CN111005086B - Phase-change temperature-regulating fiber and preparation method thereof - Google Patents
Phase-change temperature-regulating fiber and preparation method thereof Download PDFInfo
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- CN111005086B CN111005086B CN201911199948.3A CN201911199948A CN111005086B CN 111005086 B CN111005086 B CN 111005086B CN 201911199948 A CN201911199948 A CN 201911199948A CN 111005086 B CN111005086 B CN 111005086B
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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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/02—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from cellulose, cellulose derivatives, or proteins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
- C08F220/46—Acrylonitrile with carboxylic acids, sulfonic acids or salts thereof
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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
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
- D01D5/34—Core-skin structure; Spinnerette packs therefor
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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
-
- 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
Abstract
The invention overcomes the defects of the prior art, the thickness of a sheet layer of reduced graphene is thin, the sheets can be connected and wrapped to form a cavity, the phase-change microcapsule in the polyacrylonitrile core layer is difficult to separate from the polyacrylonitrile core layer from the wrapping of the polyacrylonitrile and the reduced graphene sheets, and the loss of phase-change microcapsule materials in the fiber is avoided.
Description
Technical Field
The invention relates to the technical field of phase-change temperature-regulating fibers, and particularly belongs to phase-change temperature-regulating fibers and a preparation method thereof.
Background
The phase-change material is a chemical material which absorbs heat during heating and melting and emits heat during cooling and solidification, and has a function of regulating and controlling temperature within a certain temperature range. The phase-change material is encapsulated and shaped, and is applied to the textile industry, so that the fiber with the temperature adjusting function can be produced, and the thermal physiological comfort degree of the fabric in use can be improved.
In the prior art, a blending method is generally adopted to prepare the phase-change thermoregulation viscose fiber. The phase-change material is wrapped and sealed by the polymer to form the microcapsule, so that the phase-change material is prevented from leaking, and then the microcapsule containing the phase-change material and the viscose spinning solution are subjected to blended spinning to obtain the phase-change fiber, but in the preparation process, a part of the phase-change microcapsule runs off and cannot enter the fiber, so that the phase-change enthalpy of the fiber is small.
Disclosure of Invention
The invention aims to provide a phase-change temperature-regulating fiber and a preparation method thereof, which overcome the defects of the prior art.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
phase change thermoregulation fibre, including core material and cortex material, core material include phase change material, core material and heat conduction additive, phase change material be the phase transition microcapsule, phase change material and heat conduction additive by the cladding of core material, the cortex material be the viscose fiber layer.
The preparation method of the phase-change thermoregulation fiber comprises the following steps:
(1) preparing a heat conduction additive/phase change microcapsule, namely dispersing the heat conduction additive and the phase change microcapsule into deionized water, and dropwise adding a reducing agent in the stirring process to obtain a heat conduction additive/phase change microcapsule solution;
(2) preparing a core layer material, namely adding sodium thiocyanate into a heat-conducting additive/phase-change microcapsule solution to prepare a sodium thiocyanate-containing mixed solution, then adding acrylonitrile, methyl acrylate, itaconic acid, azobisisobutyronitrile and isopropanol according to a weight ratio, and carrying out polymerization reaction to obtain the core layer material;
(3) taking cellulose pulp as an external phase fluid, taking a core layer material as an internal phase fluid, injecting the external phase fluid and the internal phase fluid at 45 ℃ into a capillary coaxial focusing microfluidic control device by injecting mercury at flow rates of 200uL/min and 110uL/min respectively, wherein the concentration is 5%, the cation at 52 ℃ is butyl, and the anion is CH3COO-The phase-change thermoregulation fiber is prepared by spinning and forming in an alkyl imidazole type ionic liquid coagulating bath, and then drawing, washing and oiling.
Further, the heat conducting additive is reduced graphene and/or expanded graphene, and the core layer material is polyacrylonitrile.
Further, the graphene oxide sheets have a thickness of 1-3 layers, the expanded graphene has a layered structure, the concentration of the phase-change microcapsule is 2wt%, and 0.5-1.0mL of a reducing agent is added to 100mL of deionized water.
Further, the reducing agent is 50% hydrazine hydrate.
