CN-122013359-A - Cellulose-based composite phase change fiber and preparation method and application thereof

CN122013359ACN 122013359 ACN122013359 ACN 122013359ACN-122013359-A

Abstract

The application relates to a cellulose-based composite fiber, and a preparation method and application thereof. The preparation method of the cellulose-based composite fiber comprises the steps of (1) preparing cellulose/photo-thermal material composite spinning solution and nano cellulose/phase change material composite spinning solution respectively, (2) extruding the cellulose/photo-thermal material composite spinning solution and the nano cellulose/phase change material composite spinning solution from an outer layer and an inner layer respectively by using extrusion equipment with coaxial spinning needles with inner and outer layers, and entering water after passing through an air gap, and (3) exchanging solvents in a coagulation bath. The cellulose-based composite fiber prepared by the method has improved heat conduction and light absorption capacity and has application prospect in the production of heat management products.

Inventors

CHEN SHENG
CHEN YUXIN
XU FENG
CAO MENGYAO
SHA JIE
ZHU JINGQIAO
Bi Ziyu
Zhong Jinchen
WANG ZIYI

Assignees

北京林业大学

Dates

Publication Date: 20260512
Application Date: 20260209

Claims (10)

1. A method of making a cellulose-based composite phase change fiber, the method comprising the steps of: (1) The preparation of the cellulose/photo-thermal material composite spinning solution comprises the steps of completely dissolving a cellulose raw material in a cellulose solvent, optionally adding a cellulose auxiliary agent, adding the photo-thermal material after the cellulose is completely dissolved, and continuously stirring until the cellulose is completely dispersed to obtain the cellulose/photo-thermal material composite spinning solution; The preparation of the nano-cellulose/phase-change material composite spinning solution comprises the steps of fully and uniformly mixing a dispersion liquid of the nano-cellulose in deionized water with the phase-change material under stirring to obtain the nano-cellulose/phase-change material composite spinning solution; (2) Extruding the nano cellulose/phase change material composite spinning solution prepared in the previous step from the inner layer of the coaxial spinning needle by using spinning solution extruding equipment with the coaxial spinning needle with an inner layer and an outer layer of the coaxial spinning needle to simultaneously extrude the two spinning solutions, passing through an air gap of 1-3 cm and then entering water, obtaining wet composite fibers through a solvent exchange process, and (3) And (3) placing the wet composite fiber prepared in the step (2) in water serving as a coagulating bath, standing for 12-24 h, or replacing the coagulating bath for multiple times, so that the wet composite fiber and the solvent of the coagulating bath are subjected to full solvent exchange, then continuously drying or intermittently drying in an oven, and finally winding on a wire roll to obtain the cellulose-based composite phase change fiber.
2. The method according to claim 1, wherein, in step (1), The cellulose raw material is selected from one or more of dissolving wood pulp, refined cotton and chemical wood pulp, and the polymerization degree is 400-1500; The cellulose solvent is selected from one or more of a superbase ionic liquid, an imidazolyl ionic liquid, a pyridyl ionic liquid and a choline-based ionic liquid, preferably 1-allyl-3-methylimidazole chloride or N-propenyl pyridine chloride; the cellulose auxiliary agent is selected from one or more of dimethyl sulfoxide (DMSO) and Dimethylformamide (DMF); the photo-thermal material is selected from one or more of carbon nanotubes, carbon black and graphene.
3. The method according to claim 1, wherein, in step (1), The cellulose raw material and the cellulose solvent are mixed according to the mass ratio of 1:20-30, the mass ratio of the cellulose solvent to the cellulose auxiliary agent is 5:1-2, and the photo-thermal material and the cellulose raw material are mixed according to the mass ratio of 0.1-1:1; the dissolution condition of the cellulose raw material is that the raw material is stirred for 1 to 6 hours at the temperature of 70 to 100 ℃ and the rotating speed of 100 to 800rpm until the raw material is completely dissolved into the cellulose solvent.
4. The method according to claim 1, wherein, in step (1), The nanocellulose is selected from one or more of mechanically cellulose nanofibrils, TEMP0 oxidized cellulose nanofibrils and carboxymethylated cellulose nanofibrils, and The phase change material is selected from one or more of paraffin, polyethylene glycol and n-octadecane.
5. The method according to claim 1, wherein, in step (1), The concentration of the cellulose/photo-thermal material composite spinning solution is 2-8wt% and the concentration of the nano cellulose/phase change material composite spinning solution is 4-24wt%; the mass ratio of the phase change material to the nanocellulose is 9-29:1; The concentration of the dispersion of nanocellulose in deionized water is 0.5-1wt%.
6. The method according to claim 1, wherein, in step (1), The preparation condition of the nano cellulose/phase change material composite spinning solution is that 15 min-1 h is stirred at the rotation speed of 500-8000rpm at the temperature of 20-100 ℃ to be fully and uniformly mixed.
7. The method according to claim 1, wherein, in the step (2), The coaxial spinning needle with inner and outer double layers is selected from one of 12G, 13G, 14G, 15G, 16G, 17G, 18G, 19G, 20G, 21G, 22G, 23G, 24G, 25G, 26G, 27G, 28G, 30G, 32G, and the spinning solution extrusion device is also provided with a feed cylinder, and/or The extrusion temperature of the outer layer is 70-100 ℃, the extrusion speed of the inner layer and the outer layer is independently 0.02-0.45 ml/min, and/or The air gap is 1-3 cm.
8. A cellulose based composite phase change fiber made by the method of any one of claims 1-7.
9. A thermal management article comprising at least the cellulose-based composite phase change fiber of claim 8, preferably the thermal management article is a fabric.
10. Use of the thermal management article of claim 9 for human body thermoregulation studies.

