryloyl chloride dissolved in 10mL of dichloromethane, heating to 35 ℃ after dropwise adding, reacting for 10 hours under the protection of nitrogen, taking anhydrous ether as a precipitator, separating out a product, and performing vacuum filtration to obtain an alkenyl phase-change functional monomer P1;
the preparation method of the hydroxylated multi-wall carbon nanotube NWCNTs-OH comprises the following steps: weighing 100mg of multi-walled carbon nanotubes (the outer diameter is 20-40 nm) and adding the multi-walled carbon nanotubes into 15mL of concentrated nitric acid solution, carrying out ultrasonic treatment for 60min, absorbing generated waste gas by adopting alkali liquor, refluxing for 6h at 120 ℃, carrying out suction filtration by using a 0.22um filter membrane, repeatedly washing by using distilled water until the filtrate is neutral, and carrying out vacuum drying for 24h at 60 ℃ to obtain hydroxylated multi-walled carbon nanotubes NWCNTs-OH;
preparation of alkenyl multi-wall carbon nano-tube N1 (using acryloyl chloride as activating modifier): adding 362mg of acryloyl chloride, 4mg of cuprous chloride polymerization inhibitor and 20mL of tetrahydrofuran into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser, heating to 50 ℃, slowly dropwise adding 300mg of hydroxylated multi-walled carbon nanotube NWCNTs-OH and 4mg of 4-dimethylaminopyridine catalyst dissolved in 10mL of tetrahydrofuran, slowly heating to 60 ℃ after dropwise adding, reacting for 4 hours while keeping the temperature, and cooling to heat to obtain an alkenyl multi-walled carbon nanotube N1;
synthesizing star-shaped solid-supported phase-change particles S1 (taking a phase-change functional monomer P1 as a phase-change material): respectively adding 10mg octachloropropyl POSS, a composite catalyst consisting of 7.6mg cuprous chloride and 36mg2, 2-bipyridine and 325mg alkenylation phase change functional monomer P1 and 2mL toluene solvent into a sealed tube, filling small magnetons, performing three cycles of liquid nitrogen freezing, vacuumizing and unfreezing, sealing the sealed tube, performing oil bath at 110 ℃, reacting for 10 hours, taking out the sealed tube, cooling with ice water, purifying, concentrating and vacuum drying by taking tetrahydrofuran as a solvent and methanol as a precipitator to obtain the star-shaped solid-supported structure phase change particles S1;
synthesis of phase-change particles C1-M1 (multi-walled carbon nanotubes N1 are grafted on the main chain of a phase-change polymer in a polymer block manner to form a coating shell): respectively adding 335mg of star-shaped solid-supported structure phase-change particles S1, a composite catalyst consisting of 7.6mg of cuprous chloride and 36mg2, 2-bipyridine and 22mg of an alkenyl multi-walled carbon nanotube N1,2mL of a toluene solvent into a sealed tube, filling small magnetons, performing three cycles of liquid nitrogen freezing, vacuumizing and unfreezing, sealing the sealed tube, performing oil bath at 110 ℃, reacting for 10 hours, taking out the sealed tube, cooling with ice water, taking tetrahydrofuran as a solvent and methanol as a precipitator, purifying, concentrating and drying in vacuum to obtain phase-change particles C1-M1;
preparation of textile fiber material F1-C1-M1 (with phase change particles C1-M1 as fiber inner core):
preparing a polyvinylidene fluoride solution: dissolving 10g of polyvinylidene fluoride (molecular weight 400000) in a mixed solvent consisting of 40mL of acetone and 20mLN, N-dimethylacetamide to obtain a polyvinylidene fluoride solution; the polyvinylidene fluoride solutions were used in the following examples;
adding the fused phase-change particles C1-M1 into a 10mL injector connected with a capillary tube of a core layer, adding a polyvinylidene fluoride solution into the 10mL injector connected with a shell layer, carrying out coaxial electrostatic spinning, controlling the flow rate of the shell layer at 0.09mm/min, controlling the flow rate of the core layer at 0.011mm/min and spinning for 2h during electrostatic spinning, collecting fibers, and carrying out hot-pressing treatment by using a hot-melt bonding machine under the process parameters of 170 ℃ of hot-pressing temperature, 25s of hot-pressing time and 0.2MPa of hot-pressing pressure to obtain a textile fiber material F1-C1-M1 with the functions of heat storage and temperature regulation;
the prepared textile fiber material F1-C1-M1 was subjected to the following performance tests:
the leakage performance test method comprises the following specific steps: attaching a fiber felt with the length of 5cm and the width of 4cm to oil absorption paper, placing the fiber felt in a 60 ℃ oven for 10min, taking out the fiber felt, and observing the leakage condition of phase change particles C1-M1 on the oil absorption paper, wherein the test result is as follows: no leakage of the phase change particles C1-M1 was observed;
the mechanical property test method comprises the following steps: the sample is cut into a rectangle with the length of 4cm and the width of 5mm, the tensile property of the sample is tested by using a uniaxial multifunctional tensile tester under the constant tensile rate of 0.1mm/min, and the test result is as follows: the breaking strength is 47.8MPa, and the tensile rate is 39.5 percent;
the temperature regulation performance test method comprises the following specific steps: wrapping the sample on a probe of a temperature recorder, heating to 60 ℃, taking out the sample, cooling to 20 ℃, and recording the temperature change of the sample, wherein the test result is as follows: a constant temperature platform lasting for 60s appears at 26.5 ℃, which shows that the platform has heat storage and temperature regulation capacity;
examples 1 to 2:
synthesis of phase change particles C1-M2 (multi-walled carbon nanotubes N1 are grafted at the end of a phase change polymer by means of POSS end capping agent to form a coating shell): adding 25mg of hydroxylated multi-walled carbon nanotube NWCNTs-OH and 335mg of star-shaped solid-supported structure phase-change particles S1 into a 50mL single-neck flask, adding magnetons, sealing the flask mouth, and reacting for 24h under magnetic stirring in a water bath condition at 40 ℃ to obtain phase-change particles C1-M2;
taking the phase change particles C1-M2 as fiber inner cores, referring to the preparation steps in the embodiment 1-1, controlling the flow rate of shell layers to be 0.07mm/min, the flow rate of core layers to be 0.008mm/min and the spinning time to be 2h during electrostatic spinning, collecting fibers, and carrying out hot pressing treatment by using a hot melt bonder under the technological parameters of the hot pressing temperature of 180 ℃, the hot pressing time of 10s and the hot pressing pressure of 0.1MPa to obtain textile fiber materials F1-C1-M2, wherein the test result is as follows: the leakage of the phase change particles C1-M2 is not observed, the breaking strength is 40.2MPa, the tensile rate is 41.9%, and a constant temperature platform lasting for 60s appears at 27.4 ℃, so that the phase change particles have the heat storage and temperature regulation capacity;
examples 1 to 3:
synthesis of phase change particles C1-M3 (multi-walled carbon nanotubes N1 were grafted to the main chain of the phase change polymer in the form of polymer blocks and then grafted to the ends of the phase change polymer in the form of POSS capping agents to form double-layered coated shells): respectively adding 335mg of star-shaped solid-supported structure phase-change particles S1 into a sealed tube, a composite catalyst consisting of 7.6mg of cuprous chloride and 36mgg2, 2-bipyridine, 15mg of an alkenyl multi-walled carbon nanotube N1,2mL of a toluene solvent, adding small magnetons, performing three cycles of liquid nitrogen freezing, vacuumizing and unfreezing, sealing the sealed tube, performing oil bath at 110 ℃, reacting for 6 hours, taking out the sealed tube, cooling with ice water, using tetrahydrofuran as a solvent and methanol as a precipitant, purifying, concentrating and performing vacuum drying, adding an obtained intermediate product into a 50mL single-neck flask, adding 10mg of hydroxylated multi-walled carbon nanotube NWCNTs-OH, putting the magnetons, sealing the mouth of the flask, and performing magnetic stirring reaction for 24 hours under the water bath condition of 40 ℃ to obtain phase-change particles C1-M3;
taking the phase change particles C1-M3 as fiber inner cores, referring to the embodiment 1-1 in the rest preparation steps, controlling the flow rate of a shell layer at 0.08mm/min, controlling the flow rate of a core layer at 0.010mm/min and spinning time at 2h during electrostatic spinning, collecting fibers, and performing hot pressing treatment by using a hot melt bonding machine under the process parameters of hot pressing temperature of 140 ℃, hot pressing time of 20s and hot pressing pressure of 0.2MPa to obtain textile fiber materials F1-C1-M3, wherein the test result is as follows: no leakage of the phase change particles C1-M3 is observed, the breaking strength is 43.6MPa, the tensile rate is 34.7%, and a constant temperature platform lasting for 80s appears at 26.1 ℃, so that the phase change particles have heat storage and temperature regulation capacities;