Further, the concentration of the sodium thiocyanate in the prepared mixed solution containing the sodium thiocyanate is 53 wt%.
Further, the weight ratio of the acrylonitrile to the methyl acrylate to the itaconic acid to the azobisisobutyronitrile to the isopropanol is 92:7.1:1.3:0.97: 2.
Further, the polymerization conditions were at 80 ℃ for 2 hours.
Furthermore, the particle size of the phase-change microcapsule is 1-20 um.
Compared with the prior art, the invention has the following implementation effects:
1. adding a polymerization raw material of polyacrylonitrile into the reduced graphene/phase-change microcapsule solution to ensure that the polyacrylonitrile is directly polymerized in the reduced graphene/phase-change microcapsule solution, thereby realizing one-step compounding of the core layer material, the heat-conducting additive and the phase-change material;
2. the adhesive fiber is used as a skin layer, and the polyacrylonitrile wrapping the heat conduction additive and the phase change material is used as a core layer, so that in the spinning process, moisture in the core layer can pass through the skin layer to volatilize, and the curing of the core layer and the compounding with the skin layer are facilitated;
3. under the heat conduction action of the reduced graphene, the reaction speed of heat absorption and heat dissipation of the phase-change microcapsule can be accelerated;
4. the thickness of the sheet layer of the reduced graphene is thin, the sheets can be connected and wrapped to form a cavity, the phase-change microcapsule has a wrapping effect on the phase-change microcapsule, so that the phase-change microcapsule in the polyacrylonitrile of the core layer is difficult to separate from the core layer in the wrapping of the polyacrylonitrile and the reduced graphene sheets, and the loss of phase-change microcapsule materials in the fiber is avoided.
Drawings
FIG. 1 is a DSC analysis chart of the phase change thermoregulation fiber of example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The phase change thermoregulation fiber of this embodiment, including sandwich layer material and cortex material, has the skin core structure, and sandwich layer material includes phase change material, sandwich layer material and heat conduction additive, and the heat conduction additive is reduction graphite alkene, and sandwich layer material is polyacrylonitrile, and phase change material is the phase change microcapsule, and phase change microcapsule and reduction graphite alkene are by the polyacrylonitrile cladding, and the cortex material is the viscose fiber layer.
The preparation method of the phase-change thermoregulation fiber comprises the following steps:
(1) preparing a reduced graphene/phase-change microcapsule, namely dispersing graphene oxide sheets and phase-change microcapsules into deionized water, wherein the thickness of the graphene oxide sheets is 1-3 layers, the particle size of the phase-change microcapsule is 1-20 mu m, the concentration of the graphene oxide sheets is 0.2 wt%, the concentration of the phase-change microcapsules is 2wt%, dripping 50% hydrazine hydrate in the stirring process, and adding 1.0mL of reducing agent into every 100mL of deionized water to obtain a reduced graphene/phase-change microcapsule solution; the aqueous solution of the graphene oxide sheets and the phase-change microcapsules is in a gel state, the phase-change microcapsules can be uniformly dispersed in a gel liquid formed by the graphene oxide sheets, and after the graphene oxide sheets are reduced by hydrazine hydrate, the graphene oxide sheets are changed into reduced graphene, so that the phase-change microcapsules are wrapped in a gel network formed by the reduced graphene.
(2) Preparing a core layer material, namely adding sodium thiocyanate into the reduced graphene/phase change microcapsule solution to prepare a mixed solution containing 53wt% of sodium thiocyanate, adding acrylonitrile, methyl acrylate, itaconic acid, azodiisobutyronitrile and isopropanol according to the weight ratio of 92:7.1:1.3:0.97:2, and polymerizing for 2 hours at 80 ℃ to obtain the core layer material; adding a polymerization raw material of polyacrylonitrile into the reduced graphene/phase-change microcapsule solution to ensure that the polyacrylonitrile is directly polymerized in the reduced graphene/phase-change microcapsule solution, winding a molecular chain formed by an acrylonitrile monomer with the reduced graphene/phase-change microcapsule, directly wrapping the reduced graphene/phase-change microcapsule material in a polymer formed by a polyacrylonitrile molecular chain, and resolving the polymer from the solution, thereby realizing one-step compounding of the core layer material, the heat-conducting additive and the phase-change material.
