CN109505027B - High-sensitivity heat-conducting air conditioner fiber and preparation method thereof - Google Patents
High-sensitivity heat-conducting air conditioner fiber and preparation method thereof Download PDFInfo
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- 239000000835 fiber Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000012782 phase change material Substances 0.000 claims abstract description 64
- 239000003094 microcapsule Substances 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000004378 air conditioning Methods 0.000 claims abstract description 29
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000002425 crystallisation Methods 0.000 claims abstract description 8
- 230000008025 crystallization Effects 0.000 claims abstract description 8
- 238000002844 melting Methods 0.000 claims abstract description 8
- 230000008018 melting Effects 0.000 claims abstract description 8
- 238000009987 spinning Methods 0.000 claims description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 36
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 36
- 229910021389 graphene Inorganic materials 0.000 claims description 36
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 24
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 14
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 13
- 239000002775 capsule Substances 0.000 claims description 13
- HANVTCGOAROXMV-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine;urea Chemical compound O=C.NC(N)=O.NC1=NC(N)=NC(N)=N1 HANVTCGOAROXMV-UHFFFAOYSA-N 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- -1 polytetramethylene Polymers 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 claims description 10
- 229920000742 Cotton Polymers 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 239000004202 carbamide Substances 0.000 claims description 9
- 239000003995 emulsifying agent Substances 0.000 claims description 9
- 239000000839 emulsion Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 239000011550 stock solution Substances 0.000 claims description 8
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 7
- 229920000053 polysorbate 80 Polymers 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 6
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 6
- 229920002472 Starch Polymers 0.000 claims description 6
- 230000001112 coagulating effect Effects 0.000 claims description 6
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 6
- HOWGUJZVBDQJKV-UHFFFAOYSA-N docosane Chemical compound CCCCCCCCCCCCCCCCCCCCCC HOWGUJZVBDQJKV-UHFFFAOYSA-N 0.000 claims description 6
- 229930195729 fatty acid Natural products 0.000 claims description 6
- 239000000194 fatty acid Substances 0.000 claims description 6
- 150000004665 fatty acids Chemical class 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 6
- 229920002866 paraformaldehyde Polymers 0.000 claims description 6
- 229920001522 polyglycol ester Polymers 0.000 claims description 6
- 238000010008 shearing Methods 0.000 claims description 6
- 239000008107 starch Substances 0.000 claims description 6
- 235000019698 starch Nutrition 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 230000015271 coagulation Effects 0.000 claims description 3
- 238000005345 coagulation Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000008098 formaldehyde solution Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000004744 fabric Substances 0.000 abstract description 4
- 238000007730 finishing process Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 230000004044 response Effects 0.000 abstract description 2
- 229920000297 Rayon Polymers 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 230000028016 temperature homeostasis Effects 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- PGXWDLGWMQIXDT-UHFFFAOYSA-N methylsulfinylmethane;hydrate Chemical compound O.CS(C)=O PGXWDLGWMQIXDT-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 230000008447 perception Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- D01D1/00—Treatment of filament-forming or like material
- D01D1/06—Feeding liquid to the spinning head
-
- 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
- D01D5/06—Wet spinning methods
-
- 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
- D01D5/12—Stretch-spinning methods
- D01D5/14—Stretch-spinning methods with flowing liquid or gaseous stretching media, e.g. solution-blowing
-
- 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
- D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Artificial Filaments (AREA)
Abstract
The invention provides a high-sensitivity heat-conducting air-conditioning fiber, wherein the content of a phase-change material microcapsule is 15.1-17.3%, the melting enthalpy value is 35-40J/g, the melting temperature is 29-33 ℃, the crystallization enthalpy value is 32-33J/g, and the crystallization temperature range is 18-21 ℃; the invention also provides a preparation method of the fiber, and the phase-change material microcapsules prepared by the invention are uniformly distributed in the fiber and are firmly combined with the fiber, so that the loss of effective substances in the fiber along with washing or friction can be avoided; tests show that after 50 times of water washing, the loss rate of the phase-change material microcapsule is only 0.1-0.3%; the fabric made of the fiber has no color flower and uneven phenomenon in the post-finishing process. The fiber prepared by the invention has the thermal conductivity of 0.48-0.52W/mK, and has rapid and sensitive response to the external temperature.