from the embodiments 1-1, 1-2 and 1-3, it can be known that the star-shaped solid-supported structure phase-change particles S1 are fixedly coated inside the multi-walled carbon nanotube N1 by adopting three coating modes through a chemical bonding method, so that the fixing effect of the star-shaped solid-supported structure phase-change particles S1 is remarkably improved, and the problem of overflow of the phase-change material in the use process of the textile fiber material F1 is effectively solved;
the multi-walled carbon nanotube N1 is grafted on the main chain of the phase-change polymer in a polymer block mode and then grafted on the end part of the phase-change polymer in a POSS (polyhedral oligomeric silsesquioxane) end-capping reagent mode to form a structure with a double-layer coating shell, and the structure design can promote the latent heat of the phase-change material to be stored and released more quickly through the excellent heat conduction capacity of the multi-walled carbon nanotube so as to obtain more excellent heat storage and temperature regulation capacity;
example 2-1:
synthesizing an alkenyl phase-change functional monomer P2 (polyethylene glycol monomethyl ether is used as a phase-change monomer, and methacryloyl chloride is used as an activation modifier): in a 100mL single-neck flask, dissolving 240mg of polyethylene glycol monomethyl ether in 20mL of dichloromethane, adding 505mg of triethylamine acid-binding agent and 0.2mg of hydroquinone polymerization inhibitor, slowly dropwise adding 209mg of methacryloyl chloride dissolved in 10mL of dichloromethane, reacting for 8 hours at room temperature and 20 ℃ under the protection of nitrogen after dropwise adding is finished, taking anhydrous ethyl ether as a precipitator, separating out a product, and performing vacuum filtration to obtain an alkenyl phase-change functional monomer P2;
preparation of hydroxylated multiwalled carbon nanotubes see example 1-1;
preparation of alkenyl multi-wall carbon nano-tube N2 (using methacryloyl chloride as an activation modifier): adding 418mg of methacryloyl chloride, 4mg of cuprous chloride polymerization inhibitor and 20mL of tetrahydrofuran into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser, heating to 50 ℃, slowly dropwise adding 300mg of hydroxylated multi-walled carbon nanotube and 4mg of 4-dimethylaminopyridine catalyst dissolved in 10mL of tetrahydrofuran, after dropwise adding, slowly heating to 60 ℃, carrying out heat preservation reaction for 4 hours, and cooling to heat to obtain an alkenyl multi-walled carbon nanotube N2;
synthesizing star-shaped solid-supported phase-change particles S2 (taking phase-change functional monomers P2 as phase-change materials): respectively adding 10mg of octachloropropyl POSS, a composite catalyst consisting of 7.6mg of cuprous chloride and 36mg2, 2-bipyridine, 352mg of an alkenyl phase-change functional monomer P2 and 2mL of a toluene solvent into a sealed tube, and obtaining star-shaped solid-supported structure phase-change particles S2 by referring to the example 1-1 in the rest preparation steps;
synthesis of phase change particles C2-M1 (multi-walled carbon nanotubes N2 are grafted on the main chain of a phase change polymer in a polymer block manner to form a coating shell): 362mg of star-shaped solid-supported structure phase-change particles S2, a composite catalyst consisting of 7.6mg of cuprous chloride and 36mg2, 2-bipyridine, 24mg of alkenyl multi-walled carbon nanotubes N2 and 2mL of toluene solvent are respectively added into a sealed tube, and the rest of preparation steps refer to example 1-1 to obtain phase-change particles C2-M1;
the phase change particles C2-M1 are used as fiber inner cores, and the rest of the preparation steps refer to example 1-1 to obtain the textile fiber material F2-C2-M1, and the test results are as follows: no leakage of the phase change particles C2-M1 is observed, the breaking strength is 43.0MPa, the tensile rate is 37.8%, and a constant temperature platform lasting for 60s appears at 26.2 ℃, which indicates that the phase change particles have heat storage and temperature regulation capacities;