(3) Taking cellulose pulp as an external phase fluid, taking a core layer material as an internal phase fluid, injecting the external phase fluid and the internal phase fluid at 45 ℃ into a capillary coaxial focusing microfluidic control device by injecting mercury at flow rates of 200uL/min and 110uL/min respectively, wherein the concentration is 5%, the cation at 52 ℃ is butyl, and the anion is CH3COO-The phase-change thermoregulation viscose fiber is obtained by spinning and forming in an alkyl imidazole type ionic liquid coagulating bath, and refining and drying the obtained tows through cutting, a mild desulfurization process, oil bath and water washing, wherein the drafting multiplying factor is 1.5 times. The adhesive fiber is used as the skin layer, the polyacrylonitrile wrapping the heat conduction additive and the phase change material is used as the core layer, and in the spinning process, moisture in the core layer can pass through the skin layer to volatilize, so that the curing of the core layer and the compounding of the skin layer are facilitated.
The prepared phase change thermoregulation fiber can accelerate the reaction speed of heat absorption and heat dissipation of the phase change microcapsule under the heat conduction effect of the reduced graphene, the thickness of a sheet layer of the reduced graphene is thin, the sheets can be connected and wrapped to form a cavity, the phase change microcapsule is wrapped, the phase change microcapsule in the polyacrylonitrile of the core layer is difficult to separate from the core layer in the wrapping of the polyacrylonitrile and the reduced graphene sheets, and the loss of phase change microcapsule materials in the fiber is avoided.
The thermal performance of the phase-change temperature-regulating fiber obtained in the present example was tested by using a thermal analyzer, and as shown in fig. 1, the temperature-regulating interval of the phase-change temperature-regulating fiber obtained in the present example was 22.7-27.0 ℃, the phase-change enthalpy was 51.5J/g, the encapsulation rate was 87%, and the phase-change enthalpy after washing 10 times was 42.2J/g.
Example 2
The phase change thermoregulation fiber of this embodiment, including sandwich layer material and cortex material, has the skin core structure, and sandwich layer material includes phase change material, sandwich layer material and heat conduction additive, and the heat conduction additive is expanded graphite and reduction graphite alkene, and sandwich layer material is polyacrylonitrile, and phase change material is the phase change microcapsule, and phase change microcapsule, expanded graphite and reduction graphite alkene are by the polyacrylonitrile cladding, and the cortex material is the viscose fiber layer.
The preparation method of the phase-change thermoregulation fiber comprises the following steps:
(1) preparing an expanded graphite/reduced graphene/phase-change microcapsule, namely mixing the expanded graphite and graphene oxide according to a weight ratio of 1:1, dispersing the mixture and a phase-change microcapsule into deionized water, wherein the thickness of graphene oxide sheets is 1-3 layers, the particle size of the phase-change microcapsule is 1-20 microns, the concentrations of the expanded graphite and the graphene oxide are 0.2 wt%, the concentration of the phase-change microcapsule is 2wt%, dropwise adding 50% hydrazine hydrate in the stirring process, and adding 0.5mL of reducing agent into every 100mL of deionized water to obtain an expanded graphite/reduced graphene/phase-change microcapsule solution;
(2) preparing a core layer material, namely adding sodium thiocyanate into an expanded graphite/reduced graphene/phase change microcapsule solution to prepare a mixed solution containing 53wt% of sodium thiocyanate, adding acrylonitrile, methyl acrylate, itaconic acid, azobisisobutyronitrile and isopropanol according to the weight ratio of 92:7.1:1.3:0.97:2, and polymerizing at 80 ℃ for 2 hours to obtain the core layer material;
(3) taking cellulose pulp as an external phase fluid, taking a core layer material as an internal phase fluid, injecting the external phase fluid and the internal phase fluid at 45 ℃ into a capillary coaxial focusing microfluidic control device by injecting mercury at flow rates of 200uL/min and 110uL/min respectively, wherein the concentration is 5%, the cation at 52 ℃ is butyl, and the anion is CH3COO-The phase-change thermoregulation viscose fiber is obtained by spinning and forming in an alkyl imidazole type ionic liquid coagulating bath, and refining and drying the obtained tows through cutting, a mild desulfurization process, oil bath and water washing, wherein the drafting multiplying factor is 1.5 times.