Description
Technical Field
The invention relates to a high-sensitivity heat-conducting air-conditioning fiber and a preparation method thereof, belonging to the technical field of fibers.
Background
The air-conditioning fiber is developed and developed for manufacturing aerospace suits, has the greatest characteristic of automatically adjusting the temperature of clothes according to the outside temperature, and is characterized in that a phase-change material with an energy conversion function exists in the fiber, so that the temperature can be adjusted by continuously absorbing and releasing energy, and the clothes can be kept in a comfortable temperature range like a small air conditioner, thereby being named as the air-conditioning fiber.
In the prior art, a phase-change material is generally prepared into microcapsules, and then the microcapsules and a viscose spinning solution are blended and spun to prepare the temperature-adjusting air-conditioning fiber, but the following defects exist:
(1) in the existing viscose wet spinning, strong alkali and strong acid are used, phase change material microcapsules are easily damaged by acid and alkali to cause loss or loss, and broken and not completely lost residual phase change materials can influence the dyeing and finishing process of fabrics to cause uneven dyeing and finishing;
(2) the bonding force between the phase-change material microcapsule and the fiber is not strong, and the phase-change material microcapsule is easy to run off in water washing and friction, so that the functionality of the fiber cannot be kept lasting;
(3) the temperature-adjusting fiber prepared in the prior art has poor temperature adjusting performance, has the defects of supercooling, overheating or small temperature change amplitude, and the prepared finished product has poor wearing comfort.
Disclosure of Invention
The invention aims to solve the technical problems and provides an air conditioner viscose fiber and a preparation method thereof, so as to realize the following purposes:
(1) the preparation method of the fiber has the advantages that the loss or the loss of the phase-change material microcapsule is less, and the fabric made of the fiber has no color flower and uneven phenomenon in the post-finishing process;
(2) the air conditioning fiber prepared by the invention is washable and abrasion resistant;
(3) the air conditioning fiber prepared by the invention has good temperature regulation performance, and the perception of the external environment temperature is more sensitive and rapid.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of air conditioning fiber comprises the following steps:
(1) preparation of graphene modified phase change material microcapsule
A. Preparation of phase change Material emulsions
Heating the phase-change material to melt, controlling the temperature to be 85 ℃, stirring at the speed of 1200r/min, then adding the phase-change material into emulsified water accounting for 70 percent of the total amount, shearing for 2 minutes at the speed of 5000rpm of a homogenizer, then dropwise adding the rest emulsified water at the speed of 4.5ml/min, and shearing for 3 minutes at the high speed of 10000rpm of the homogenizer to prepare the phase-change material emulsion.
The mass ratio of the phase-change material to the emulsified water is 10: 26;
the emulsified water is prepared by mixing water and an emulsifier, wherein the mass ratio of the emulsifier to the water is 1: 24;
the emulsifier is Tween-80;
the phase-change material comprises n-octadecane, polytetramethylene glycol and n-docosane, and the mass ratio of the n-octadecane to the polytetramethylene glycol is 5:3: 1.
Preparation of melamine urea formaldehyde resin capsule wall material
Adding 37% of formaldehyde solution into a reaction kettle, stirring, adding 75% of urea, adjusting the pH value of a reaction system to 4, slowly heating to 78 ℃ at the speed of 2 ℃/min, and reacting for 2 hours; adding melamine, reacting for 45 minutes, adjusting the pH value to 8.5 when the viscosity of the prepolymer reaches 20s, then adding urea, keeping the temperature for 20 minutes, cooling to 50 ℃, adding starch tertiary amino alkyl ether, stirring uniformly, and adjusting the pH value to 7.5 when the temperature is reduced to 35 ℃ to obtain the melamine urea-formaldehyde resin capsule wall material.