example 2-2:
synthesis of phase change particles C2-M2 (multi-walled carbon nanotubes N2 grafted at the end of the phase change polymer by means of POSS capping agent to form a coating shell): adding 25mg of hydroxylated multi-walled carbon nanotube NWCNTs-OH and 362mg of star-shaped solid-supported structure phase-change particles S2 into a 50mL single-neck flask, and obtaining phase-change particles C2-M2 by the rest preparation steps according to the embodiment 1-2;
the phase change particles C2-M2 are used as fiber inner cores, and the other preparation steps refer to the examples 1-2, so that the textile fiber material F2-C2-M2 is prepared, and the test results are as follows: no leakage of phase change particles C2-M2 is observed, the breaking strength is 38.7MPa, the tensile rate is 40.2%, and a constant temperature platform lasting for 60s appears at 25.8 ℃, which indicates that the phase change particles have heat storage and temperature regulation capacities;
examples 2 to 3:
synthesis of phase change particles C2-M3 (multi-walled carbon nanotubes N2 were grafted to the main chain of the phase change polymer in the form of polymer blocks and then grafted to the ends of the phase change polymer in the form of POSS capping agents to form double-layered coated shells): 362mg of star-shaped solid-supported structure phase-change particles S2, a composite catalyst consisting of 7.6mgg of cuprous chloride and 36mgg of 2, 2-bipyridine, 16mg of an alkenyl multi-walled carbon nanotube N2 and 2mL of a toluene solvent are respectively added into a sealed tube, an obtained intermediate product is added into a 50mL single-neck flask, then 10mg of a hydroxylated multi-walled carbon nanotube NWCNTs-OH is added, and the rest preparation steps refer to examples 1-3 to obtain phase-change particles C2-M3;
the phase change particles C2-M3 are used as fiber inner cores, and the other preparation steps refer to examples 1-3 to prepare textile fiber materials F2-C2-M3, and the test results are as follows: no leakage of phase change particles C2-M3 is observed, the breaking strength is 40.5MPa, the tensile rate is 35.6%, and a constant temperature platform lasting for 80s appears at 24.3 ℃, so that the phase change particles have heat storage and temperature regulation capacities;
example 3-1:
synthesizing an alkenyl phase-change functional monomer P3 (polyethylene glycol monomethyl ether is used as a phase-change monomer, and 5-hexenoyl chloride is used as an activation modifier): in a 100mL single-neck flask, dissolving 240mg of polyethylene glycol monomethyl ether in 20mL of dichloromethane, adding 505mg of triethylamine acid-binding agent and 0.2mg of hydroquinone polymerization inhibitor, slowly dropwise adding 265mg of 5-hexenoyl chloride dissolved in 10mL of dichloromethane, reacting for 10 hours under the protection of nitrogen at room temperature after dropwise adding is finished, taking anhydrous ether as a precipitator, separating out a product, and performing vacuum filtration to obtain an alkenyl phase-change functional monomer P3;
preparation of hydroxylated multiwalled carbon nanotubes see example 1-1;
preparation of alkenyl multi-wall carbon nano-tube N3 (5-hexenoyl chloride is used as an activation modifier): adding 530mg of 5-hexenoyl chloride, 4mg of cuprous chloride polymerization inhibitor and 20mL of tetrahydrofuran into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser, heating to 60 ℃, slowly dropwise adding 300mg of hydroxylated multi-walled carbon nanotube and 4mg of 4-dimethylaminopyridine catalyst dissolved in 10mL of tetrahydrofuran, after dropwise adding, slowly heating to 70 ℃, carrying out heat preservation reaction for 6 hours, and cooling to heat to obtain an alkenyl multi-walled carbon nanotube N3;
synthesizing star-shaped solid-supported structure phase-change particles S3 (taking phase-change functional monomers P3 as phase-change materials): respectively adding 10mg of octachloropropyl POSS, a composite catalyst consisting of 7.6mg of cuprous chloride and 36mg2, 2-bipyridine, 404mg of an alkenyl phase-change functional monomer P3 and 2mL of a toluene solvent into a sealed tube, and obtaining star-shaped solid-supported structure phase-change particles S3 by referring to the example 1-1 in the rest preparation steps;