The thermal performance of the phase-change temperature-regulating fiber obtained in the embodiment is tested by using a thermal analyzer, the phase-change temperature of the phase-change temperature-regulating fiber obtained in the embodiment is 22.1-27.7 ℃, the phase-change enthalpy is 49.7J/g, the encapsulation rate is 71%, and the phase-change enthalpy after 10 times of water washing is 34.2J/g.
Example 3
The phase change thermoregulation fiber comprises a core layer material and a skin layer material, and has a skin-core structure, wherein the core layer material comprises a phase change material, a core layer material and a heat conduction additive, the heat conduction additive is expanded graphite, the core layer material is polyacrylonitrile, the phase change material is a phase change microcapsule, the phase change microcapsule and the expanded graphite are coated by the polyacrylonitrile, and the skin layer material is a viscose fiber layer.
The preparation method of the phase-change thermoregulation fiber comprises the following steps:
(1) preparing expanded graphite/phase change microcapsules, namely dispersing the expanded graphite and the phase change microcapsules into deionized water, wherein the concentration of the expanded graphite is 0.2 wt%, and the concentration of the phase change microcapsules is 2wt%, so as to obtain an expanded graphite/reduced graphene/phase change microcapsule solution;
(2) preparing a core layer material, namely adding sodium thiocyanate into an expanded graphite/phase change microcapsule solution to prepare a mixed solution containing 53wt% of sodium thiocyanate, then adding acrylonitrile, methyl acrylate, itaconic acid, azodiisobutyronitrile and isopropanol according to the weight ratio of 92:7.1:1.3:0.97:2, and polymerizing for 2 hours at 80 ℃ to obtain the core layer material;
(3) taking cellulose pulp as an external phase fluid, taking a core layer material as an internal phase fluid, injecting the external phase fluid and the internal phase fluid at 45 ℃ into a capillary coaxial focusing microfluidic control device by injecting mercury at flow rates of 200uL/min and 110uL/min respectively, wherein the concentration is 5%, the cation at 52 ℃ is butyl, and the anion is CH3COO-The phase-change thermoregulation viscose fiber is obtained by spinning and forming in an alkyl imidazole type ionic liquid coagulating bath, and refining and drying the obtained tows through cutting, a mild desulfurization process, oil bath and water washing, wherein the drafting multiplying factor is 1.5 times.
The thermal performance of the phase-change temperature-regulating fiber obtained in the embodiment is tested by using a thermal analyzer, the phase-change temperature of the phase-change temperature-regulating fiber obtained in the embodiment is 22.3-28.9 ℃, the phase-change enthalpy is 48.6J/g, the encapsulation rate is 62%, and the phase-change enthalpy after 10 times of water washing is 23.2J/g.
Comparative example 1
The main difference from example 1 is that the addition amount of graphene oxide sheets in preparing the reduced graphene/phase change microcapsule is 0.
The thermal performance of the phase-change temperature-regulating fiber obtained in the embodiment is tested by using a thermal analyzer, the phase-change temperature of the phase-change temperature-regulating fiber obtained in the embodiment is 21.1-26.2 ℃, the phase-change enthalpy is 51.6J/g, the encapsulation rate is 64%, and the phase-change enthalpy after 10 times of water washing is 21.3J/g.
Comparative example 2
The difference from example 1 is that the addition amount of the phase change microcapsule when preparing the reduced graphene/phase change microcapsule is 0.
The thermal performance of the phase change temperature adjusting fiber obtained in the embodiment is tested by using a thermal analyzer, and the phase change enthalpy of the phase change temperature adjusting fiber obtained in the embodiment is 0J/g.
The temperature-regulating fiber in the embodiment 1 of the invention has high encapsulation efficiency, the temperature-regulating performance of the temperature-regulating fiber after being washed for 10 times is still kept above 80%, the phase-change microcapsule used in the invention is a two-element phase-change material temperature-regulating microcapsule of the Bridgy, and the temperature-regulating interval is 20-26 ℃.