The mass ratio of melamine to formaldehyde is 1: 32;
the mass ratio of urea to formaldehyde is 1: 2.2;
the mass ratio of the starch tertiary amino alkyl ether to the formaldehyde is 1: 10.
Preparation of graphene aqueous dispersion
Ultrasonically dispersing graphene in an aqueous solution, and standing to obtain a uniform graphene dispersion solution; and adding a dispersing agent Tween 80 (the mass is 0.3 percent of that of the graphene A) to obtain a stable graphene dispersion liquid, wherein the concentration of the graphene is 0.4 percent by weight.
And polymerization reaction
Stirring the phase change material emulsion in a 70 ℃ water bath for 15 minutes, then dropwise adding the melamine urea formaldehyde resin capsule wall material, dropwise adding citric acid within half an hour at a speed of 50ul/s to reduce the pH of the system to 4.0, keeping the pH for 20 minutes, and adding the graphene aqueous dispersion liquid; and then continuously dripping citric acid at the dripping speed of 25 ul/s, reducing the pH to 2-3, stopping dripping, keeping the stirring speed at 500r/min in the dripping process, then heating to 80 ℃, curing for 2 hours, standing, pouring out supernatant, adding water for washing, carrying out suction filtration, repeating for 2 times, and carrying out vacuum drying to obtain the graphene modified phase-change material microcapsule.
The mass of the graphene is 0.9% of that of the phase-change material;
the particle size D97 of the phase change material microcapsule is 1-2 μm.
The mass ratio of the melamine urea formaldehyde resin capsule wall material to the phase change material is 1: 4.
(2) Preparation of the spinning dope
Adding the cotton pulp, paraformaldehyde and DMSO into a reaction kettle, heating to 125 ℃, stirring at the rotating speed of 2000r/min, dissolving for 1 hour, then cooling to 105 ℃, stirring at the rotating speed of 600r/min, dissolving for 1 hour, then filtering, standing at normal temperature and defoaming in vacuum to prepare a spinning stock solution;
the cotton pulp has a pH of 6.8-7 and a DP of 550.
The mass ratio of the cotton pulp to paraformaldehyde to DMSO is 1: 0.7: 20;
the viscosity of the spinning solution is 180s, and the content of alpha cellulose is 4.6%;
continuously exhausting air in the dissolving process, and recovering redundant formaldehyde in the kettle;
and standing for vacuum defoaming for 13 hours.
(3) Preparation of blended spinning solution
Adding the graphene modified phase-change material microcapsule into a spinning stock solution, adding fatty acid polyglycol ester, stirring and mixing uniformly to prepare a blended spinning solution;
the mass ratio of the fatty acid polyglycol ester to the spinning solution is 1: 25;
the mass ratio of the phase-change material microcapsule to the alpha cellulose in the spinning solution is 0.175: 1.
(4) Spinning formation
Adding the blended spinning solution into an adjusted coagulating bath for spinning, and uniformly stirring, wherein the coagulating bath is a DMSO (dimethyl sulfoxide) aqueous solution, and the concentration of DMSO is 28%; the temperature of the coagulation bath is 35 ℃; soaking and growing: 700 mm, nozzle draft: -3.5%; inter-disc drafting of 18%, two-bath drafting of 33%, three-bath drafting of 27% and spinning speed of 32 m/min; the water temperature of the second bath is 55 ℃, and the water temperature of the third bath is 70 ℃.
The melamine urea formaldehyde resin capsule wall material prepared by the invention can be used for coating a phase change material to prepare microcapsules, and can be well and firmly combined with fibers to prevent the loss or loss of the microcapsules.
The graphene can endow the fiber with good thermal conductivity, and the prepared air-conditioning fiber has better temperature regulation effect by adopting the specific ratio of the graphene to the phase-change material, combining the type and the proportion of the phase-change material and the ratio of the phase-change material microcapsule to the cellulose.