synthesis of phase change particles C3-M1 (multi-walled carbon nanotubes N3 are grafted on the main chain of a phase change polymer in a polymer block manner to form a coating shell): respectively adding 414mg of star-shaped solid-supported structure phase-change particles S3, a composite catalyst consisting of 7.6mg of cuprous chloride and 36mg2, 2-bipyridine, 29mg of alkenyl multi-walled carbon nanotube N3 and 2mL of toluene solvent into a sealed tube, and obtaining phase-change particles C3-M1 by the rest preparation steps according to example 1-1;
the phase change particles C3-M1 are used as fiber inner cores, and the rest of the preparation steps refer to the example 1-1, so that the textile fiber material F3-C3-M1 is obtained, and the test result is as follows: no leakage of the phase change particles C3-M1 is observed, the breaking strength is 48.1MPa, the tensile rate is 41.2%, and a constant temperature platform lasting for 60s appears at 29.0 ℃, so that the phase change particles have heat storage and temperature regulation capacities;
example 3-2:
synthesis of phase change particles C3-M2 (multi-walled carbon nanotubes N3 are grafted at the end of a phase change polymer by means of POSS end capping agent to form a coating shell): adding 25mg of hydroxylated multi-walled carbon nanotube NWCNTs-OH and 414mg of star-shaped solid-supported structure phase-change particles S3 into a 50mL single-neck flask, and obtaining phase-change particles C3-M2 by the rest preparation steps according to the embodiment 1-2;
the phase-change particles C3-M2 are used as the fiber inner core, and the other preparation steps are referred to the examples 1-2, so that the textile fiber material F3-C3-M2 is prepared, and the test result is as follows: no leakage of phase change particles C3-M2 is observed, the breaking strength is 42.0MPa, the tensile rate is 39.5%, and a constant temperature platform lasting for 60s appears at 30.3 ℃, which indicates that the phase change particles have heat storage and temperature regulation capacity;
examples 3 to 3:
synthesis of phase change particles C3-M3 (multi-walled carbon nanotubes N3 were grafted to the main chain of the phase change polymer in the form of polymer blocks and then grafted to the ends of the phase change polymer in the form of POSS capping agents to form double-layered coated shells): respectively adding 414mg of star-shaped solid-supported structure phase-change particles S3, a composite catalyst consisting of 7.6mgg of cuprous chloride and 36mgg of 2, 2-bipyridyl, 19mg of alkenyl multi-walled carbon nanotubes N3 and 2mL of toluene solvent into a sealed tube, adding the obtained intermediate product into a 50mL single-neck flask, then adding 10mg of hydroxylated multi-walled carbon nanotubes NWCNTs-OH, and referring to examples 1-3 in the rest preparation steps, thus obtaining phase-change particles C3-M3;
the phase change particles C3-M3 are used as fiber inner cores, and the other preparation steps refer to examples 1-3 to prepare textile fiber materials F3-C3-M3, and the test results are as follows: no leakage of the phase change particles C3-M3 is observed, the breaking strength is 43.1MPa, the tensile rate is 35.7%, and a constant temperature platform lasting for 80s appears at 28.7 ℃, which indicates that the phase change particles have heat storage and temperature regulation capacities;
example 4-1:
synthesizing an alkenyl phase-change functional monomer P4 (polyethylene glycol monomethyl ether is used as a phase-change monomer, and undecylene chloride is used as an activation modifier): dissolving 240mg of polyethylene glycol monomethyl ether in 20mL of dichloromethane in a 100mL single-neck flask, adding 505mg of triethylamine acid-binding agent and 0.2mg of hydroquinone polymerization inhibitor, slowly dropwise adding 405mg of undecylenic chloride dissolved in 10mL of dichloromethane, heating to 35 ℃ after dropwise adding, reacting for 10 hours under the protection of nitrogen, taking anhydrous ether as a precipitator, separating out a product, and performing vacuum filtration to obtain an alkenyl phase-change functional monomer P4;
preparation of hydroxylated multiwalled carbon nanotubes see example 1-1;
preparation of alkenyl multi-wall carbon nano-tube N4 (with undecylene acyl chloride as an activation modifier): adding 810mg of undecylenyl chloride, 4mg of cuprous chloride polymerization inhibitor and 20mL of tetrahydrofuran into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser, heating to 60 ℃, slowly dropwise adding 300mg of hydroxylated multi-walled carbon nanotubes and 4mg of 4-dimethylaminopyridine catalyst dissolved in 10mL of tetrahydrofuran, after dropwise adding, slowly heating to 80 ℃, reacting for 6 hours under heat preservation, and cooling to heat, so as to obtain an alkenylated multi-walled carbon nanotube N4;