Description

Cellulose-based composite phase change fiber and preparation method and application thereof Technical Field The application belongs to the technical field of phase change materials, and particularly relates to a cellulose-based composite phase change fiber, and a preparation method and application thereof. Background Along with the promotion of living standard and the development of urban, the demand of personal wearing scenes for thermal comfort is continuously increased, and the heat management processes such as heating and refrigeration often bring higher energy consumption. The Phase Change Material (PCM) can reversibly change phase and absorb or release latent heat in the heating and cooling processes, so that the storage and release of heat energy are realized, and the PCM is widely used in the fields of temperature buffering and heat energy storage. The solid-liquid phase-change materials such as paraffin, polyethylene glycol, n-octadecane and the like have the advantages of higher latent heat, adjustable phase-change temperature zone and the like, but the problems of melting leakage, insufficient heat transfer efficiency, performance decay after recycling and the like still easily occur in practical application, thereby limiting the phase-change efficiency and long-term stability. In order to realize the structural utilization of the phase change material and facilitate the subsequent processing integration, the PCM is often compounded with the polymer matrix and builds a fibrous form, and especially the PCM is coated in the fiber through a core-shell structure, so that the packaging stability can be improved and the leakage risk can be reduced in the continuous forming process. Cellulose sources are wide in range, renewable and have a good fiber forming basis, and is an important matrix for constructing phase change fibers, and can be used for stabilizing a phase change system and assisting in packaging. However, the phase change fiber facing engineering application generally focuses on the mechanical properties of the fiber besides requiring higher phase change heat storage capacity, and further introduces functions such as photo-thermal conversion to improve the acquisition and utilization efficiency of external energy. Therefore, a cellulose-based composite phase-change fiber technical scheme which can give consideration to phase-change performance, mechanical performance and photo-thermal performance in a fiber structure is developed, and has important research and application values. At present, the preparation method of the phase-change fiber mainly comprises the routes of melt spinning, wet spinning, electrostatic spinning and the like. Among them, melt spinning often requires higher processing temperatures, which can easily cause leakage, migration, or thermal aging of the phase change material. Although the electrostatic spinning is convenient for constructing the porous/nano structure, the problems of low yield, high cost, difficult continuous large-scale preparation and the like are common. In contrast, wet spinning process conditions are relatively mild and have high continuous forming capability, and are considered to be one of the important ways to realize the engineering preparation of phase-change fibers. At present, the phase change fiber is mainly prepared by a hollow fiber post-impregnation method and a wet spinning method. The hollow fiber post-impregnation method generally prepares fibers with a cavity structure, and introduces solid-liquid phase materials into the cavity through melt impregnation or vacuum adsorption and other modes to obtain a heat storage function. The method has great dependence on the formation quality of the hollow structure and the subsequent dipping process, and the continuous production stability and the consistency of the fiber structure are easily influenced by process fluctuation. In contrast, wet spinning is more continuous in forming capability and therefore more commonly used in phase change fiber preparation and amplification. In the wet spinning process, the prior art more commonly adopts coaxial wet spinning to form a core-shell structure, the outer layer is a formable polymer solution which can be quickly solidified in the solidification process and form a continuous shell, the inner layer is a feeding system containing phase change materials, and the feeding system can be microcapsule suspension, emulsion or dispersion liquid, and can also be a molten phase change material and a modification system thereof. The spinning solution enters a coagulating bath after coaxial spinning, and the outer layer is preferentially coagulated and formed and coats the phase change component of the inner layer, so that the drapable and windable continuous filament is obtained. In the solidification and post-treatment stage, organic solvents such as ethanol, isopropanol, acetone and the like or a mixed system thereof are often used as solidification or displace