By adopting the technical scheme, the invention has the beneficial effects that:
(1) the content of the phase-change material microcapsules in the prepared fiber is 15.1-17.3%, the melting enthalpy value is 35-40J/g, the melting temperature is 29-33 ℃, the crystallization enthalpy value is 32-33J/g, and the crystallization temperature range is 18-21 ℃.
(2) According to the fiber prepared by the invention, the phase-change material microcapsules are uniformly distributed in the fiber and are firmly combined with the fiber, so that the loss of effective substances of the fiber along with washing or friction can be avoided; tests show that after 50 times of water washing, the loss rate of the phase-change material microcapsule is only 0.1-0.3%; the fabric made of the fiber has no color flower and uneven phenomenon in the post-finishing process.
(3) The fiber prepared by the invention has the thermal conductivity of 0.48-0.52W/mK, and has rapid and sensitive response to the external temperature.
In the temperature rise stage of the environment temperature of 20-40 ℃, the air conditioning fiber starts to absorb heat at 29 ℃, and the self temperature rise rate is gradually reduced. When the ambient temperature is 31 ℃, the temperature difference between the air-conditioning fiber prepared by the invention and the common fiber under the same condition is the largest, and the temperature is 6.5-7 ℃ lower than that of the common fiber; in the temperature rise process with the ambient temperature of 29-33 ℃, the air-conditioning fiber prepared by the invention is 5 ℃ lower than the common fiber on average; in the temperature rise process with the ambient temperature of 34-40 ℃, the air-conditioning fiber prepared by the invention is averagely 2.5 ℃ lower than the common fiber; after 1 hour at 40 degrees celsius ambient temperature, the temperature gradually reached ambient temperature.
In the cooling stage of the ambient temperature of 40-10 ℃, the air conditioning fiber prepared by the invention starts to release heat at 21 ℃, and the cooling rate of the air conditioning fiber is gradually reduced. When the ambient temperature is 20 ℃, the air-conditioning fiber prepared by the invention has the largest temperature difference compared with the common fiber, and the temperature is 5.5-6 ℃ higher than that of the common fiber; in the descending process of the ambient temperature of 21-18 ℃, the air conditioning fiber prepared by the invention is averagely 4 ℃ higher than the common fiber, and in the descending process of the ambient temperature of 17-10 ℃, the air conditioning fiber prepared by the invention is averagely 2 ℃ higher than the common fiber. After 1 hour at 10 degrees celsius ambient temperature, the temperature gradually reached ambient temperature.
(4) The phase change thermoregulation fiber prepared by the invention has the advantages of 1.9dtex of titer, 2.82-2.84cN/dtex of dry breaking strength, 17.8-18.1 percent of dry breaking elongation and 0.74-0.77 cN/dtex of hook strength.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and description, and is in no way intended to limit the invention.
Embodiment 1 a method for preparing air conditioning fibers, comprising the steps of:
(1) preparation of graphene modified phase change material microcapsule
A. Preparation of phase change Material emulsions
Heating the phase-change material to melt, controlling the temperature to be 85 ℃, stirring at the speed of 1200r/min, then adding the phase-change material into emulsified water accounting for 70 percent of the total amount, shearing for 2 minutes at the speed of 5000rpm of a homogenizer, then dropwise adding the rest emulsified water at the speed of 4.5ml/min, and shearing for 3 minutes at the high speed of 10000rpm of the homogenizer to prepare the phase-change material emulsion.
The mass ratio of the phase-change material to the emulsified water is 10: 26;
the emulsified water is prepared by mixing water and an emulsifier, wherein the mass ratio of the emulsifier to the water is 1: 24;
the emulsifier is Tween-80;
the phase-change material comprises n-octadecane, polytetramethylene glycol and n-docosane, and the mass ratio of the n-octadecane to the polytetramethylene glycol is 5:3: 1.