synthesizing star-shaped solid-supported phase-change particles S4 (taking phase-change functional monomers P4 as phase-change materials): respectively adding 10mg of octachloropropyl POSS, a composite catalyst consisting of 7.6mg of cuprous chloride and 36mg2, 2-bipyridine, 535mg of an alkenyl phase-change functional monomer P4 and 2mL of a toluene solvent into a sealed tube, and referring to the embodiment 1-1 in the rest preparation steps to obtain a star-shaped solid-supported structure phase-change particle S4;
synthesis of phase change particles C4-M1 (multi-walled carbon nanotubes N4 are grafted on the main chain of a phase change polymer in a polymer block manner to form a coating shell): 545mg of star-shaped solid-supported structure phase-change particles S4, a composite catalyst consisting of 7.6mg of cuprous chloride and 36mg2, 2-bipyridine, 43mg of alkenylated multi-walled carbon nanotubes N4 and 2mL of toluene solvent are respectively added into a sealed tube, and the rest of preparation steps refer to example 1-1 to obtain phase-change particles C4-M1;
the phase change particles C4-M1 are used as fiber inner cores, and the rest of the preparation steps refer to the example 1-1, so that the textile fiber material F4-C4-M1 is obtained, and the test result is as follows: no leakage of the phase change particles C4-M1 is observed, the breaking strength is 44.1MPa, the tensile rate is 36.2%, and a constant temperature platform lasting for 60s appears at 32.4 ℃, so that the phase change particles have heat storage and temperature regulation capacities;
example 4-2:
synthesis of phase change particles C4-M2 (multi-walled carbon nanotubes N4 grafted at the end of the phase change polymer by means of POSS capping agent to form a coating shell): adding 25mg of hydroxylated multi-walled carbon nanotube NWCNTs-OH and 545mg of star-shaped solid-supported structure phase change particles S4 into a 50mL single-neck flask, and obtaining phase change particles C4-M2 by the rest preparation steps according to the embodiment 1-2;
the phase change particles C4-M2 are used as fiber inner cores, and the other preparation steps refer to the examples 1-2, so that the textile fiber material F4-C4-M2 is prepared, and the test results are as follows: no leakage of phase change particles C4-M2 is observed, the breaking strength is 42.8MPa, the tensile rate is 44.0%, and a constant temperature platform lasting for 60s appears at 31.7 ℃, so that the phase change particles have heat storage and temperature regulation capacities;
examples 4 to 3:
synthesis of phase change particles C4-M3 (multi-walled carbon nanotubes N2 were grafted to the main chain of the phase change polymer in the form of polymer blocks and then grafted to the ends of the phase change polymer in the form of POSS capping agents to form double-layered coated shells): 545mg of star-shaped solid-supported structure phase-change particles S4, a composite catalyst consisting of 7.6mg of cuprous chloride and 36mg2, 2-bipyridine, 29mg of alkenyl multi-walled carbon nanotubes N4 and 2mL of toluene solvent are respectively added into a sealed tube, the obtained intermediate product is added into a 50mL single-neck flask, then 10mg of hydroxylated multi-walled carbon nanotubes NWCNTs-OH are added, and the rest preparation steps refer to examples 1-3 to obtain phase-change particles C4-M3;
the phase-change particles C4-M3 are used as the fiber inner core, and the other preparation steps are referred to the examples 1-3, so that the textile fiber material F4-C4-M3 is prepared, and the test result is as follows: the leakage of phase change particles C4-M3 is not observed, the breaking strength is 41.9MPa, the tensile rate is 37.2%, and a constant temperature platform lasting for 80s appears at 32.0 ℃, so that the heat storage and temperature regulation capacity is realized;
from examples 1-3, 2-3, 3-3, and 4-3, it can be seen that the melting temperature of the alkenylated fatty acid chloride activation modifier gradually increases as the length of the fatty chain increases, and the melting temperature of the methyl branch chain contained in the same fatty chain condition is lower.