The specific heat-conducting additive, the compounding mode of the phase-change material and the heat-conducting additive, the preparation mode of the phase-change material/the heat-conducting additive and the core layer material, and the selection of the core layer and the skin layer material in the invention make outstanding technical contributions to the invention.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (7)
1. The phase-change temperature-regulating fiber comprises a core layer material and a skin layer material, wherein the core layer material comprises a phase-change material, a core layer polymer and a heat-conducting additive, the phase-change material is a phase-change microcapsule, the phase-change material and the heat-conducting additive are coated by the core layer polymer, and the skin layer material is a viscose fiber layer; the method is characterized by comprising the following steps:
(1) preparing a heat-conducting additive/phase-change microcapsule, namely dispersing graphene oxide sheets and the phase-change microcapsule into deionized water, and dropwise adding a reducing agent in the stirring process to obtain a heat-conducting additive/phase-change microcapsule solution;
(2) preparing a core layer material, namely adding sodium thiocyanate into a heat-conducting additive/phase-change microcapsule solution to prepare a sodium thiocyanate-containing mixed solution, then adding acrylonitrile, methyl acrylate, itaconic acid, azobisisobutyronitrile and isopropanol according to a weight ratio, and carrying out polymerization reaction to obtain the core layer material;
(3) taking cellulose pulp as an external phase fluid, taking a core layer material as an internal phase fluid, injecting the external phase fluid and the internal phase fluid at 45 ℃ into a capillary coaxial focusing microfluidic control device by injecting mercury at flow rates of 200uL/min and 110uL/min respectively, wherein the concentration is 5%, the cation at 52 ℃ is butyl, and the anion is CH3COO-Spinning and forming in an alkyl imidazole type ionic liquid coagulating bath, and preparing phase-change temperature-regulating fibers through a drawing process, a washing process and an oiling process;
the heat conducting additive is reduced graphene, the thickness of the graphene oxide sheet is 1-3 layers, the concentration of the phase-change microcapsule is 2wt%, and 0.5-1.0mL of reducing agent is added into each 100mL of deionized water.
2. The method for preparing the phase-change temperature-regulating fiber according to claim 1, wherein the core polymer is polyacrylonitrile.
3. The method for preparing phase-change thermoregulation fiber according to claim 1, wherein the reducing agent is 50% hydrazine hydrate.
4. The method for preparing phase-change temperature-regulating fiber according to claim 1, wherein the concentration of sodium thiocyanate in the prepared sodium thiocyanate-containing mixed solution is 53 wt%.
5. The method for preparing the phase change thermoregulation fiber according to claim 1, wherein the weight ratio of the acrylonitrile, the methyl acrylate, the itaconic acid, the azobisisobutyronitrile and the isopropanol is 92:7.1:1.3:0.97: 2.
6. The method of claim 1, wherein the polymerization is carried out at 80 ℃ for 2 hours.
7. The method for preparing phase-change thermoregulation fiber according to claim 1, wherein the phase-change microcapsule has a particle size of 1-20 um.
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| CN111962181A (en) * | 2020-08-28 | 2020-11-20 | 广东工业大学 | Phase-change composite fiber and preparation method thereof |
| CN112111807B (en) * | 2020-08-31 | 2023-02-17 | 浙江理工大学 | Conductive multifunctional fiber with skin-core structure and preparation method thereof |
| CN112796003B (en) * | 2021-01-09 | 2022-05-13 | 青岛邦特生态纺织科技有限公司 | Intelligent temperature-adjusting acrylic fiber with high-sensitivity heat absorption and release functions and preparation method thereof |
| CN113403704B (en) * | 2021-06-01 | 2022-06-28 | 深圳减字科技有限公司 | Preparation method of temperature-adjusting fiber, temperature-adjusting fiber and fabric |
| CN114420458B (en) * | 2021-12-21 | 2023-06-09 | 深圳大学 | Flexible electrode, preparation method thereof and flexible supercapacitor |
| CN115305063A (en) * | 2022-09-15 | 2022-11-08 | 武汉纺织大学 | Preparation method of millimeter-scale core-shell phase change capsule based on solution wet spinning |
| CN115559020B (en) * | 2022-10-12 | 2024-04-12 | 青岛尼希米生物科技有限公司 | Phase-change temperature-regulating fiber and preparation method and application thereof |
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