Preparation of melamine urea formaldehyde resin capsule wall material
Adding 37% of formaldehyde solution into a reaction kettle, stirring, adding 75% of urea, adjusting the pH value of a reaction system to 4, slowly heating to 78 ℃ at the speed of 2 ℃/min, and reacting for 2 hours; adding melamine, reacting for 45 minutes, adjusting the pH value to 8.5 when the viscosity of the prepolymer reaches 20s, then adding urea, keeping the temperature for 20 minutes, cooling to 50 ℃, adding starch tertiary amino alkyl ether, stirring uniformly, and adjusting the pH value to 7.5 when the temperature is reduced to 35 ℃ to obtain the melamine urea-formaldehyde resin capsule wall material.
The mass ratio of melamine to formaldehyde is 1: 32;
the mass ratio of urea to formaldehyde is 1: 2.2;
the mass ratio of the starch tertiary amino alkyl ether to the formaldehyde is 1: 10.
Preparation of graphene aqueous dispersion
Ultrasonically dispersing graphene in an aqueous solution, and standing to obtain a uniform graphene dispersion solution; and adding a dispersing agent Tween 80 (the mass is 0.3 percent of that of the graphene A) to obtain a stable graphene dispersion liquid, wherein the concentration of the graphene is 0.4 percent by weight.
And polymerization reaction
Stirring the phase change material emulsion in a 70 ℃ water bath for 15 minutes, then dropwise adding the melamine urea formaldehyde resin capsule wall material, dropwise adding citric acid within half an hour at a speed of 50ul/s to reduce the pH of the system to 4.0, keeping the pH for 20 minutes, and adding the graphene aqueous dispersion liquid; and then continuously dripping citric acid at the dripping speed of 25 ul/s, reducing the pH to 2-3, stopping dripping, keeping the stirring speed at 500r/min in the dripping process, then heating to 80 ℃, curing for 2 hours, standing, pouring out supernatant, adding water for washing, carrying out suction filtration, repeating for 2 times, and carrying out vacuum drying to obtain the graphene modified phase-change material microcapsule.
The mass of the graphene is 0.9% of that of the phase-change material;
the particle size D97 of the phase change material microcapsule is 1-2 μm.
The mass ratio of the melamine urea formaldehyde resin capsule wall material to the phase change material is 1: 4.
(2) Preparation of the spinning dope
Adding the cotton pulp, paraformaldehyde and DMSO into a reaction kettle, heating to 125 ℃, stirring at the rotating speed of 2000r/min, dissolving for 1 hour, then cooling to 105 ℃, stirring at the rotating speed of 600r/min, dissolving for 1 hour, then filtering, standing at normal temperature and defoaming in vacuum to prepare a spinning stock solution;
the cotton pulp has a pH of 6.8-7 and a DP of 550.
The mass ratio of the cotton pulp to paraformaldehyde to DMSO is 1: 0.7: 20;
the viscosity of the spinning solution is 180s, and the content of alpha cellulose is 4.6%;
continuously exhausting air in the dissolving process, and recovering redundant formaldehyde in the kettle;
and standing for vacuum defoaming for 13 hours.
(3) Preparation of blended spinning solution
Adding the graphene modified phase-change material microcapsule into a spinning stock solution, adding fatty acid polyglycol ester, stirring and mixing uniformly to prepare a blended spinning solution;
the mass ratio of the fatty acid polyglycol ester to the spinning solution is 1: 25;
the mass ratio of the phase-change material microcapsule to the alpha cellulose in the spinning solution is 0.175: 1.
(4) Spinning formation
Adding the blended spinning solution into an adjusted coagulating bath for spinning, wherein the coagulating bath is a DMSO water solution, and the concentration of DMSO is 28%; the temperature of the coagulation bath is 35 ℃; soaking and growing: 700 mm, nozzle draft: -3.5%; inter-disc drafting of 18%, two-bath drafting of 33%, three-bath drafting of 27% and spinning speed of 32 m/min; the water temperature of the second bath is 55 ℃, and the water temperature of the third bath is 70 ℃.