Claims (8)
1. A preparation method of a textile fiber material with heat storage and temperature regulation functions is characterized by comprising the following steps:
step1, synthesizing an alkenyl phase-change functional monomer by using polyethylene glycol monomethyl ether as a phase-change material and alkenyl fatty acyl chloride as an activation modifier; preparing an alkenyl multi-walled carbon nanotube by using alkenyl fatty acyl chloride as an activation modifier;
the alkenyl multi-walled carbon nano-tube is subjected to esterification reaction through hydroxyl functional groups of the hydroxylated multi-walled carbon nano-tube and acyl chloride functional groups of alkenyl fatty acyl chloride to obtain the alkenyl multi-walled carbon nano-tube;
step2, taking an organic-inorganic hybrid material which is in a star-shaped three-dimensional structure and is terminated by a chlorine functional group as an initiator, taking an alkenyl phase-change functional monomer as a polymerization monomer, generating star-shaped solid-supported structure phase-change particles by an atom transfer radical polymerization reaction method, and encapsulating a layer of multi-wall carbon nanotube coating shell with a function of rapidly promoting latent heat storage/release on the star-shaped solid-supported structure phase-change particles to obtain phase-change particles;
the initiator is octachloropropyl POSS;
and step3, preparing the textile fiber material with the heat storage and temperature regulation functions by using the phase-change particles as fiber inner cores and polyvinylidene fluoride as fiber shell layers and adopting a coaxial electrostatic spinning method.
2. The method for preparing textile fiber material with heat storage and temperature regulation functions as claimed in claim 1, wherein in the step2, the phase-change particles are synthesized by a method that alkenyl multi-wall carbon nanotubes are grafted on a phase-change polymer main chain in a polymer block manner to form a coating shell.
3. The method for preparing the textile fiber material with the functions of heat storage and temperature regulation according to claim 1, wherein in the step2, the phase-change particles are synthesized by a method that alkenyl multi-wall carbon nanotubes are grafted on the end of a phase-change polymer in an initiator-terminated mode to form a coating shell.
4. The method for preparing a textile fiber material with heat storage and temperature regulation functions as claimed in claim 1, wherein in the step2, the phase-change particles are synthesized by a method that alkenyl multi-wall carbon nanotubes are grafted on a main chain of a phase-change polymer in a polymer block mode, and then are grafted on the end part of the phase-change polymer in an initiator end-capping mode to form a double-layer coating shell.
5. The method for preparing the textile fiber material with the functions of heat storage and temperature regulation according to claim 1, wherein the alkenyl fatty acyl chloride activation modifier is one or a combination of more of acryloyl chloride, methacryloyl chloride, 5-hexenoyl chloride and undecylenic chloride.
6. The method for preparing the textile fiber material with the functions of heat storage and temperature regulation according to claim 1, wherein in the step3, the flow rate of the shell layer is controlled to be 0.07-0.09mm/min, the flow rate of the core layer is controlled to be 0.008-0.011mm/min during electrostatic spinning, and the spinning fiber is obtained through spinning.
7. The method for preparing a textile fiber material with heat storage and temperature regulation functions as claimed in claim 6, wherein in the step3, the spinning fiber is subjected to hot pressing treatment under the process parameters of the hot pressing temperature of 140-180 ℃, the hot pressing time of 10-30s and the hot pressing pressure of 0.1-0.2 MPa.
8. Textile fiber material with heat storage and temperature regulation functions, prepared by the method for preparing textile fiber material according to any one of claims 1-7.
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