(1) The content of the phase-change material microcapsules in the prepared fiber is 15.1-17.3%, the melting enthalpy value is 35-40J/g, the melting temperature is 29-33 ℃, the crystallization enthalpy value is 32-33J/g, and the crystallization temperature range is 18-21 ℃.
(2) According to the fiber prepared by the invention, the phase-change material microcapsules are uniformly distributed in the fiber and are firmly combined with the fiber, so that the loss of effective substances in the fiber along with washing or friction can be avoided; tests show that after 50 times of water washing, the loss rate of the phase-change material microcapsule is only 0.1-0.3%.
In the temperature rise stage of the environment temperature of 20-40 ℃, the air conditioning fiber starts to absorb heat at 29 ℃, and the self temperature rise rate is gradually reduced. When the ambient temperature is 31 ℃, the temperature difference between the air-conditioning fiber prepared by the invention and the common fiber under the same condition is the largest, and the temperature is 6.5-7 ℃ lower than that of the common fiber; in the temperature rise process with the ambient temperature of 29-33 ℃, the air-conditioning fiber prepared by the invention is 5 ℃ lower than the common fiber on average; in the temperature rise process with the ambient temperature of 34-40 ℃, the air-conditioning fiber prepared by the invention is averagely 2.5 ℃ lower than the common fiber;
in the cooling stage of the ambient temperature of 40-10 ℃, the air conditioning fiber prepared by the invention starts to release heat at 21 ℃, and the cooling rate of the air conditioning fiber is gradually reduced. When the ambient temperature is 20 ℃, the air-conditioning fiber prepared by the invention has the largest temperature difference compared with the common fiber, and the temperature is 5.5-6 ℃ higher than that of the common fiber; in the descending process of the ambient temperature of 21-18 ℃, the air conditioning fiber prepared by the invention is averagely 4 ℃ higher than the common fiber, and in the descending process of the ambient temperature of 17-10 ℃, the air conditioning fiber prepared by the invention is averagely 2 ℃ higher than the common fiber.
(3) The phase change thermoregulation fiber prepared by the invention has the advantages of 1.9dtex of titer, 2.82-2.84cN/dtex of dry breaking strength, 17.8-18.1 percent of dry breaking elongation and 0.74-0.77 cN/dtex of hook strength.
All percentages used in the present invention are mass percentages unless otherwise indicated.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (1)
1. A preparation method of high-sensitivity heat-conducting air conditioning fiber is characterized by comprising the following steps: the content of the phase-change material microcapsules in the fiber is 15.1-17.3%, the melting enthalpy value is 35-40J/g, the melting temperature is 29-33 ℃, the crystallization enthalpy value is 32-33J/g, and the crystallization temperature range is 18-21 ℃; the preparation method comprises the steps of preparing the graphene modified phase-change material microcapsule, preparing a spinning stock solution, preparing a blended spinning solution and spinning and forming;
the preparation method of the graphene modified phase-change material microcapsule comprises the following steps:
A. preparation of phase change Material emulsions
Heating the phase-change material to melt, controlling the temperature to be 85 ℃, stirring at the speed of 1200r/min, then adding the phase-change material into emulsified water accounting for 70% of the total amount, shearing for 2 minutes at 5000rpm of a homogenizer, then dropwise adding the rest emulsified water at the speed of 4.5mL/min, and shearing for 3 minutes at a high speed of 10000rpm of the homogenizer to prepare phase-change material emulsion;
the mass ratio of the phase-change material to the emulsified water is 10: 26;
the emulsified water is prepared by mixing water and an emulsifier, wherein the mass ratio of the emulsifier to the water is 1: 24;
the emulsifier is Tween-80;
the phase-change material consists of n-octadecane, polytetramethylene glycol and n-docosane in a mass ratio of 5:3: 1;
B. preparation of melamine urea formaldehyde resin capsule wall material
Adding 37% of formaldehyde solution into a reaction kettle, stirring, adding 75% of urea, adjusting the pH value of a reaction system to 4, slowly heating to 78 ℃ at the speed of 2 ℃/min, and reacting for 2 hours; adding melamine, reacting for 45 minutes, adjusting the pH value to 8.5 when the viscosity of the prepolymer reaches 20s, then adding urea, keeping the temperature for 20 minutes, cooling to 50 ℃, adding starch tertiary amino alkyl ether, stirring uniformly, and adjusting the pH value to 7.5 when the temperature is reduced to 35 ℃ to obtain a melamine urea-formaldehyde resin capsule wall material;
the mass ratio of melamine to formaldehyde is 1: 32;
the mass ratio of urea to formaldehyde is 1: 2.2;
the mass ratio of the starch tertiary amino alkyl ether to the formaldehyde is 1: 10;
C. preparation of graphene aqueous dispersion
Ultrasonically dispersing graphene in an aqueous solution, and standing to obtain a uniform graphene dispersion solution; adding Tween 80 serving as a dispersant to obtain a stable graphene dispersion liquid, wherein the concentration of the graphene is 0.4 wt%;
the mass of the dispersant Tween 80 is 0.3 percent of that of the graphene;
D. polymerisation reaction
Stirring the phase change material emulsion in a 70 ℃ water bath for 15 minutes, then dropwise adding the melamine urea formaldehyde resin capsule wall material, dropwise adding citric acid within half an hour at a speed of 50uL/s to reduce the pH of the system to 4.0, keeping the pH for 20 minutes, and adding the graphene aqueous dispersion liquid; continuously dropwise adding citric acid at a speed of 25 uL/s, reducing the pH to 2-3, stopping dropwise adding, keeping the stirring speed at 500r/min in the dropwise adding process, then heating to 80 ℃, curing for 2 hours, standing, pouring out supernatant, adding water for washing, performing suction filtration, repeating for 2 times, and performing vacuum drying to obtain the graphene modified phase-change material microcapsule;
the mass of the graphene is 0.9% of that of the phase-change material;
the particle size D97 of the phase-change material microcapsule is 1-2 μm;
the mass ratio of the melamine urea formaldehyde resin capsule wall material to the phase change material is 1: 4;
the preparation method comprises the steps of preparing a spinning stock solution, adding cotton pulp, paraformaldehyde and DMSO into a reaction kettle, heating to 125 ℃, stirring at a rotating speed of 2000r/min, dissolving for 1 hour, then cooling to 105 ℃, stirring at a rotating speed of 600r/min, dissolving for 1 hour, then filtering, standing at normal temperature and defoaming in vacuum to obtain the spinning stock solution;
the cotton pulp has pH of 6.8-7 and DP of 550;
the mass ratio of the cotton pulp to paraformaldehyde to DMSO is 1: 0.7: 20;
the viscosity of the spinning solution is 180s, and the content of alpha cellulose is 4.6%;
preparing a blending spinning solution, namely adding a graphene modified phase-change material microcapsule into a spinning stock solution, adding fatty acid polyglycol ester, stirring and mixing uniformly to prepare the blending spinning solution;
the mass ratio of the fatty acid polyglycol ester to the spinning solution is 1: 25;
the mass ratio of the phase-change material microcapsule to the alpha cellulose in the spinning solution is 0.175: 1;
the spinning forming comprises the steps of adding the blended spinning solution into an adjusted coagulating bath for spinning, and uniformly stirring, wherein the coagulating bath is a DMSO (dimethyl sulfoxide) aqueous solution, and the concentration of DMSO is 28%; the temperature of the coagulation bath is 35 ℃; soaking and growing: 700 mm, nozzle draft: -3.5%; inter-disc drafting of 18%, two-bath drafting of 33%, three-bath drafting of 27% and spinning speed of 32 m/min; the water temperature of the second bath is 55 ℃, and the water temperature of the third bath is 70 ℃.
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